CN106565963A - Preparation of epoxy-terminated hyperbranched polyester modified nano silica organic-inorganic hybrid material - Google Patents
Preparation of epoxy-terminated hyperbranched polyester modified nano silica organic-inorganic hybrid material Download PDFInfo
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Abstract
The invention discloses a preparation method of an epoxy-terminated hyperbranched polyester modified nano silica organic-inorganic hybrid material. The preparation method is characterized in that hyperbranched polyester is grafted on the surface of nano silica through reaction of alcohol and acid, and the material is obtained after carrying out termination through epoxy compounds. According to the prepared hyperbranched polyester-grafted nano silica organic-inorganic hybrid material, hyperbranched polymers are grafted on the surface, so that grafting ratio of the surface of nano silica is increased; the hyperbranched polymers form a wrapping layer on the surface of silica, so that dispersity of nano silica in an epoxy resin coating is improved; besides, terminal groups of the hyperbranched polyester on the surface of modified nano silica are epoxy groups, and the epoxy groups can participate in the curing process of the epoxy resin coating, so that molecular structures of the epoxy resin system are regulated; and therefore, the material has more excellent comprehensive performances in the epoxy resin coating compared with ordinary grafting modified nano silica, and is suitable for preparing the epoxy resin coating with good adhesive force, strength, abrasion resistance and ageing resistance.
Description
Technical field
The present invention relates to a kind of nanometer organic-inorganic hybrid material, more particularly to a kind of epoxy terminated hyper-branched polyester changes
The preparation method of property nano silicon organic-inorganic hybrid material.
Background technology
Epoxy resin has that caking property is strong, good corrosion resistance, electrical apparatus insulation, mechanical strength are good, and shrinkage factor it is low,
The advantages of easy processing molding, it is widely used in coating, adhesive, electric insulant, advanced composite material matrix etc. each
Individual field.But the shortcomings of having that matter is crisp, impact resistance is poor after its solidification, easily ftracture.Nano silicon is a kind of conventional
In the coating additive for improving the multiple performances such as epoxy coating pliability, ageing resistance, heat stability, impact strength,
But its surface has the hydroxyl of different bond styles, there is the characteristic of hydrophilic oleophobic, causes which to hold in epoxy coating
Easily occur to reunite, and nanoparticle is poor with the interfacial interaction power of matrix, so as to reduce its activeness and quietness epoxy resin
The effect of coating.Therefore, it is necessary during nano silicon that carrying out surface is modified used in epoxy-resin systems.
In order to improve dispersibility of the nano silicon in epoxy coating and mutual with epoxy resin interface
Effect, it is possible to use coupling agent or polymerizable acrylate carry out surface and be modified, and such as will contain end ring in anhydrous conditions
γ-the glycidyl ether oxygen propyl trimethoxy silicane of epoxide（KH560）The surface of nano silicon is grafted on, so both may be used
To improve nano silicon dispersibility in the epoxy, it is also possible to which nano silicon is solidificated in epoxy-resin systems
In, contribute to nano silicon dispersion in the epoxy and the interaction with epoxy resin-base, but use
The modified nano silicon of this quadrat method, coupling agent or polymer it is relatively low in the percent grafting of nano-silica surface, for
The peptizaiton in epoxy coating of nano silicon is limited.In order to improve the percent grafting of nano-silica surface,
A kind of feasible method is to prepare nanometer organic-inorganic hybrid material in nano-silica surface graft polymers.Peng
Yang etc.（Toughening of epoxy resin with poly(methyl methacrylate) grafted
silica core-shell particles）Mention using the mode of atom transfer radical polymerization in nano silicon table
Face grafting polymethyl methacrylate obtains PMMA-g-SiO2 nanometer organic inorganic hybridization particles, and is applied in epoxy resin
Realize the effect of the activeness and quietness of epoxy resin and do not reduce the glass transition temperature and thermostability of resin, but research
Show the interaction that may insure between epoxy resin-base and modifying agent containing epoxy terminated polymer, in asphalt mixtures modified by epoxy resin
Effect with more preferable activeness and quietness epoxy resin in fat/amine system.
