CN104844783A - Fluorine-containing normal-temperature epoxy curing agent of block structure as well as preparation method and application of curing agent - Google Patents
Fluorine-containing normal-temperature epoxy curing agent of block structure as well as preparation method and application of curing agent Download PDFInfo
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Abstract
The invention discloses a fluorine-containing normal-temperature epoxy curing agent of a block structure as well as a preparation method and the application of the curing agent, and belongs to the field of chemical synthesis. The fluorine-containing normal-temperature epoxy curing agent of the block structure is obtained by reacting a block polymer containing epoxy and fluorine groups with polyamine, and the preparation method is simple and low in cost; the curing agent can be co-cured with the epoxy resin to prepare materials having excellent as chemical resistance, pollution resistance, weather fastness, shading property, high caking property, and hydrophobic and oleophobic properties; excellent effects can be achieved.
Description
Technical field
The invention belongs to chemical synthesis field, fluorine-containing normal temperature epoxy solidifying agent being specifically related to a kind of block structure and preparation method thereof and application.
Background technology
Epoxy resin is the thermoset macromolecule material that a class possesses good adhesion, corrosion-resistant, the performance such as electric insulation and high strength, is widely used in the fields such as tamanori, coating, insulating material and matrix material.But along with the development of society, people are more and more stricter to the waterproof of material, oil-stain-preventing, the performance requriements such as wear-resisting, and pure epoxy resin performance can not meet the requirement of practical application.
Because the electronegativity of fluorine atom is large, F-C key is stablized, and makes fluorochemicals have lower surface energy.At present, industrial physics interpolation fluorochemical monomer or the fluoropolymer in the epoxy of mostly adopting, to reduce its surface energy, improves water-oil resistance and stability.Wherein, fluoropolymer because of its modified effect excellent, cost is lower relative to fluorochemical monomer, and is widely used in the modification of epoxy resin.In various fluoropolymer, applying maximum one is fluorinated block copolymer.On the one hand, owing to introducing the non-fluorine segment with specific function in fluorinated block copolymer, improve the performance of multipolymer; On the other hand, decrease the consumption of fluorochemicals, reduce cost.But because fluorine-containing groups polarity differs comparatively large with epoxy resin, in the process of adding fluorinated block copolymer modified epoxy, easily there is the phenomenon be separated, giving full play to of impact effect.
In the real world applications process of modified epoxy, usually need add solidifying agent and epoxy resin generation chemical reaction, form netted space polymer, matrix material aggregate envelope among reticulate body, make the build solid that line style resin becomes tough and tensile.Amine epoxy resin solidifying agent is the class solidifying agent commonly used the most, but usually need hot conditions with its solidification, and with small molecules amine curing agent solidify water-fast, the resistance to greasy dirt of the epoxy resin obtained, chemical resistance is difficult to meet the needs of production development to high-performance coating, greatly limit it and apply.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the fluorine-containing normal temperature epoxy solidifying agent providing a kind of block structure.
Another object of the present invention is to the preparation method of the fluorine-containing normal temperature epoxy solidifying agent that above-mentioned block structure is provided.
Another object of the present invention is the application of the fluorine-containing normal temperature epoxy solidifying agent providing above-mentioned block structure.
Object of the present invention is achieved through the following technical solutions:
A fluorine-containing normal temperature epoxy solidifying agent for block structure, its structural formula is:
Wherein, R is H or carbonatoms is the alkyl of 1 ~ 10; R
1for H or-CH
3; X is
or-CH
2o-; Rf is carbon chain lengths is C
1~ C
10fluoro-alkyl, fluoro-alkyl refers to hydrogen atom wherein by the some or all of displacement of fluorine atom; The integer of m=3 ~ 250; The integer of n=2 ~ 250; Y is the part removing NR in polyamine structure.
Described polyamine is preferably one in aliphatic polyamine or its mixture; Be more preferably at least one in triethylene tetramine, tetraethylene pentamine and diethylenetriamine.
