CN103865033B - Many carboxyls cage-type silsesquioxane modified epoxy and the application in coating thereof - Google Patents
Many carboxyls cage-type silsesquioxane modified epoxy and the application in coating thereof Download PDFInfo
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Abstract
The invention belongs to epoxy coating field, disclose a kind of many carboxyls cage-type silsesquioxane (CSQ) modified epoxy and the application in coating thereof.CSQ modified epoxy is prepared by following methods: is fed intake in reactor by CSQ and epoxy resin 1:4～1:7 in mass ratio, and adds catalyst and organic solvent, uniformly mixes；Under the conditions of 105～115 DEG C, react 2～4h, filter discharging, obtain the CSQ modified epoxy containing high activity hydroxyl.Then utilizing hydroxyl and the polyisocyanate-based curing reaction that carries out, a kind of high rigidity expediting setting type coating of preparation, wherein the mass ratio of organic coating and firming agent is 30:50～70:25.The hardness of CSQ modified epoxy of the present invention is high, wearability is good, drying speed, and the coating therefore prepared based on this modified epoxy has hardness height, good toughness, drying speed, resistance to impact is good and antiseptic property is excellent advantage.
Description
Technical field
The invention belongs to epoxy coating field, particularly to a kind of many carboxyls cage-type silsesquioxane modified epoxy tree
Fat and the application in coating thereof.
Background technology
Along with expanding economy, user is more and more higher to the performance requirement of epoxy-based lacquers, not only requires that it has excellent attached
Put forth effort and wearability, and just so the quick-drying of epoxy resin can be required the highest from dry after 24h after requiring brushing.Ring
Containing groups such as carboxyl, hydroxyl, epoxy radicals on epoxy resins strand, therefore there is excellent mechanical performance and physicochemical property.Ring
Epoxy resins coating becomes cancellated macromole by cross-linking with firming agent in dry run.But at epoxy resin paint
In, simple using firming agent cured epoxy resin, solidfied material fragility is big, impact strength is low for it, easy to crack, when by External Force Acting
Time, it is very easy to destroyed.So becoming inevitable with other component modification epoxies.The way generally used is with flexible by epoxy
Macromolecular material is blended, or by epoxy and soft segment grafting, copolymerization.The method of modifying of most common of which is by ring
Epoxy resins and alkyd resin modification by copolymerization, although this modification mode can effectively reduce the fragility of epoxy resin, balance every
Mechanical property, but the hardness of epoxy resin while improving toughness, can be reduced, and owing to the degree of branching of alkyd resin is relatively low, single
Pure epoxy and the molecular resin amount synthesized by alkyd resin are big not, are difficult to be fully cured film forming to keep out solvent in the short time
The infiltration of molecule, so the solvent resistance of coating should be ensured, requires that again paint film is dried rapidly, and this requirement is extremely difficult to.For
Increase crosslink density, does not the most make the easy efflorescence of epoxy resin, has organic nothing of highly-branched degree because crosslink density is too high
Machine hybrid is undoubtedly optimal selection.
Along with appearance and the further maturation of hybrid technology, the nanometer material of nano material since 20 century
Material causes the extensive concern of people with the combination property of its brilliance.In organic/inorganic hybridization material field of polymer technology especially
One big focus, carries out activeness and quietness by inorganic nano-particle to polymer, overcomes tradition toughened system at toughening polymer
While cause the shortcoming that its intensity reduces.By the synergism between organic component and inorganic component, hybrid material is showed
Go out the combination property of high-molecular organic material and inorganic functional material.Such that it is able to optimize the phase interaction of storeroom further
With, the effective performance improving material.It is known that generally had a problem that, i.e. by inorganic nano-particle toughening epoxy
Inorganic nano-particle can not be compatible with epoxy resin, and this inevitably results in nanoparticle reunion in the epoxy.Therefore, cage
This brand-new hybrid material of type silsesquioxane enters the visual field of people.The molecular dimension of cage-type silsesquioxane be 1～
3nm, inside has the structure of similar silicon dioxide.Outside can connect organic group R, and cage-type silsesquioxane has stronger
Structural symmetry, dimensionally stable and high temperature resistant, in view of the designability of R group, by the modification to R group, can improve ring
The compatibility between epoxy resins and cage-type silsesquioxane, effectively avoids reunion and the two-phase laminated flow of electrodeless particle.Simultaneously when
When cage-type silsesquioxane introduces soft segment, epoxy resin can be allowed to reach preferable toughening effect.But, at home and abroad
To in epoxide modified research, only embody cage-type silsesquioxane and carry out physical blending, cage model sesquialter silicon with epoxy resin
Siloxane modified epoxy resin can effectively embody the pliability of cage-type silsesquioxane, and its hybrid material has again asphalt mixtures modified by epoxy resin
The excellent corrosion resistance of fat and high rigidity.But this method of modifying is often relatively difficult, it is mainly reflected in cage model sesquialter silicon
The difficult dispersion in the epoxy of oxygen alkane, and this method of modifying produces any impact hardly to the dry speed of epoxy resin.