In recent years, it is excellent due to the unique structure of dissaving polymer and performance characteristics and achievable large-scale production
Point, is quickly become the focus of polymeric material field research.Ji-Fang Fu etc.（Morphology, toughness
mechanism, and thermal properties of hyperbranched epoxy modified diglycidyl
ether of bisphenol A(DGEBA) interpenetrating polymer networks. 2008(19):1597-
1607.）Significantly can increase during using epoxy terminated hyper-branched polyester modified bisphenol A epoxy resin/dimethyl diphenyl methane system
The notch impact strength of strong system, but can also there is a certain degree of drop in the glass transition temperature of system and thermostability
It is low.For this purpose, epoxy radicals are grafted on nano-silica surface prepares the modified nanometer of epoxy terminated Aromatic Hyperbranched Polyesters
Organic-inorganic hybrid material, you can to improve above-mentioned problem, it is also possible to enhance nano silicon in epoxy coating
In the compatibility, in addition nanoparticle be solidificated in epoxy resin-base, be also beneficial to nano silicon and epoxy matrix
Interact.
The content of the invention
It is an object of the invention to provide a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization
The preparation method of material, will be containing epoxy terminated by the reaction between the hydroxyl and epoxychloropropane of nano-silica surface
Hyper-branched polyester be grafted on nano-silica surface.
A kind of preparation method of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material, which is special
It is to realize being grafted hyper-branched polyester in nano-silica surface using alcohol and sour reaction to levy, and is then sealed through epoxide
What end obtained, the preparation method is comprised the following steps.
A) 5 ~ 10 weight portion nano silicons are scattered in the organic solvent of 500 ~ 1000 weight portions, add 5 ~ 10 weights
The epoxy terminated silane coupler of amount part, 8 ~ 12h of graft reaction at 60 ~ 120 DEG C, product are filtered, wash, are dried, you can obtained
Modified manometer silicon dioxide of the surface for amino.
B) take the above-mentioned modified manometer silicon dioxide of 5 ~ 10 weight portions to be scattered in the organic solvent of 500 ~ 1000 weight portions,
0.05 ~ 0.1 part by weight of catalyst and 5 ~ 10 parts by weight of polyol are added, nitrogen 5 ~ 10h of heating reflux reaction is passed through,
Then stop being passed through nitrogen, decompression sucking filtration to objects system bubble-free is produced, you can obtain superbrnaching end-hydroxy polyester modified Nano
Silicon dioxide, i.e. first generation terminal hydroxy group modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 5 ~ 10 weight portions and be scattered in 500 ~ 1000 weight portions
In organic solvent, 10 ~ 15 weight portion anhydrous inorganic salts, then 5 ~ 10 parts by weight epoxy compound of Deca are added, the mixture exists
Nitrogen reacts 5 ~ 10h under the conditions of protecting 60 ~ 120 DEG C, adds water-soluble salt and the washing of 50 ~ 100 weight portions, then after the completion of reaction
Product is leached by decompression sucking filtration, you can obtain the epoxy terminated hyper-branched polyester modified manometer silicon dioxide of the first generation.
Repeat step b) is obtained second filial generation terminal hydroxy group modified manometer silicon dioxide, and repeat step c) is obtained the
Secondary epoxy terminated hyper-branched polyester polymer modification nano silicon organic-inorganic hybrid material.It is obtained by that analogy
The epoxy terminated hyper-branched polyester polymer modification nano silicon organic-inorganic hybrid material of different algebraically.
Preferably, in preparation method of the present invention, the particle diameter of the nano silicon for being used is 20 ~ 60nm, surface hydroxyl
Base content is not less than 1.5mmol/g, using being at least dried 2h at first 120 DEG C.
Preferably, in preparation method of the present invention, described epoxy terminated silane coupler is γ-glycidyl ether oxygen third
Base trimethoxy silane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-aminopropyltriethoxy
One or more in dimethoxysilane.