The preparation method of the fluorine-containing normal temperature epoxy solidifying agent of described block structure, comprises following concrete steps:
(1) containing the preparation of epoxy section prepolymer: by monomer, 0.3 ~ 40 mass parts epoxy chloropropane of 100 mass parts containing epoxy group(ing), 0.01 ~ 50 mass parts coordination agent and 0.5 ~ 100 mass parts organic solvent mix, cryosel bath is freezing, vacuumizes, leads to 3 ~ 5 nitrogen with the oxygen in removing system; Under nitrogen protection, be warming up to 60 ~ 120 DEG C, add 0.01 ~ 100 mass parts of catalyst, reaction 1.5 ~ 25h, product is through cold diethyl ether precipitation, and vacuum-drying, to constant weight, obtains containing epoxy section prepolymer;
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: that 100 mass parts fluorochemical monomers, 20 ~ 650 mass parts steps (1) are prepared mixes containing epoxy section prepolymer, 0.01 ~ 50 mass parts coordination agent and 0.5 ~ 100 mass parts organic solvent, cryosel bath is freezing, vacuumizes, drum 3 ~ 5 nitrogen deoxygenations; Then under nitrogen protection, be warming up to 60 ~ 120 DEG C, add 0.01 ~ 100 mass parts of catalyst reaction 1.5 ~ 25h, product is through cold diethyl ether precipitation, and vacuum-drying, to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical;
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get segmented copolymer 100 mass parts containing epoxy and fluorin radical prepared by step (2), add aliphatic polyamine 26 ~ 144 mass parts, react 8 ~ 12h at 0 ~ 35 DEG C; By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent that translucent solid is block structure.
The monomer containing epoxy group(ing) described in step (1) is preferably at least one in (methyl) glycidyl acrylate and glycidyl allyl ether;
Fluorochemical monomer described in step (2) is preferably at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid-1H, 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester; Be more preferably at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate and dodecafluorhe-ptylacrylate;
Step (1) and the coordination agent described in (2) are preferably the straight-chain paraffin of dipyridyl and derivative or many nitrogen; Be more preferably 2,2 '-dipyridyl (Dpy) or pentamethyl-diethylenetriamine (PMDETA);
Step (1) and the organic solvent described in (2) are preferably benzene class, heterocycle or ketone compounds; Be more preferably toluene, ethyl acetate, butylacetate or butanone;
Step (1) and the catalyzer described in (2) are preferably transition metal halide; Be more preferably cuprous bromide or iron protochloride;
Step (1) and the cryosel described in (2) are bathed freezing temperature and are preferably-4 DEG C, utilize in 100 grams of trash ices and add CaCl
26H
2o 20g stirs and obtains;
Step (1) and the vacuum drying condition optimization described in (2) are carry out vacuum-drying under normal temperature.
Aliphatic polyamine described in step (3) is preferably one in aliphatic polyamine or its mixture; Be more preferably at least one in triethylene tetramine, tetraethylene pentamine and diethylenetriamine.
Solvent described in step (3) is by polyamine, the organic solvent that dissolves containing the segmented copolymer of epoxy and fluorin radical, can be mainly at least one in ethyl acetate, butylacetate, toluene and butanone.
The application in epoxy resin cured product prepared by the fluorine-containing normal temperature epoxy solidifying agent of described block structure.The fluorine-containing normal temperature epoxy solidifying agent of this block structure can be used in the preparation of the functional epoxy cured articles such as epoxy structural rubber, epoxy mortar and epoxy protective paint.During practical application, by the stoichiometric of the number ring epoxy resins of amine active hydrogen, condition of cure is: solidify one week at 0 ~ 50 DEG C.
The present invention, relative to prior art, has following advantage and effect:
The present invention is will containing the segmented copolymer of epoxy and fluorin radical and polynary amine epoxy hardener pre-reaction, after obtaining the fluorine-containing normal temperature epoxy solidifying agent of block structure, then with epoxy resin composite curing.Due to fluorine-containing macromole solidifying agent band can with epoxy resin direct reaction, fluoro-containing group is combined with epoxy resin by chemical bond, and therefore consistency improves, and fluorine-containing part is not easily separated out, thus modification epoxy resin better.Due to the introducing of non-fluorine segment in fluorinated block copolymer, reduce production cost.Found by test, compared with commercially available Common curing agents, after using the curing agent modified epoxy resin of fluorine-containing normal temperature epoxy of the block structure of block structure of the present invention, its surface hydrophobicity oleophobic property, thermotolerance and mechanical property all have lifting.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Testing method: measure contact angle by GB/T 24368-2009; Tensile strength and elongation at break is surveyed by ASTM D638-08; Shock strength is surveyed by GB/T 1043-1979.
