CN110078894A - A kind of naphthalenediol type hyperbranched epoxy resin and its preparation method and application - Google Patents
A kind of naphthalenediol type hyperbranched epoxy resin and its preparation method and application Download PDFInfo
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- CN110078894A CN110078894A CN201910267404.XA CN201910267404A CN110078894A CN 110078894 A CN110078894 A CN 110078894A CN 201910267404 A CN201910267404 A CN 201910267404A CN 110078894 A CN110078894 A CN 110078894A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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Abstract
A kind of naphthalenediol type hyperbranched epoxy resin and its preparation method and application, belongs to technical field of polymer materials.It is raw material that preparation method, which is using the naphthalenediol of commercialization and polynary glycidol ether, is passed through nitrogen protection, under catalyst quaternary ammonium salt or quaternary phosphonium salt effect, does not add any solvent, one-step synthesis method naphthalenediol type hyperbranched epoxy resin.Being added in the linear epoxy resin of bisphenol A-type using naphthalenediol type hyperbranched epoxy resin of the invention can be obtained a kind of modified resin, prepare a kind of high solid anti-corrosive paint of epoxy resin as film forming matter.Its paint film has high resistance to medium and excellent impact resistance.Naphthalenediol type hyperbranched epoxy resin of the invention can be not only used for heavy antisepsis epoxy systems, may be simultaneously used for the fields such as composite material, electronic package material.
Description
Technical field
The present invention relates to a kind of naphthalenediol type hyperbranched epoxy resins and its preparation method and application, belong to high molecular material
Technical field.
Background technique
Dissaving polymer has the characteristics that low-viscosity, highly dissoluble and high functionality, in high molecular material and coating etc.
Field has broad application prospects.
Epoxy resin and its solidfied material have shrinking percentage small, chemical resistance and machine good with a variety of surface cementabilities
Tool performance and excellent electrical properties are the biggish kinds of application amount in thermosetting resin, are widely used in anticorrosive paint
In.However epoxy coating weatherability and impact resistance are poor, corrosion resistance also needs to be further increased, with environmentally friendly dynamics
It increases, high solid anti-corrosive paint of epoxy resin is following developing direction.Since dissaving polymer is with unique low viscous
Property, it can be blended with linear epoxy resin to reduce the viscosity of high solid anti-corrosive paint of epoxy resin system and improve the system
Mobility prepares high solid epoxy coating.
Currently, the type of Hyperbranched Epoxy Compounds mainly has polyester type hyperbranched epoxy resin, polyether type hyperbranched ring
Oxygen resin, polyester polyether type hyperbranched epoxy resin, polyalkamer type hyperbranched epoxy resin and the hyperbranched asphalt mixtures modified by epoxy resin of polyether sulfone type
Rouge.The polymerization of proton translocation method is the most common method of synthesis of super branched resin, and Li Xiaoyu etc. (ZL200810105407.5) is used
Commercialized raw materials benzenediol or bisphenol-A are A2Monomer and trihydroxymethylpropanyltri diglycidyl ether are B3Monomer, it is poly- through proton translocation
Unification step bisphenol synthesis class polyether type hyperbranched epoxy resin, A2+B3Synthetic method, monomer structure is different, resulting product
Performance would also vary from, and can regulate and control monomer according to performance requirement, have flexibility.
Summary of the invention
It is anti-by proton translocation the purpose of the present invention is being raw material using the naphthalenediol and polynary glycidol ether that are commercialized
It answers, one-step synthesis naphthalenediol type hyperbranched epoxy resin, naphthalene unit is to be conjugated big planar structure, has high cohesive performance, institute
Resin is added in the linear epoxy resin of bisphenol A-type a kind of modified resin can be obtained, prepared as film forming matter a kind of high
Solid part anti-corrosive paint of epoxy resin, paint film have high barrier property, and antiseptic property is excellent.
A kind of naphthalenediol type hyperbranched epoxy resin/epoxy resin provided by the present invention and its preparation method and application,
It is characterized in that, reactor is added by naphthalenediol and polynary glycidol ether in the naphthalenediol type hyperbranched epoxy resin together,
Under nitrogen protection, when system reaches 80-150 DEG C, catalyst is added, reacts 1-16h；After reaction, cooling discharge obtains
To a kind of naphthalenediol type hyperbranched epoxy resin, wherein naphthalenediol, polynary glycidol ether molar ratio are 2:4-6, naphthalenediol with
Catalyst volume molar ratio is preferably 2:0.0014-0.017.