Preferably, in preparation method of the present invention, described organic solvent be tetrahydrofuran, acetone, toluene, dimethylbenzene,
One or more in dimethyl sulfoxide, N,N-dimethylformamide, ethanol.
Preferably, in preparation method of the present invention, described polyol be tetramethylolmethane, trimethylolpropane,
Dipropylene glycol, 2,2- dimethylolpropionic acids, 2,2- dihydromethyl propionic acids, the one kind in 4,4'- double (4'- hydroxyphenyl) valeric acids
Or it is several.
Preferably, in preparation method of the present invention, described anhydrous inorganic salts are sodium carbonate, potassium carbonate, ammonium carbonate, carbonic acid
One or more in hydrogen sodium.
Preferably, in preparation method of the present invention, described epoxide is epoxy prapanol, epoxychloropropane, phenyl
One or more in glycidyl ether, polypropylene glycol diglycidyl ether.
Wherein, the nano silicon or modified manometer silicon dioxide be with ultrasound means be scattered in it is described organic molten
In agent, the ultrasonic disperse time is no less than 30min.
The size of hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material prepared by the present invention, surface
Group and content can be controlled by synthesis conditions such as material choice, modified number of times.The percent grafting of nano silicon
Change with the consumption of modified number of times and polyol or epoxide.
The hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material that the present invention is prepared can be used as changing
Property agent, is applied to prepare in epoxy coating.
Hyper-branched polyester engrafted nanometer silicon dioxide organic-inorganic hybrid material prepared by the present invention, due to its surface grafting
Dissaving polymer, improves the percent grafting of nano-silica surface；Hyper-branched polyester is in silica surface shape simultaneously
Into integument, dispersibility of the nano silicon in epoxy coating is improved；Additionally, modified manometer silicon dioxide table
The end group of face hyper-branched polyester is epoxy radicals, can participate in the solidification process of epoxy coating, realize to epoxy resin body
It is the regulation and control of molecular structure.Thus the nano silicon than common graft modification has more excellent in epoxy coating
Combination property, go for preparing with good adhesion, intensity, wearability, ageing resistance epoxy coating.
Raw material in preparation method of the present invention is industrial chemicals, is realized by simple synthesis technique, gentle reaction
Epoxy terminated hyperbranched poly ester polymer is grafted in nano-silica surface, silica surface group Effective Regulation is reached
Purpose, not only increase percent grafting of the polymer in nano-silica surface, while improving nano silicon in ring
Dispersibility in oxygen tree grease coating material, to realize nanoparticle solid in epoxy-resin systems for the epoxy radicals on hybrid material surface in addition
Change, enhance the interaction between epoxy resin-base and nano-hybrid material.
Specific experiment mode
The technology of preparing of the present invention is further described below in conjunction with specific embodiment, lists the following example and compare
Example, in order that the present invention is explained in more detail, but patent of the present invention is not limited only to these embodiments.
Embodiment 1：The preparation of amine-terminated hyperbrancedization polyester graft nano silicon organic-inorganic hybrid material：
a）5 weight portion nano silicons and 500 weight portions are added in equipped with thermometer, the 1000mL there-necked flasks of agitator
Toluene, after ultrasonic disperse 30min, 5 weight portion γ of Deca-glycidyl ether oxygen propyl trimethoxy silicane under stirring
（KH560）, then 8h is reacted at 70 DEG C, product is filtered, is washed, drying, you can obtain the modified Nano two that surface is amino
Silicon oxide.