Embodiment 1
(1) containing the preparation of epoxy section prepolymer: by 100g glycidyl methacrylate, 40g epoxy chloropropane, 0.01g 2; 2 '-dipyridyl and 0.5g butanone join in the there-necked flask of band high speed agitator, thermometer and prolong; mix; freezing through cryosel bath; vacuumize, repeat drum 3 nitrogen; be warming up to 95 DEG C under nitrogen protection; add 0.8g cuprous bromide; maintaining nitrogen purge; reaction 1.5h; product is through cold diethyl ether precipitation, and normal-temperature vacuum is dried to constant weight, obtains containing epoxy section prepolymer.
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: that 100g trifluoroethyl methacrylate monomer, 55g step (1) are prepared mixes containing epoxy section prepolymer, 0.5g pentamethyl-diethylenetriamine and 100g toluene; freezing through cryosel bath; vacuumize, repeat 3 bulging nitrogen; be warming up to 60 DEG C under nitrogen protection; add 100g cuprous bromide; maintaining nitrogen purge; reaction 25h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical.
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get the block polymer 100g containing epoxy and fluorin radical prepared by step (2), be dissolved in toluene with 26g diethylenetriamine, react 12h at 10 DEG C.By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent C1 that translucent solid is block structure.
(4) the fluorine-containing normal temperature epoxy solidifying agent C1 of the block structure using 15g step (3) to prepare mixes with 100g epoxy resin E51, solidifies one week, obtain epoxy resin cured product G1 at 0 DEG C.Distinguish the contact angle of Measurement and Computation G1, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
Embodiment 2
(1) containing the preparation of epoxy section prepolymer: 100g glycidyl allyl ether, 6g epoxy chloropropane, 50g pentamethyl-diethylenetriamine and 100g toluene are joined in the there-necked flask of band high speed agitator, thermometer and prolong; mix; freezing through cryosel bath; vacuumize, repeat drum 3 nitrogen; be warming up to 120 DEG C under nitrogen protection; add 0.01g cuprous bromide; maintaining nitrogen purge; reaction 25h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains containing epoxy section prepolymer.
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: prepared by 100g vinylformic acid trifluoro ethyl ester monomer, 100g step (1) containing epoxy section prepolymer, 0.01g 2; 2 '-dipyridyl and 0.5g butylacetate mix; freezing through cryosel bath; vacuumize, repeat 3 bulging nitrogen; be warming up to 120 DEG C under nitrogen protection; add 0.01g iron protochloride; maintaining nitrogen purge; reaction 1.5h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical.
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get the block polymer 100g containing epoxy and fluorin radical prepared by step (2), be dissolved in toluene with the triethylene tetramine of 64g, react 9h at 20 DEG C.By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent C2 that translucent solid is block structure.
(4) the fluorine-containing normal temperature epoxy solidifying agent C2 of the block structure using 12g step (3) to prepare mixes with 100g epoxy resin E51, solidifies one week, obtain epoxy resin cured product G2 at 50 DEG C.Distinguish the contact angle of Measurement and Computation G2, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
Embodiment 3
(1) containing the preparation of epoxy section prepolymer: by 100g glycidyl acrylate, 0.3g epoxy chloropropane, 5g 2; 2 '-dipyridyl and 50g ethyl acetate join in the there-necked flask of band high speed agitator, thermometer and prolong; mix; freezing through cryosel bath; vacuumize, repeat drum 3 nitrogen; be warming up to 60 DEG C under nitrogen protection; add 100g iron protochloride; maintaining nitrogen purge; reaction 3h; product is through cold diethyl ether precipitation, and normal-temperature vacuum is dried to constant weight, obtains containing epoxy section prepolymer.
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: prepared by 100g vinylformic acid hexafluoro butyl ester, 90g step (1) containing epoxy section prepolymer, 50g 2; 2 '-dipyridyl and 100g toluene mix; freezing through cryosel bath; vacuumize, repeat 3 bulging nitrogen; be warming up to 70 DEG C under nitrogen protection; add 0.9g cuprous bromide; maintaining nitrogen purge; reaction 2.5h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical.
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get the block polymer 100g containing epoxy and fluorin radical prepared by step (2), be dissolved in ethyl acetate with the triethylene tetramine of 54g, react 8h at 35 DEG C.By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent C3 that translucent solid is block structure.