Therefore, synthesize that a kind of hardness is high, wearability is good, the epoxy resin of drying speed, always manufacturer are pursued, but at this
Aspect research both domestic and external is still at present blank.
Therefore, seeking a kind of technique simply, product possesses again the modified epoxy tree of hardness height, good toughness, fast drying simultaneously
The production method of fat, tool is of great significance.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, the 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 the preparation of a kind of above-mentioned many carboxyls cage-type silsesquioxane modified epoxy
Method.
Still a further object of the present invention is to provide a kind of many carboxyls cage-type silsesquioxane modified epoxy in coating
Application.
The purpose of the present invention is realized by following proposal:
A kind of many carboxyls cage-type silsesquioxane modified epoxy, is prepared by following methods:
Many carboxyls cage-type silsesquioxane and epoxy resin 1:4～1:7 in mass ratio are fed intake in reactor, and adds
By reaction system gross mass 0.15～the catalyst of 0.3% and the organic solvent accounting for resin total amount 20%, uniformly mix；105～
React 2～4h under the conditions of 115 DEG C, filter discharging, obtain the many carboxyls cage-type silsesquioxane modified epoxy containing high activity hydroxyl
Resin；
Described many carboxyls cage-type silsesquioxane, structural formula is: (SiO1.5)m(C6H4COOH)m(m=8、10、12)；
Described catalyst refers to chromium acetylacetonate, tetrabutylphosphoniuacetate acetate, triethanolamine, triphenyl phosphorus, benzyl dimethylamine
With at least one in benzyl triphenyl phosphonium chloride thing.
The organic solvent fingernail benzene used in the preparation of described modified epoxy is or/and dimethylbenzene.
Preferably, described epoxy resin refers to 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 asphalt mixtures modified by epoxy resin
At least one in fat, glycidyl ester type epoxy resin and glycidyl amine type epoxy resin.
The present invention also provides for the application in coating of the above-mentioned many carboxyls cage-type silsesquioxane modified epoxy, i.e. uses
Above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity expediting setting type coating of preparation, its bag
The mass ratio including organic coating and firming agent, organic coating and firming agent is 30:50～70:25；First each for organic coating component
Dispersed with stirring, carries out curing reaction after adding firming agent mixing, it is thus achieved that use the high rigidity expediting setting type coating of state；Its
In, organic coating comprises the following component by system gross mass percentages:
Described firming agent refers to polyisocyanate-based firming agent；
Described pigment refers at least one in titanium dioxide, phthalocyanine blue, phthalocyanine green and white carbon black；
Described filler refers at least one in calcium carbonate, white carbon, Kaolin, magnesium hydroxide and barium sulfate.
Described auxiliary agent refers at least one in dispersant, levelling agent and drier.
Preferably, described polyisocyanate-based firming agent refers to TDI trimer, IPDI trimer, TDI and trimethylolpropane
Addition compound product, IPDI and the addition compound product of trimethylolpropane, the addition compound product of XDI and trimethylolpropane and HDI contracting two
At least one in urea.
Described many carboxyls cage-type silsesquioxane modified epoxy uses front retarder thinner to be diluted to admittedly contain
Amount is 70～80%.
Preferably, described retarder thinner fingernail benzene, dimethylbenzene, Petroleum, raffinate oil, ethyl acetate, butyl acetate, 100#
At least one in solvent naphtha and 200# solvent naphtha.
Preferably, adding ethyl acetate to solid content before described firming agent uses is 30～40%.
Preferably, at least one in described drier finger ring alkanoic acid metallic soap and isooctyl acid metallic soap.