B) modified manometer silicon dioxide for taking 5 weight portion amino is scattered in 500 parts by weight of toluene, adds 0.05 weight
Amount part p-methyl benzenesulfonic acid and 10 weight portions 4, double (4'- hydroxyphenyl) valeric acids of 4'-, are passed through nitrogen heating reflux reaction 10h, then stop
Nitrogen is passed through only, decompression sucking filtration to objects system bubble-free is produced, you can obtain superbrnaching end-hydroxy polyester modified nano-silica
Silicon, i.e. first generation Amino End Group modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 5 weight portions and be scattered in 500 weight portion tetrahydrofurans
In, 15 weight portion Anhydrous potassium carbonates, then 10 parts by weight epoxy chloropropane of Deca are added, the mixture protects 60 DEG C of bars in nitrogen
10h is reacted under part, 100 weight portion water-soluble salts after the completion of reaction, are added（Water-soluble salt such as Sodium Chloride, similarly hereinafter）And washing, and
Product is leached by the sucking filtration that reduces pressure afterwards, you can obtain epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material
Material（The epoxy terminated modified manometer silicon dioxide of the first generation）.
D) first generation terminal hydroxy group modified manometer silicon dioxide repeat step b) is obtained into second filial generation superbrnaching end-hydroxy polyester
Polymer modification nano silicon, as second filial generation terminal hydroxy group modified manometer silicon dioxide.
E) second filial generation terminal hydroxy group modified manometer silicon dioxide repeat step c) is obtained into epoxy terminated hyperbranched poly polyisocyanate polyaddition
The epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material of thing modified manometer silicon dioxide, the as second filial generation
Material.Different algebraically epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material is obtained by that analogy
Material.
Embodiment 2：The preparation of amine-terminated hyperbrancedization polyester graft nano silicon organic-inorganic hybrid material：
a）10 weight portion nano silicons and 1000 weight are added in equipped with thermometer, the 1000mL there-necked flasks of agitator
Part dimethylbenzene, after ultrasonic disperse 60min, 10 weight portion N- β (aminoethyl)-γ of Deca-aminopropyl trimethoxy under stirring
Silane, then reacts 12h at 120 DEG C, and product is filtered, washed, drying, you can obtain the modified nano-silica that surface is amino
SiClx.
B) modified manometer silicon dioxide for taking 10 weight portion amino is scattered in 1000 parts by weight of xylene, adds 0.1
Weight portion p-methyl benzenesulfonic acid and 5 weight portions 2,2- dimethylolpropionic acids, are passed through nitrogen heating reflux reaction 5h, then stop being passed through
Nitrogen, decompression sucking filtration to objects system bubble-free are produced, you can obtain superbrnaching end-hydroxy polyester modified manometer silicon dioxide, i.e., and the
Generation Amino End Group modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 10 weight portions to be scattered in 1000 parts by weight of toluene,
10 weight portion Carbon Dioxide ammoniums, then 5 parts by weight epoxy propanol of Deca are added, the mixture is under the conditions of nitrogen protects 120 DEG C
Reaction 5h, adds 50 weight portion water-soluble salts and washing after the completion of reaction, product is leached by the sucking filtration that then reduces pressure, you can obtain end ring
Epoxide hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material（The epoxy terminated modified nano-silica of the first generation
Silicon）.
D) first generation terminal hydroxy group modified manometer silicon dioxide repeat step b) is obtained into second filial generation superbrnaching end-hydroxy polyester
Polymer modification nano silicon, as second filial generation terminal hydroxy group modified manometer silicon dioxide.
E) second filial generation terminal hydroxy group modified manometer silicon dioxide repeat step c) is obtained into epoxy terminated hyperbranched poly polyisocyanate polyaddition
The epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material of thing modified manometer silicon dioxide, the as second filial generation
Material.Different algebraically epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material is obtained by that analogy
Material.
Embodiment 3：The preparation of amine-terminated hyperbrancedization polyester graft nano silicon organic-inorganic hybrid material：
a）9 weight portion nano silicons and 800 weight portions are added in equipped with thermometer, the 1000mL there-necked flasks of agitator
Dimethyl sulfoxide, after ultrasonic disperse 50min, 9 weight portion N- β (aminoethyl)-γ of Deca-aminopropyltriethoxy diformazan under stirring
TMOS, then reacts 10h at 100 DEG C, and product is filtered, washed, drying, you can obtain the modified Nano that surface is amino
Silicon dioxide.