(4) the fluorine-containing normal temperature epoxy solidifying agent C3 of the block structure using 8g step (3) to prepare mixes with 100g epoxy resin E51, solidifies one week, obtain epoxy resin cured product G3 at 15 DEG C.Distinguish the contact angle of Measurement and Computation G3, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
Embodiment 4
(1) containing the preparation of epoxy section prepolymer: 100g glycidyl allyl ether, 1.41g epoxy chloropropane, 5g pentamethyl-diethylenetriamine and 70g toluene are joined in the there-necked flask of band high speed agitator, thermometer and prolong; mix; freezing through cryosel bath; vacuumize, repeat drum 3 nitrogen; be warming up to 95 DEG C under nitrogen protection; add 3g cuprous bromide; maintaining nitrogen purge; reaction 3h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains containing epoxy section prepolymer.
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: that 100g Hexafluorobutyl mathacrylate monomer, 650g step (1) are prepared mixes containing epoxy section prepolymer, 5g pentamethyl-diethylenetriamine and 60g butanone; freezing through cryosel bath; vacuumize, repeat 3 bulging nitrogen; be warming up to 100 DEG C under nitrogen protection; add 0.9g iron protochloride; maintaining nitrogen purge; reaction 2.5h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical.
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get the block polymer 100g containing epoxy and fluorin radical prepared by step (2), be dissolved in butanone with the tetraethylene pentamine of 144g, react 10h at 35 DEG C.By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent C4 that translucent solid is block structure.
(4) the fluorine-containing normal temperature epoxy solidifying agent C4 of the block structure using 9g step (3) to prepare mixes with 100g epoxy resin E51, solidifies one week, obtain epoxy resin cured product G4 at 25 DEG C.Distinguish the contact angle of Measurement and Computation G4, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
Embodiment 5
(1) containing the preparation of epoxy section prepolymer: by 100g glycidyl methacrylate, 4.5g epoxy chloropropane, 5g 2; 2 '-dipyridyl and 70g butylacetate join in the there-necked flask of band high speed agitator, thermometer and prolong; mix; freezing through cryosel bath; vacuumize, repeat drum 3 nitrogen; be warming up to 90 DEG C under nitrogen protection; add 3.5g cuprous bromide; maintaining nitrogen purge; reaction 3.5h; product is through cold diethyl ether precipitation, and normal-temperature vacuum is dried to constant weight, obtains containing epoxy section prepolymer.
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: that 100g dodecafluorhe-ptylacrylate monomer, 60g step (1) are prepared mixes containing epoxy section prepolymer, 5.5g pentamethyl-diethylenetriamine and 90g butanone; freezing through cryosel bath; vacuumize, repeat 3 bulging nitrogen; be warming up to 110 DEG C under nitrogen protection; add 4.9g iron protochloride; maintaining nitrogen purge; reaction 20h; product precipitates through cold diethyl ether; normal-temperature vacuum is dried to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical.
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get the block polymer 100g containing epoxy and fluorin radical prepared by step (2), be dissolved in butylacetate with the diethylenetriamine of 27g, react 12h at 0 DEG C.By reaction mixture underpressure distillation, boil off solvent, residuum falls in furnace pot, is placed in vacuum-drying in baking oven, obtains the fluorine-containing normal temperature epoxy solidifying agent C5 that translucent solid is block structure.
(4) the fluorine-containing normal temperature epoxy solidifying agent C5 of the block structure using 10g step (3) to prepare mixes with 100g epoxy resin E51, solidifies one week, obtain epoxy resin cured product G5 at 30 DEG C.Distinguish the contact angle of Measurement and Computation G5, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
Comparative example 1
Use 10g solidifying agent diethylenetriamine (DETA) to mix with 100g epoxy resin E51, solidify one week at 30 DEG C, obtain epoxy resin cured product E1.Distinguish the contact angle of Measurement and Computation E1, tensile strength, elongation at break and resistance to impact shock, the results are shown in Table 1.
From the performance of coating in embodiment and comparative example, compared with common commercially available epoxy hardener, adopt and there is the fluorine-containing epoxy hardener that excellent durable, weather-proof, chemical-resistant fluorine-containing material make block structure, and with its cured epoxy resin at 0 ~ 50 DEG C, the performance of solidify material has remarkable lifting, thus reaches the effect of the technology of the present invention raising.
Table 1 uses the performance of curable epoxide thing prepared by solidifying agent of the present invention
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a fluorine-containing normal temperature epoxy solidifying agent for block structure, is characterized in that its structural formula is:
Wherein, R is H or carbonatoms is the alkyl of 1 ~ 10; R
1for H or-CH
3; X is
or-CH
2o-; Rf is carbon chain lengths is C
1~ C
10fluoro-alkyl, the integer of m=3 ~ 250; The integer of n=2 ~ 250; Y is the part removing NR in aliphatic polybasic amine structure.