Naphthalenediol used in the present invention is 1,2- naphthalenediol, 1,3- naphthalenediol, 1,4- naphthalenediol, 1,5- naphthalenediol, 1,6-
One of naphthalenediol, 1,7- naphthalenediol, 2,3- naphthalenediol, 2,6- naphthalenediol, 2,7- naphthalenediol or a variety of mixtures, wherein excellent
It is selected as one of 1,4- naphthalenediol, 1,5- naphthalenediol, 1,6- naphthalenediol, 2,3- naphthalenediol, 2,7- naphthalenediol.
Polynary glycidol ether used in the present invention is preferably trihydroxymethylpropanyltri diglycidyl ether, the shrink of glycerine three
One or more mixtures of glycerin ether, pentaerythrite triglycidyl ether.
Catalyst used in the present invention is tetrabutylammonium chloride, tetrabutylammonium bromide, Ethyltriphenylphosphonium brimide, ethyl three
Tetraphenylphosphonium chloride phosphorus, ethyl-trimethyl phosphonium bromide, ethyl-trimethyl phosphorus chloride one or more mixtures, wherein preferably four fourths
One or more mixtures of base ammonium bromide, Ethyltriphenylphosphonium brimide.
A kind of application of naphthalenediol type hyperbranched epoxy resin is added by a kind of resulting naphthalenediol type hyperbranched epoxy resin
It is added in linear epoxy resin and a kind of modified resin can be obtained, a kind of bi-component corrosion-proof dope is prepared with this.
Described a kind of bi-component corrosion-proof dope and the preparation method comprises the following steps: in terms of mass fraction, raw material includes following substance:
Component A:
One of naphthalenediol type hyperbranched epoxy resin type or a variety of mixtures: 1-10 parts；
One of bisphenol A type epoxy resin type or a variety of mixtures: 19-80 parts；
Organic solvent: 20-90 parts；
B component:
Epoxy hardener；
Press epoxide equivalent by component A and B component: active hydrogen equivalent weight is to obtain the painting of bi-component anti-corrosion after 1:0.8-1.2 is mixed
Material；
Naphthalenediol type hyperbranched epoxy resin/epoxy resin composite anticorrosion coating is obtained in room temperature curing when use.
Other auxiliary agents, such as levelling agent, defoaming agent can also be added in the bi-component corrosion-proof dope.
Naphthalenediol type hyperbranched epoxy resin prepared by the present invention, molecular weight is controllable and narrowly distributing, simple process are not necessarily to
Post-processing is suitble to produce in enormous quantities.The compact in paint film obtained using naphthalenediol type hyperbranched epoxy resin prepared by the present invention
Height, antiseptic property are excellent.
Naphthalenediol type hyperbranched epoxy resin prepared by the present invention can be not only used for heavy antisepsis epoxy systems, simultaneously also
It can be used for the fields such as composite material, electronic package material.
Reaction of the invention is exemplified below:
Detailed description of the invention
Fig. 1 is the nuclear-magnetism figure of embodiment 1；
Fig. 2 is the nuclear-magnetism figure of embodiment 7；
Fig. 3 is the nuclear-magnetism figure of embodiment 8；
Fig. 4 is the nuclear-magnetism figure of embodiment 9；
Fig. 5 is the nuclear-magnetism figure of embodiment 10.
Specific embodiment
The invention will be further elaborated combined with specific embodiments below.It should be understood that the present invention is not limited to following implementations
Example, the method is conventional method unless otherwise instructed, and the material can obtain unless otherwise instructed from public commercial source
?.
Coating prepared by the present invention is coated in the metal surface by degreasing and rust removal processing, after 25~120 DEG C of solidifications
It uses.Physical mechanical property test is carried out to coating and respectively in 5%NaOH, 3.5%NaCl, 10%H2SO4And distilled water
Middle progress solution immersion test and the experiment of 3.5%NaCl neutrality salt spray resistance, as a result, it has been found that the paint adhesion of preparation is 1 grade,
Shock resistance reaches 120cm, flexibility 0.5mm, and acid resistance was up to 1000 hours, and alkali resistance was up to 2700 hours, water resistance and resistance to
Salt was up to 2700 hours, and salt fog resistance was up to 2800 hours.With electrochemical impedance spectrum analysis, after indicating that paint film has impregnated 2000 hours
Impedance value is still 10 under low frequency9Ω illustrates that paint film has good protective effect to metallic matrix.