B) modified manometer silicon dioxide for taking 9 weight portion amino is scattered in 800 weight portion dimethyl sulfoxides, is added
0.08 weight portion p-methyl benzenesulfonic acid and 9 weight portions 2,2- dihydromethyl propionic acids, are passed through nitrogen heating reflux reaction 8h, then stop
Nitrogen is passed through, decompression sucking filtration to objects system bubble-free is produced, you can obtain superbrnaching end-hydroxy polyester modified manometer silicon dioxide,
That is first generation Amino End Group modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 9 weight portions to be scattered in 800 parts by weight of ethanol, then
12 weight portion anhydrous sodium bicarbonates, then 9 weight portion phenyl glycidyl ether of Deca, the mixture is added to protect 90 DEG C of bars in nitrogen
8h is reacted under part, 90 weight portion water-soluble salts and washing after the completion of reaction, is added, product is leached by the sucking filtration that then reduces pressure, you can obtained
Epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material（The epoxy terminated modified nano-silica of the first generation
SiClx）.
D) first generation terminal hydroxy group modified manometer silicon dioxide repeat step b) is obtained into second filial generation superbrnaching end-hydroxy polyester
Polymer modification nano silicon, as second filial generation terminal hydroxy group modified manometer silicon dioxide.
E) second filial generation terminal hydroxy group modified manometer silicon dioxide repeat step c) is obtained into epoxy terminated hyperbranched poly polyisocyanate polyaddition
The epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material of thing modified manometer silicon dioxide, the as second filial generation
Material.Different algebraically epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material is obtained by that analogy
Material.
Embodiment 4：The preparation of amine-terminated hyperbrancedization polyester graft nano silicon organic-inorganic hybrid material：
a）7 weight portion nano silicons and 700 weight portions are added in equipped with thermometer, the 1000mL there-necked flasks of agitator
Acetone, after ultrasonic disperse 40min, 7 weight portion γ of Deca-glycidyl ether oxygen propyl trimethoxy silicane, N- β under stirring
(aminoethyl)-γ-aminopropyltrimethoxysilane, then reacts 9h at 90 DEG C, and product is filtered, washed, drying, you can
To the modified manometer silicon dioxide that surface is amino.
B) modified manometer silicon dioxide for taking 7 weight portion amino is scattered in 700 pbw acetones, adds 0.07 weight
Amount part p-methyl benzenesulfonic acid and 7 weight portion tetramethylolmethanes, are passed through nitrogen heating reflux reaction 7h, then stop being passed through nitrogen, reduce pressure
Sucking filtration is produced to objects system bubble-free, you can obtain superbrnaching end-hydroxy polyester modified manometer silicon dioxide, i.e. first generation end ammonia
Base modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 7 weight portions and be scattered in 700 weight portion N, N- dimethyl
In Methanamide, 13 parts by weight sodium carbonate, then 7 weight portion polypropylene glycol diglycidyl ether of Deca are added, the mixture is in nitrogen
7h being reacted under the conditions of 80 DEG C of gas shielded, 80 weight portion water-soluble salts and washing being added after the completion of reaction, the sucking filtration that then reduces pressure is by product
Leach, you can obtain epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material（First generation end ring oxygen
Base modified manometer silicon dioxide）.
D) first generation terminal hydroxy group modified manometer silicon dioxide repeat step b) is obtained into second filial generation superbrnaching end-hydroxy polyester
Polymer modification nano silicon, as second filial generation terminal hydroxy group modified manometer silicon dioxide.
E) second filial generation terminal hydroxy group modified manometer silicon dioxide repeat step c) is obtained into epoxy terminated hyperbranched poly polyisocyanate polyaddition
The epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material of thing modified manometer silicon dioxide, the as second filial generation
Material.Different algebraically epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material is obtained by that analogy
Material.