Preferably, described dispersant is polycarboxylic acids amine type, modified polyorganosiloxane type, modified polyacrylate type and polycarboxylic acids
At least one in ammonium salt type etc..
Preferably, described levelling agent is organic silicon modified by polyether, polyester modification hydroxyl organosilicon, isocyanate-modified
At least one in organosilicon, polyacrylate and fluorin modified crylic acid ester copolymer.
The mechanism of the present invention is:
(1) present invention utilizes the carboxyl on CSQ and the epoxy radicals on epoxy resin to react, and CSQ is introduced asphalt mixtures modified by epoxy resin
In fat, and generation has highly active hydroxyl simultaneously.From molecular level, CSQ is introduced in epoxy resin, form height crosslinking close
The macromole of degree so that it is existing CSQ on strand, has again an epoxy, has both remained the corrosion resistance of epoxy resin, high rigidity
Advantage, epoxy resin can be carried out the most toughness reinforcing again by CSQ simultaneously.
(2) the high rigidity expediting setting type coating of the present invention utilizes hydroxyl to carry out curing reaction with polyisocyanate-based, because of
This response speed is fast and can carry out at a lower temperature, can effectively carry while ensureing material hardness and wearability
High coating from dryness.
The present invention relative to prior art, has following prominent advantage and a beneficial effect:
(1) the CSQ modified epoxy of the present invention uses chemical bonds, improves the molecule compatibility, has adhesive force
Good (0 grade), richness are good, toughness strong (1mm), and mechanical strength height (6H), resistance to impact good (45kg cm), antiseptic property are excellent
Advantage.
(2) the lowest meeting of ratio shared by CSQ makes the toughening effect of modified resin undesirable, and the ratio shared by CSQ is too
Height, the most easily occurs gel during CSQ modified epoxy.Present invention optimizes the proportioning of CSQ and epoxy resin, and
By first introducing in epoxy resin by CSQ, whole course of reaction is the gentleest, but also does not has the generation of any by-product.Both
Ensure that crosslink density, do not have again gel, and basis can also be provided for follow-up curing reaction.
(2) the high rigidity expediting setting type coating of the present invention is by groups such as CSQ modified epoxy, pigment, filler, firming agent
Become, solidified by polyisocyanate-based firming agent, greatly improve molecular weight and the dry rate of resin, do not affecting
The defect that after solving CSQ modified epoxy while mechanical performance, dry speed is slow, integrates the advantage of various resin, has
Excellent mechanical property, both ensure that the hardness of coating, maintained preferable pliability and corrosion resistance；Hardness is high
(6H), good toughness (1mm), drying speed (5h), the feature of resistance to impact good (45kg cm).
(3) raw material of the present invention be easy to get, technique simple, the coating solids height, the good leveling property that prepare, be prone to film simultaneously.
Response speed is fast and can carry out at a lower temperature, can effectively improve while ensureing material hardness and wearability
Coating from dryness.Its popularization and application will meet the demand of manufacturer and market thereof.
Detailed description of the invention
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 catalyst, organic solvent formula as shown in table 1, by CSQ
Put into reactor with epoxy resin, then input catalyst triphenyl phosphorus and organic solvent toluene uniformly mix respectively；It is warming up to 105
～in the range of 110 DEG C, insulation reaction 3 hours, to acid number difference less than terminating reaction during 0.1mgKOH/g.Shown in table 1
Ethyl acetate and the consumption of butyl acetate to be diluted to solid part be 75%, filter discharging, i.e. prepare the use containing high activity hydroxyl
State CSQ modified epoxy.
Table 1CSQ modified epoxy prepare formula table
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it includes organic coating and firming agent, and it is 30% that firming agent adds ethyl acetate to solid content before using；Organic coating
It is shown in table 9 with the weight ratio of firming agent；First as listed by table 9, pigment, filler, auxiliary agent each component and content proportioning thereof feed intake, and help
In agent, drier is aphthenic acids metallic soap, and dispersant is polycarboxylic acids amine type, and levelling agent is polyester modification hydroxyl organosilicon；At a high speed
Stir at least 5 minutes, prepare organic coating；Add firming agent again to stir mixing, carry out curing reaction, it is thus achieved that use state
High rigidity expediting setting type coating, 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 catalyst, organic solvent formula as shown in table 2, by CSQ
Put into reactor with epoxy resin, then input catalyst tetrabutylphosphoniuacetate acetate and organic solvent dimethylbenzene uniformly mix respectively；
Being warming up in the range of 110～115 DEG C, insulation reaction 2 hours, to acid number difference less than terminating reaction during 0.1mgKOH/g.