Embodiment 1:
In the 20L jacketed glass kettle equipped with mechanical stirring, reflux condenser and nitrogen ingress pipe, it is passed through High Purity Nitrogen
Gas displacement 10min, and nitrogen is kept to be continually fed into lower addition 105.823g trihydroxymethylpropanyltri diglycidyl ether, unlatching is stirred
Mix, add 20.020g 2,7- naphthalenediol, collet oil bath is warming up to 100 DEG C, it is to be dissolved completely after, the 0.060g tetrabutyl is added
Ammonium bromide, system temperature are gradually heated to 130 DEG C, after being maintained at 130 DEG C of reaction 3h, continue to be heated to 150 DEG C, be added
0.040g Ethyltriphenylphosphonium brimide is maintained at 150 DEG C of reaction 2h.After reaction, 50 DEG C of dischargings are cooled to, are obtained blackish green
Viscous liquid 2,7- naphthalenediol type hyperbranched epoxy resin, physical and chemical parameter are shown in Table 1.
Embodiment 2:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 98.260g trihydroxymethylpropanyltri diglycidyl ether into, changes 0.060g tetrabutylammonium bromide into 0.058g tetra-
Butylammonium bromide changes 0.040g Ethyltriphenylphosphonium brimide into 0.037g Ethyltriphenylphosphonium brimide.Other and 1 phase of embodiment
Together.
Embodiment 3:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 90.710g trihydroxymethylpropanyltri diglycidyl ether into, changes 0.06g tetrabutylammonium bromide into 0.054g tetra- fourth
Base ammonium bromide changes 0.040g Ethyltriphenylphosphonium brimide into 0.035g Ethyltriphenylphosphonium brimide.Other and 1 phase of embodiment
Together.
Embodiment 4:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 83.15g trihydroxymethylpropanyltri diglycidyl ether into, changes 0.06g tetrabutylammonium bromide into 0.051g tetra- fourth
Base ammonium bromide changes 0.04g Ethyltriphenylphosphonium brimide into 0.032g Ethyltriphenylphosphonium brimide.Other are same as Example 1.
Embodiment 5:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 75.59g trihydroxymethylpropanyltri diglycidyl ether into, changes 0.06g tetrabutylammonium bromide into 0.047 tetrabutyl
Ammonium bromide changes 0.040g Ethyltriphenylphosphonium brimide into 0.030g Ethyltriphenylphosphonium brimide.Other are same as Example 1.
Embodiment 6:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 113.38g trihydroxymethylpropanyltri diglycidyl ether into, changes 0.06g tetrabutylammonium bromide into 0.065g tetra- fourth
Base ammonium bromide changes 0.04g Ethyltriphenylphosphonium brimide into 0.042g Ethyltriphenylphosphonium brimide.Other are same as Example 1.
Embodiment 7:
Present implementation is in the preparation of naphthalenediol type hyperbranched epoxy resin, and by 20.020g 2,7- naphthalenediol is changed into
20.020g 1,4-Naphthohydroquinone, other are same as Example 1, obtain the orange hyperbranched epoxy of viscous liquid 1,4-Naphthohydroquinone type
Resin, physical and chemical parameter are shown in Table 1.
Embodiment 8:
Present implementation is in the preparation of naphthalenediol type hyperbranched epoxy resin, and by 20.020g 2,7- naphthalenediol is changed into
20.020g 1,5- naphthalenediol, other are same as Example 1, obtain brown viscous shape liquid 1, the hyperbranched epoxy of 5- naphthalenediol type
Resin, physical and chemical parameter are shown in Table 1.
Embodiment 9:
Present implementation is in the preparation of naphthalenediol type hyperbranched epoxy resin, and by 20.020g 2,7- naphthalenediol is changed into
20.020g 1,6- naphthalenediol, other are same as Example 1, obtain orange viscous liquid 1, the hyperbranched epoxy of 6- naphthalenediol type
Resin, physical and chemical parameter are shown in Table 1.