Embodiment 5：The preparation of amine-terminated hyperbrancedization polyester graft nano silicon organic-inorganic hybrid material：
a）8 weight portion nano silicons and 900 weight portions are added in equipped with thermometer, the 1000mL there-necked flasks of agitator
The mixed solvent of any mixing ratio of tetrahydrofuran, acetone, after ultrasonic disperse 70min, 8 weight portion N- β (ammonia of Deca under stirring
Ethyl)-γ-aminopropyltrimethoxysilane, N- β (aminoethyl)-γ-any mixing ratio of aminopropyltriethoxy dimethoxysilane
Mixture, 11h is then reacted at 80 DEG C, product is filtered, washing, be dried, you can obtain the modified Nano that surface is amino
Silicon dioxide.
B) modified manometer silicon dioxide for taking 8 weight portion amino is scattered in 900 weight portion tetrahydrofurans, acetone, then plus
Enter 0.09 weight portion p-methyl benzenesulfonic acid and 8 weight portion 2,2- dimethylolpropionic acids, third any mixing ratio of 2,2- dihydroxymethyls it is mixed
Compound, is passed through nitrogen heating reflux reaction 9h, then stops being passed through nitrogen, and decompression sucking filtration to objects system bubble-free is produced, you can
Obtain superbrnaching end-hydroxy polyester modified manometer silicon dioxide, i.e. first generation Amino End Group modified manometer silicon dioxide.
C) take the above-mentioned first generation terminal hydroxy group modified manometer silicon dioxide of 8 weight portions and be scattered in 900 weight portion N, N- dimethyl
In the mixed solvent of any mixing ratio of Methanamide, ethanol, 14 weight portion ammonium carbonate, sodium bicarbonate, then 8 weight portion of Deca are added
The mixture of any mixing ratio of polypropylene glycol diglycidyl ether, phenyl glycidyl ether, the mixture protect 100 DEG C in nitrogen
Under the conditions of react 9h, 70 weight portion water-soluble salts and washing are added after the completion of reaction, then reduce pressure sucking filtration product is leached, you can
To epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material（The epoxy terminated modified Nano of the first generation two
Silicon oxide）.
D) first generation terminal hydroxy group modified manometer silicon dioxide repeat step b) is obtained into second filial generation superbrnaching end-hydroxy polyester
Polymer modification nano silicon, as second filial generation terminal hydroxy group modified manometer silicon dioxide.
E) second filial generation terminal hydroxy group modified manometer silicon dioxide repeat step c) is obtained into epoxy terminated hyperbranched poly polyisocyanate polyaddition
The epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material of thing modified manometer silicon dioxide, the as second filial generation
Material.Different algebraically epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material is obtained by that analogy
Material.
The advanced feature of the present invention is verified below by contrast test：
Comparative example 1
Weigh 30g bisphenol A type epoxy resin E-51（Epoxide number 0.48 ~ 0.54）, 10g mixed solvents（Dimethylbenzene and n-butyl alcohol matter
Amount is than being 7:3）, stir as first component.
Weigh 24g amine epoxy curing agent modified by cardanol NX-2015（Ahew 151）, 16g mixed solvents, stirring
Uniformly as second component.
By two components of first and second at room temperature by weight ratio 1:1 it is uniform mix, with tinplate be by viscous material,
Tinplate pre-treatment is performed according to standard GB/T9271-2008, is finally coated the mode that the coating of mix homogeneously is brushed
On tinplate and place 7 days.Paint film adhesion method of testing is performed according to standard GB 1720-1979, and paint film impact resistance is surveyed
Method for testing is performed according to standard GB/T 1732-93, and epoxy batten tensile strength test testing standard is GB/T1040-2006, is surveyed
Test result is listed in table 1.
Comparative example 2
Weigh 30g bisphenol A type epoxy resin E-51（Epoxide number 0.48 ~ 0.54）, 10g mixed solvents（Dimethylbenzene and n-butyl alcohol matter
Amount is than being 7:3）, 0.5g nano silicons, in 300r/min ball milling 3h, as first component.
Weigh 24g amine epoxy curing agent modified by cardanol NX-2015（Ahew 151）, 16g mixed solvents, stirring
Uniformly as second component.