Being diluted to solid part with the consumption of the 200# solvent naphtha shown in table 2 and butyl acetate is 75%, filters discharging, i.e. prepares and live containing height
The CSQ modified epoxy of property hydroxyl.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 40% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is aphthenic acids metallic soap, and dispersant is polycarboxylic acids amine type, and levelling agent is polyester modification
Hydroxyl organosilicon and organic silicon modified by polyether；Its method is with embodiment 1.
Table 2CSQ modified epoxy prepare formula table
Embodiment 3
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy with embodiment 2, concrete formula such as table 3 institute
Show.Finally being diluted to solid part with the consumption of the 200# solvent naphtha shown in table 3 is 70%, filters discharging, i.e. prepares the hydroxyl Han high activity
The CSQ modified epoxy of base.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 35% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is aphthenic acids metallic soap, and dispersant is polycarboxylic acids amine type and modified polyorganosiloxane type,
Levelling agent is polyacrylate and organic silicon modified by polyether；Its method is with embodiment 1.
Table 3CSQ modified epoxy prepare formula table
Embodiment 4
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy with embodiment 2, concrete formula such as table 4 institute
Show.Finally being diluted to solid part with the consumption of the dimethylbenzene shown in table 4 and ethyl acetate is 80%, filters discharging, i.e. prepares containing height
The CSQ modified epoxy of activity hydroxy.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 30% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is aphthenic acids metallic soap and isooctyl acid metallic soap, and dispersant is modified polyorganosiloxane type
With modified polyacrylate type, levelling agent is fluorin modified crylic acid ester copolymer and isocyanate-modified organosilicon；Its method is same
Embodiment 1.
Table 4CSQ modified epoxy prepare formula table
Embodiment 5
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy is as follows:
Many carboxyls cage-type silsesquioxane, epoxy resin and catalyst, organic solvent formula as shown in table 5, by CSQ
Put into reactor with epoxy resin, then input catalyst acetyl acetone chromium and organic solvent dimethylbenzene uniformly mix respectively；Heat up
In the range of 110～115 DEG C, insulation reaction 4 hours, to acid number difference less than terminating reaction during 0.1mgKOH/g.Finally
Being diluted to solid part with the consumption of the 100# solvent naphtha shown in table 5 is 80%, filters discharging, i.e. prepares the CSQ containing high activity hydroxyl
Modified epoxy.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 40% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is isooctyl acid metallic soap, and dispersant is polycarboxylic acids amine type, and levelling agent is polyester modification
Hydroxyl organosilicon；Its method is with embodiment 1.
Table 5CSQ modified epoxy prepare formula table
Embodiment 6
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy with embodiment 5, concrete formula such as table 6 institute
Show.Finally being diluted to solid part with the consumption with ethyl acetate of raffinating oil shown in table 6 is 75%, filters discharging, i.e. prepares containing height
The CSQ modified epoxy of activity hydroxy.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 40% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is aphthenic acids metallic soap and isooctyl acid metallic soap, dispersant be polycarboxylic acids ammonium salt type and
Modified acroleic acid ester type, levelling agent is organic silicon modified by polyether and isocyanate-modified organosilicon；Its method is with embodiment 1.
Table 6CSQ modified epoxy prepare formula table
Embodiment 7
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy with embodiment 2, concrete formula such as table 7 institute
Show.Finally being diluted to solid part with the consumption of the toluene shown in table 7 and ethyl acetate is 70%, filters discharging, i.e. prepares and live containing height
The CSQ modified epoxy of property hydroxyl.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 35% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is isooctyl acid metallic soap, and dispersant is polycarboxylic acids amine type and polycarboxylic acids ammonium salt type, stream
Flat agent is isocyanate-modified organosilicon；Its method is with embodiment 1.
Table 7CSQ modified epoxy prepare formula table
Embodiment 8
The preparation method of many carboxyls cage-type silsesquioxane modified epoxy with embodiment 5, concrete formula such as table 8 institute
Show.Finally being diluted to solid part with the consumption of the Petroleum shown in table 6 and butyl acetate is 80%, filters discharging, i.e. prepares containing height
The CSQ modified epoxy of activity hydroxy.