Embodiment 10:
Present implementation is in the preparation of naphthalenediol type hyperbranched epoxy resin, and by 20.020g 2,7- naphthalenediol is changed into
20.020g 2,3- naphthalenediol, other are same as Example 1, obtain thick pale yellow shape liquid 2, the hyperbranched ring of 3- naphthalenediol type
Oxygen resin, physical and chemical parameter are shown in Table 1.
Embodiment 11:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 105.823g glycerin triglycidyl ether into, other are same as Example 1, obtains blackish green thick naphthalene
Two phenolic hyperbranched epoxy resins, physical and chemical parameter are shown in Table 1.
Embodiment 12:
Present implementation contracts 105.823g trimethylolpropane tris in the preparation of naphthalenediol type hyperbranched epoxy resin
Water glycerin ether changes 105.823g pentaerythrite glycidol ether into, other are same as Example 1, obtains blackish green thick naphthalene
Two phenolic hyperbranched epoxy resins, physical and chemical parameter are shown in Table 1.
Embodiment 13:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 1
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 13.71g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Coating obtained is sprayed on and is removed by oil removing
The metal surface of rust processing, solidifies seven days at room temperature, in case test performance.Paint film thickness bottom is tested according to GB/T1764-79；Paint
Film pencil hardness test is according to GB/T6739-06；Paint film adhesion is tested according to GB/T1720-79；Paint film shock resistance test is pressed
According to GB/T1732-93；Paint film flexibility is tested according to GB/T1720-93；Paint film water resistance test is according to GB/T1733-93；Paint
Film chemical reagent resistance is tested according to GB/T1793-79；The test of paint film salt spray resistance is according to GB/T1771-91, paint film test
Using complete paint film.With the chemical property of electrochemical impedance spectroscopy test paint film, the results of property tested is shown in Table 2 and table
3。
Embodiment 14:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 13
Type hyperbranched epoxy resin changes 2.25g naphthalenediol type hyperbranched epoxy resin into, changes 24.25g epoxy resin E51 into 22.75g
Epoxy resin E51 changes 13.71g curing agent R730 into 13.62g curing agent R730.Other are identical as embodiment 13, are prepared into
It to high solid anti-corrosive paint of epoxy resin, is tested according to the testing standard in embodiment 13, the performance knot tested
Fruit is shown in Table 2 and table 3.
Embodiment 15:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 13
Type hyperbranched epoxy resin changes 2.75g naphthalenediol type hyperbranched epoxy resin into, and 24.25g epoxy resin E51 changes 22.25g ring into
Oxygen resin E51,13.71g curing agent R730 changes 15.62g curing agent R730 into.Other are identical as embodiment 13, and height is prepared
Solid part anti-corrosive paint of epoxy resin, is tested according to the testing standard in embodiment 13, and the results of property tested is shown in
Table 2 and table 3.
Embodiment 16:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 7
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 11.09g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Other are according to the testing standard in embodiment 13
It is tested, the results of property tested is shown in Table 2 and table 3.
Embodiment 17:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 16
Type hyperbranched epoxy resin changes 2.25g naphthalenediol type hyperbranched epoxy resin into, changes 24.25g epoxy resin E51 into 22.75g
Epoxy resin E51 changes 13.09g curing agent R730 into 15.7g curing agent R730.Other are identical as embodiment 13, are prepared
High solid anti-corrosive paint of epoxy resin is tested according to the testing standard in embodiment 13, the results of property tested
It is shown in Table 2 and table 3.
Embodiment 18:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 8
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 15.73g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Other are according to the testing standard in embodiment 13
It is tested, the results of property tested is shown in Table 2 and table 3.
Embodiment 19:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 18
Type hyperbranched epoxy resin changes 2.25g naphthalenediol type hyperbranched epoxy resin into, changes 24.25g epoxy resin E51 into 22.75g
Epoxy resin E51 changes 15.73g curing agent R730 into 15.99g curing agent R730.Other are identical as embodiment 13, are prepared into
It to high solid anti-corrosive paint of epoxy resin, is tested according to the testing standard in embodiment 13, the performance knot tested
Fruit is shown in Table 2 and table 3.