By two components of first and second at room temperature by weight ratio 1:1 it is uniform mix, with tinplate be by viscous material,
Tinplate pre-treatment is performed according to standard GB/T9271-2008, is finally coated the mode that the coating of mix homogeneously is brushed
On tinplate and place 7 days.Paint film adhesion method of testing is performed according to standard GB 1720-1979, and paint film impact resistance is surveyed
Method for testing is performed according to standard GB/T 1732-93, and epoxy batten tensile strength test testing standard is GB/T1040-2006, is surveyed
Test result is listed in table 1.
Comparative example 3
Weigh 30g bisphenol A type epoxy resin E-51（Epoxide number 0.48 ~ 0.54）, 10g mixed solvents（Dimethylbenzene and n-butyl alcohol matter
Amount is than being 7:3）, the epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material of the 0.5g first generation,
300r/min ball milling 3h, as first component.
Weigh 24g amine epoxy curing agent modified by cardanol NX-2015（Ahew 151）, 16g mixed solvents, stirring
Uniformly as second component.
By two components of first and second at room temperature by weight ratio 1:1 it is uniform mix, with tinplate be by viscous material,
Tinplate pre-treatment is performed according to standard GB/T9271-2008, is finally coated the mode that the coating of mix homogeneously is brushed
On tinplate and place 7 days.Paint film adhesion method of testing is performed according to standard GB 1720-1979, and paint film impact resistance is surveyed
Method for testing is performed according to standard GB/T 1732-93, and epoxy batten tensile strength test testing standard is GB/T1040-2006, is surveyed
Test result is listed in table 1.
Comparative example 4
Weigh 30g bisphenol A type epoxy resin E-51（Epoxide number 0.48 ~ 0.54）, 10g mixed solvents（Dimethylbenzene and n-butyl alcohol matter
Amount is than being 7:3）, the epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material of the 0.5g second filial generations,
300r/min ball milling 3h, as first component.
Weigh 24g amine epoxy curing agent modified by cardanol NX-2015（Ahew 151）, 16g mixed solvents, stirring
Uniformly as second component.
By two components of first and second at room temperature by weight ratio 1:1 it is uniform mix, with tinplate be by viscous material,
Tinplate pre-treatment is performed according to standard GB/T9271-2008, is finally coated the mode that the coating of mix homogeneously is brushed
On tinplate and place 7 days.Paint film adhesion method of testing is performed according to standard GB 1720-1979, and paint film impact resistance is surveyed
Method for testing is performed according to standard GB/T 1732-93, and epoxy batten tensile strength test testing standard is GB/T1040-2006, is surveyed
Test result is listed in table 1.
Comparative example 5
Weigh 30g bisphenol A type epoxy resin E-51（Epoxide number 0.48 ~ 0.54）, 10g mixed solvents（Dimethylbenzene and n-butyl alcohol matter
Amount is than being 7:3）, the epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material of the 0.5g third generations,
300r/min ball milling 3h, as first component.
Weigh 24g amine epoxy curing agent modified by cardanol NX-2015（Ahew 151）, 16g mixed solvents, stirring
Uniformly as second component.
By two components of first and second at room temperature by weight ratio 1:1 it is uniform mix, with tinplate be by viscous material,
Tinplate pre-treatment is performed according to standard GB/T9271-2008, is finally coated the mode that the coating of mix homogeneously is brushed
On tinplate and place 7 days.Paint film adhesion method of testing is performed according to standard GB 1720-1979, and paint film impact resistance is surveyed
Method for testing is performed according to standard GB/T 1732-93, and epoxy batten tensile strength test testing standard is GB/T1040-2006, is surveyed
Test result is listed in table 1.
The properties of epoxy coating prepared by 1. embodiment of table 1 ~ 5
| Performance | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Adhesive force (level) | Two | Two | One | One | One |
| Impact strength (cm) | 10 | 10 | 20 | 25 | 35 |
| Tensile strength (MPa) | 18 | 16 | 20 | 21 | 23 |
By relatively can be seen that in the case of two composition weight number of first, second, ratio, solidification temperature all same to parameter,
With the increase of the epoxy-modified nano silicon algebraically of organic-inorganic hybrid material middle-end, the attachment of epoxy coating
Power, impact strength and tensile strength are improved to some extent.