Using above-mentioned many carboxyls cage-type silsesquioxane modified epoxy is raw material, a kind of high rigidity fast setting of preparation
Type coating, it is 35% that firming agent adds ethyl acetate to solid content before using, organic coating and each component of firming agent and content thereof
Proportioning is shown in table 9；In auxiliary agent, drier is aphthenic acids metallic soap, and dispersant is modified polyacrylate type, and levelling agent is poly-
Acrylate；Its method is with embodiment 1.
Table 8CSQ modified epoxy prepare formula table
Table 9 formulation for coating material based on CSQ modified epoxy table (percentage by weight %)
Firming agent used in the present embodiment is directly buied from market, and adding a small amount of ethyl acetate before use will
Its solid content reduces to 30～40%.
Those skilled in the art can according to actual needs, and it is suitable to select in each component of the present invention and content ratio range thereof
Auxiliary agent and determine its consumption.
The performance test of high rigidity expediting setting type coating based on CSQ modified epoxy, operates as follows:
Test sample preparation method: use tinplate as base material, with sand paper, the tinplate sheet polishing got ready is removed
The oil stain in face, is washed with deionized water only, dries, and finally uses spreader to be coated.Coating layer thickness is in 30 ± 5 μm, 30～60
Test performance after solidifying 10～60min at DEG C, the results are shown in Table 10.
(1) mensuration of hardness: with reference to standard GB/T/T6739-86, prepares the drawing pencil that one group of hardness is 6B～6H,
The pencil hardness of film is measured by manual method.On the table top be placed on film plate level, hand-held pencil angle at 45 °, with uniformly
Speed on coated surface, firmly push about 1cm, and stay on film and scratch.Repeat to scratch to the pencil of same hardness label
5 roads, if any 2 roads or the above base plate not scratching model, then use the pencil of the big label of hardness instead, until finding film to be wiped
Hinder 2 roads or more than.A label less than this pencil hardness is the pencil hardness of film.
(2) mensuration of adhesive force: with reference to standard GB/T/T9286-1998, cuts on paint film with a stroke cutter that 6 roads are parallel to be cut
Trace, should cut through the entire depth of paint film；Then at 6 road cut channels as drawing on the former vertical direction, many little sides are formed
Lattice, then the pressure sensitive adhesive tape of standard determines the progression of film adhesive.
(3) corrosion resistance test: with reference to standard GB/T/T1771-91, uses Q235 steel as base material, after spraying, is coated with
The thickness of layer is 150 ± 5 μm, carries out neutral salt spray test the most after drying.
(4) pliability 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 Mandrel Bends test plate (panel).It is broken whether observation paint film produces reticulate pattern, crackle and peeling etc.
Bad phenomenon, reference standard determines suppleness.
(5) test of drying time: with reference to standard GB/T/T1728-79, by spray painting on tinplate, survey respectively
Determine the surface drying time of coating, do solid work the time.
(6) resistance to impact test: with reference to standard GB/T/T1732-93, by spray painting on tinplate, by adjusting
The height that weight is descending, measures the impact resistance of paint film.
The performance indications of table 10 coating 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 |
| Adhesive force | 0 | 1 | 1 | 1 | 0 | 0 | 1 | 0 |
| Corrosion-resistant (96h) | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Pliability (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 (kg cm) | 30 | 20 | 35 | 45 | 45 | 30 | 35 | 35 |
The coating that the present invention prepares as can be seen from Table 10 has excellent mechanical property, both ensure that the hard of coating
Degree, maintains preferable pliability and corrosion resistance.
At home and abroad in epoxide modified research, only embodying CSQ and carry out physical blending with epoxy resin, CSQ changes
Property epoxy resin can effectively embody the pliability of CSQ, and its hybrid material has again the excellent corrosion resistance of epoxy resin
And high rigidity.But this method of modifying is often relatively difficult, it is mainly reflected in CSQ difficult dispersion in the epoxy.And
This method of modifying produces any impact hardly to the dry speed of epoxy resin.Therefore, a kind of hardness of synthesis height, wearability
Good, the epoxy resin of drying speed, always manufacturer are pursued, but the most blank in the research that this part is at home and abroad.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. carboxyl cage-type silsesquioxane modified epoxy more than a kind, it is characterised in that prepared by following methods:
Many carboxyls cage-type silsesquioxane and epoxy resin 1:4～1:7 in mass ratio are fed intake in reactor, and adds by anti-
Answer system gross mass 0.15～the catalyst of 0.3% and account for the organic solvent of resin gross mass 20%, uniformly mixing；105～
React 2～4h under the conditions of 115 DEG C, filter discharging, obtain the many carboxyls cage-type silsesquioxane modified epoxy containing high activity hydroxyl
Resin；
Described catalyst refers to chromium acetylacetonate, tetrabutylphosphoniuacetate acetate, triethanolamine, triphenyl phosphorus, benzyl dimethylamine and benzyl
At least one in base triphenylphosphonium chloride；
Described organic solvent fingernail benzene is or/and dimethylbenzene.