Embodiment 20:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 9
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 14.45g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Other are according to the testing standard in embodiment 13
It is tested, the results of property tested is shown in Table 2 and table 3.
Embodiment 21:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 20
Type hyperbranched epoxy resin changes 2.25g naphthalenediol type hyperbranched epoxy resin into, changes 24.25g epoxy resin E51 into 22.75g
Epoxy resin E51 changes 14.45g curing agent R730 into 14.28g curing agent R730.Other are identical as embodiment 13, are prepared into
It to high solid anti-corrosive paint of epoxy resin, is tested according to the testing standard in embodiment 13, the performance knot tested
Fruit is shown in Table 2 and table 3.
Embodiment 22:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 10
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 14.76g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Other are according to the testing standard in embodiment 13
It is tested, the results of property tested is shown in Table 2 and table 3.
Embodiment 23:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by the 1.75g naphthalenediol in embodiment 22
Type hyperbranched epoxy resin changes 2.25g naphthalenediol type hyperbranched epoxy resin into, changes 24.25g epoxy resin E51 into 22.75g
Epoxy resin E51 changes 14.76g curing agent R730 into 14.85g curing agent R730.Other are identical as embodiment 13, are prepared into
It to high solid anti-corrosive paint of epoxy resin, is tested according to the testing standard in embodiment 13, the performance knot tested
Fruit is shown in Table 2 and table 3.
Embodiment 24:
Present implementation is in the preparation of high solid anti-corrosive paint of epoxy resin, by naphthalenediol type made from embodiment 11
Hyperbranched epoxy resin 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, after being sufficiently mixed, are added
6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent stir 20min, mix
It closes uniformly, obtains bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 14.97g curing agent R730 of component is added,
15min is stirred, filtering and discharging obtains high solid anti-corrosive paint of epoxy resin.Other are according to the testing standard in embodiment 13
It is tested, the results of property tested is shown in Table 2 and table 3.
Embodiment 25:
Present implementation surpasses naphthalenediol type made from embodiment 12 in the preparation of high solid anti-corrosive paint of epoxy resin
Branch epoxy resins 1.75g and 24.25g epoxy resin E51 are stirred 1h in a kettle, and after being sufficiently mixed, 6.25g is added
Dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent, stir 20min, and mixing is equal
It is even, obtain bi-component epoxide-resin coating composition one, solid part is up to 80%.Two 14.65g curing agent R730 of component, stirring is added
15min, filtering and discharging obtain high solid anti-corrosive paint of epoxy resin.Other are carried out according to the testing standard in embodiment 13
Test, the results of property tested are shown in Table 2 and table 3.
Embodiment 26:(is a kind of reference example or comparative example)
25g epoxy resin E51 is added to instead by present implementation in the preparation of high solid anti-corrosive paint of epoxy resin
It answers in kettle, 6.25g dimethylbenzene and butanone mixed solvent (volume ratio 6:4), 0.16g levelling agent and 0.16g defoaming agent is added, stirs
20min is mixed, is uniformly mixed, obtains bi-component epoxide-resin coating composition one.Two 14.54g curing agent R730 of component, stirring is added
15min, filtering and discharging obtain anti-corrosive paint of epoxy resin.
The molecular weight data and monomer residue rate of 1 naphthalenediol type hyperbranched epoxy resin of table
2 coating physical mechanical property data of table
3 coating media-resistant data of table
+: indicate that the time is still increasing.
Claims (10)
1. a kind of preparation method of naphthalenediol hyperbranched epoxy resin, which is characterized in that the hyperbranched asphalt mixtures modified by epoxy resin of naphthalenediol type
Reactor is added by naphthalenediol and polynary glycidol ether in rouge together, under nitrogen protection, when system reaches 80-150 DEG C, adds
Enter catalyst, reacts 1-16h；After reaction, cooling discharge obtains a kind of naphthalenediol type hyperbranched epoxy resin.
2. a kind of preparation method of naphthalenediol hyperbranched epoxy resin described in accordance with the claim 1, which is characterized in that wherein naphthalene
Diphenol, polynary glycidol ether molar ratio are 2:4-6, and naphthalenediol and catalyst volume molar ratio are preferably 2:0.0014-0.017.