Claims (10)
1. a kind of preparation method of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic-inorganic hybrid material, its feature
It is that the preparation method is comprised the following steps:
A) 5 ~ 10 weight portion nano silicons are scattered in the organic solvent of 500 ~ 1000 weight portions, add 5 ~ 10 weight portions
Epoxy terminated silane coupler, 8 ~ 12h of graft reaction at 60 ~ 120 DEG C, product are filtered, wash, are dried, you can obtain surface
For the modified manometer silicon dioxide of amino;
B) take the above-mentioned modified manometer silicon dioxide of 5 ~ 10 weight portions to be scattered in the organic solvent of 500 ~ 1000 weight portions, then plus
Enter 0.05 ~ 0.1 part by weight of catalyst and 5 ~ 10 parts by weight of polyol, be passed through nitrogen 5 ~ 10h of heating reflux reaction, then
Stopping is passed through nitrogen, and decompression sucking filtration to objects system bubble-free is produced, you can obtain superbrnaching end-hydroxy polyester modified nano-silica
SiClx, i.e. first generation terminal hydroxy group modified manometer silicon dioxide;
C) take the organic solvent that the above-mentioned terminal hydroxy group modified manometer silicon dioxide of 5 ~ 10 weight portions is scattered in 500 ~ 1000 weight portions
In, 10 ~ 15 weight portion anhydrous inorganic salts, then 5 ~ 10 parts by weight epoxy compound of Deca are added, the mixture is protected in nitrogen
5 ~ 10h is reacted under the conditions of 60 ~ 120 DEG C, water-soluble salt and the washing of 50 ~ 100 weight portions after the completion of reaction, is added, then reduce pressure sucking filtration
Product is leached, you can obtain epoxy terminated hyper-branched polyester polymer modification nano silicon organic-inorganic hybrid material.
2. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that the particle diameter of the nano silicon is 20 ~ 60nm, and the adsorbed hydroxyl content is not less than
1.5mmol/g, using being at least dried 2h at first 120 DEG C.
3. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described epoxy terminated silane coupler is γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane, γ-glycidyl ether oxygen propyl trimethoxy silicane, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, N- β (ammonia
Ethyl) one or more in-γ-aminopropyltriethoxy dimethoxysilane.
4. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described organic solvent for tetrahydrofuran, acetone, toluene, dimethylbenzene, dimethyl sulfoxide, N, N-
One or more in dimethylformamide, ethanol.
5. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, it is characterized in that described polyol be tetramethylolmethane, trimethylolpropane, dipropylene glycol,
2,2- dimethylolpropionic acids, 2,2- dihydromethyl propionic acids, one or more in 4,4'- double (4'- hydroxyphenyl) valeric acids.
6. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described anhydrous inorganic salts are the one kind in sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate
Or it is several.
7. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described epoxide is epoxy prapanol, epoxychloropropane, phenyl glycidyl ether, poly-
One or more in propylene glycol diglycidylether.
8. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described nano silicon or modified manometer silicon dioxide are scattered in the means of ultrasound
In the organic solvent, the ultrasonic disperse time is no less than 30min.
9. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization material according to claim 1
The preparation method of material, is characterized in that described preparation method also includes：First generation terminal hydroxy group modified manometer silicon dioxide is repeated
Step b) obtains second filial generation terminal hydroxy group modified manometer silicon dioxide.
10. a kind of epoxy terminated hyper-branched polyester modified manometer silicon dioxide organic inorganic hybridization according to claim 9
The preparation method of material, is characterized in that described preparation method also includes：By second filial generation terminal hydroxy group modified manometer silicon dioxide weight
Multiple step c) obtains the epoxy terminated hyper-branched polyester polymer modification nano silicon organic-inorganic hybrid material of the second filial generation.
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