One many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 1, it is characterised in that: preparation
Many carboxyls cage-type silsesquioxane described in method, structural formula is: (SiO1.5)m(C6H4COOH)m；Wherein m=8,10,12.
One many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 1, it is characterised in that: described
Epoxy resin refer to bisphenol A type epoxy resin, bisphenol f type epoxy resin, methylol bisphenol A type epoxy resin, hydrogenated bisphenol A type
Epoxy resin, organic-silicon-modified bisphenol A type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy
At least one in resin and glycidyl amine type epoxy resin.
4. the modified epoxy of carboxyl cage-type silsesquioxane more than kind application in coating, it is characterised in that: use right
Requiring that the many carboxyls cage-type silsesquioxane modified epoxy described in 1 is raw material, a kind of high rigidity expediting setting type of preparation is coated with
Material, it includes the mass ratio of organic coating and firming agent, organic coating and firming agent is 30:50～70:25；First organic coating
Each component dispersed with stirring, carries out curing reaction after adding firming agent mixing, it is thus achieved that use the high rigidity expediting setting type of state
Coating；
Wherein, organic coating comprises the following component by system gross mass percentages:
Described firming agent refers to polyisocyanate-based firming agent；
Described pigment refers at least one in titanium dioxide, phthalocyanine blue, phthalocyanine green and white carbon black；
Described filler refers at least one in calcium carbonate, white carbon, Kaolin, magnesium hydroxide and barium sulfate；
Described auxiliary agent refers at least one in dispersant, levelling agent and drier；
Described many carboxyls cage-type silsesquioxane modified epoxy uses front retarder thinner to be diluted to solid content
70～80%.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: described polyisocyanate-based firming agent refers to that TDI trimer, IPDI trimer, TDI add with trimethylolpropane
Become in addition compound product and the HDI biuret of product, IPDI and the addition compound product of trimethylolpropane, XDI and trimethylolpropane
At least one.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: described retarder thinner fingernail benzene, dimethylbenzene, Petroleum, raffinate oil, ethyl acetate, butyl acetate, 100# solvent
At least one in oil and 200# solvent naphtha.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: it is 30～40% that described firming agent adds ethyl acetate to solid content before using.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: at least one in described drier finger ring alkanoic acid metallic soap and isooctyl acid metallic soap.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: described dispersant is at least in polycarboxylic acids amine type, modified polyorganosiloxane type and modified polyacrylate type
Kind.
A kind of many carboxyls cage-type silsesquioxane modified epoxy the most according to claim 4 application in coating,
It is characterized in that: described levelling agent is organic silicon modified by polyether, polyester modification hydroxyl organosilicon, isocyanate-modified organic
At least one in silicon, polyacrylate and fluorin modified crylic acid ester copolymer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410090694.2A CN103865033B (en) | 2014-03-12 | 2014-03-12 | Many carboxyls cage-type silsesquioxane modified epoxy and the application in coating thereof |
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| 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 |
| CN114046008B (en) * | 2021-11-17 | 2023-06-16 | 瑞宇建设有限公司 | Waterproof building outer wall heat insulation structure and construction method thereof |
| CN114292404B (en) * | 2021-12-30 | 2023-06-06 | 广东盈骅新材料科技有限公司 | POSS modified oxazoline derivative, preparation method thereof and epoxy resin composition |
| CN115093785B (en) * | 2022-08-03 | 2023-12-19 | 长园长通新材料(东莞)有限公司 | Weather-resistant 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 |
| 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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|---|
| 多官能化POSS合成及其共聚物制备与性能研究;王占彬;《中国优秀硕士论文全文数据库 工程科技I辑》;20101015;第20-21、33-36页 * |
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