3. a kind of preparation method of naphthalenediol hyperbranched epoxy resin described in accordance with the claim 1, which is characterized in that naphthalenediol
For 1,2- naphthalenediol, 1,3- naphthalenediol, 1,4- naphthalenediol, 1,5- naphthalenediol, 1,6- naphthalenediol, 1,7- naphthalenediol, 2,3- naphthalene two
One of phenol, 2,6- naphthalenediol, 2,7- naphthalenediol or a variety of mixtures, wherein preferably 1,4-Naphthohydroquinone, 1,5- naphthalenediol,
One of 1,6- naphthalenediol, 2,3- naphthalenediol, 2,7- naphthalenediol.
4. a kind of preparation method of naphthalenediol hyperbranched epoxy resin described in accordance with the claim 1, which is characterized in that polynary contracting
Water glycerin ether is preferably trihydroxymethylpropanyltri diglycidyl ether, glycerin triglycidyl ether, pentaerythrite three-glycidyl
One or more mixtures of ether.
5. a kind of preparation method of naphthalenediol hyperbranched epoxy resin described in accordance with the claim 1, which is characterized in that catalyst
For tetrabutylammonium chloride, tetrabutylammonium bromide, Ethyltriphenylphosphonium brimide, ethyltriphenyl phosphonium chloride phosphorus, ethyl-trimethyl bromination
One or more mixtures of phosphorus, ethyl-trimethyl phosphorus chloride, wherein preferably tetrabutylammonium bromide, Ethyltriphenylphosphonium brimide
One or more mixtures.
6. the naphthalenediol hyperbranched epoxy resin being prepared according to the described in any item methods of claim 1-5.
7. adding according to the application for the naphthalenediol hyperbranched epoxy resin that the described in any item methods of claim 1-5 are prepared
Being added in linear epoxy resin can be obtained a kind of modified resin or is used to prepare anticorrosive paint.
8. a kind of bi-component corrosion-proof dope, it is characterised in that: in terms of mass fraction, raw material includes following substance:
Component A:
One of naphthalenediol type hyperbranched epoxy resin or a variety of mixtures: 1-10 parts；The hyperbranched ring of naphthalenediol type
Oxygen resin is the naphthalenediol hyperbranched epoxy resin that the described in any item methods of claim 1-5 are prepared；
One of bisphenol A type epoxy resin type or a variety of mixtures: 19-80 parts；
Organic solvent: 20-90 parts；
B component:
Epoxy hardener；
Press epoxide equivalent by component A and B component: active hydrogen equivalent weight is after 1:0.8-1.2 is mixed, to obtain bi-component corrosion-proof dope.
9. a kind of bi-component corrosion-proof dope according to claim 8, it is characterised in that: in the bi-component corrosion-proof dope
It is additionally added other auxiliary agents.
10. a kind of bi-component corrosion-proof dope according to claim 8, it is characterised in that: other auxiliary agents are selected from stream
One or more of flat agent, defoaming agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111848924A (en) * | 2020-08-25 | 2020-10-30 | 江南大学 | Synthetic method and application of low-viscosity fluorine-containing hyperbranched polyether type epoxy resin |
| CN113754861A (en) * | 2021-09-09 | 2021-12-07 | 北京化工大学 | Polycyclic aryl hyperbranched epoxy resin, preparation method thereof, photoluminescent solution and anticorrosive paint obtained by polycyclic aryl hyperbranched epoxy resin and application of photoluminescent solution and anticorrosive paint |
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| WO2003057754A1 (en) * | 2002-01-10 | 2003-07-17 | Vantico Ag | Highly functional polymers |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2003057754A1 (en) * | 2002-01-10 | 2003-07-17 | Vantico Ag | Highly functional polymers |
| CN101570592A (en) * | 2008-04-30 | 2009-11-04 | 北京化工大学 | Polyether type hyperbranched epoxy resin and preparation method thereof |
| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848924A (en) * | 2020-08-25 | 2020-10-30 | 江南大学 | Synthetic method and application of low-viscosity fluorine-containing hyperbranched polyether type epoxy resin |
| CN113754861A (en) * | 2021-09-09 | 2021-12-07 | 北京化工大学 | Polycyclic aryl hyperbranched epoxy resin, preparation method thereof, photoluminescent solution and anticorrosive paint obtained by polycyclic aryl hyperbranched epoxy resin and application of photoluminescent solution and anticorrosive paint |
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