2. the preparation method of the fluorine-containing normal temperature epoxy solidifying agent of block structure according to claim 1, is characterized in that comprising following concrete steps:
(1) containing the preparation of epoxy section prepolymer: by monomer, 0.3 ~ 40 mass parts epoxy chloropropane of 100 mass parts containing epoxy group(ing), 0.01 ~ 50 mass parts coordination agent and 0.5 ~ 100 mass parts organic solvent mix, cryosel bath is freezing, vacuumizes, leads to 3 ~ 5 nitrogen deoxygenations; Under nitrogen protection, be warming up to 60 ~ 120 DEG C, add 0.01 ~ 100 mass parts of catalyst, reaction 1.5 ~ 25h, product is through cold diethyl ether precipitation, and vacuum-drying, to constant weight, obtains containing epoxy section prepolymer;
(2) containing the preparation of the segmented copolymer of epoxy and fluorin radical: that 100 mass parts fluorochemical monomers, 20 ~ 650 mass parts steps (1) are prepared mixes containing epoxy section prepolymer, 0.01 ~ 50 mass parts coordination agent and 0.5 ~ 100 mass parts organic solvent, cryosel bath is freezing, vacuumizes, drum 3 ~ 5 nitrogen deoxygenations; Then under nitrogen protection, be warming up to 60 ~ 120 DEG C, add 0.01 ~ 100 mass parts of catalyst reaction 1.5 ~ 25h, product is through cold diethyl ether precipitation, and vacuum-drying, to constant weight, obtains the segmented copolymer containing epoxy and fluorin radical;
(3) preparation of the fluorine-containing normal temperature epoxy solidifying agent of block structure: get segmented copolymer 100 mass parts containing epoxy and fluorin radical prepared by step (2), add aliphatic polyamine 26 ~ 144 mass parts, react 8 ~ 12h at 0 ~ 35 DEG C; By reaction mixture underpressure distillation, boil off solvent, residuum vacuum-drying, obtain the fluorine-containing normal temperature epoxy solidifying agent that translucent solid is block structure.
3. preparation method according to claim 2, is characterized in that:
Described in step (1) is at least one in (methyl) glycidyl acrylate and glycidyl allyl ether containing the monomer of epoxy group(ing).
4. preparation method according to claim 2, is characterized in that:
Fluorochemical monomer described in step (2) is at least one in vinylformic acid trifluoro ethyl ester, trifluoroethyl methacrylate, vinylformic acid hexafluoro butyl ester, Hexafluorobutyl mathacrylate, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester, methacrylic acid-1H, 1H-perfluoro monooctyl ester and methacrylic acid 17 fluorine certain herbaceous plants with big flowers ester.
5. preparation method according to claim 2, is characterized in that:
Step (1) and the coordination agent described in (2) are the straight-chain paraffin of dipyridyl and derivative or many nitrogen.
6. preparation method according to claim 2, is characterized in that:
Step (1) and the organic solvent described in (2) are benzene class, heterocycle or ketone compounds.
7. preparation method according to claim 2, is characterized in that:
Step (1) and the catalyzer described in (2) are transition metal halide;
Step (1) and the vacuum drying condition described in (2) are carry out vacuum-drying under normal temperature.
8. preparation method according to claim 2, is characterized in that:
Aliphatic polyamine described in step (3) is at least one in triethylene tetramine, tetraethylene pentamine and diethylenetriamine.
9. the application in epoxy resin cured product prepared by the fluorine-containing normal temperature epoxy solidifying agent of block structure according to claim 1.
10. application according to claim 9, is characterized in that: the application in epoxy structural rubber, epoxy mortar or epoxy protective paint prepared by the fluorine-containing normal temperature epoxy solidifying agent of described block structure.
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| CN114031895A (en) * | 2021-11-15 | 2022-02-11 | 浙江豪德盛绝缘材料有限公司 | Preparation method of high-corrosion-resistance epoxy resin |
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| CN111848926B (en) * | 2020-07-02 | 2023-01-06 | 深圳飞扬骏研新材料股份有限公司 | Fluorine modified curing agent and preparation method thereof |
| CN114031895A (en) * | 2021-11-15 | 2022-02-11 | 浙江豪德盛绝缘材料有限公司 | Preparation method of high-corrosion-resistance epoxy resin |
| CN114031895B (en) * | 2021-11-15 | 2022-07-05 | 浙江豪德盛绝缘材料有限公司 | Preparation method of high-corrosion-resistance epoxy resin |
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