CN115010832A - Petroleum resin modified polyamine epoxy resin curing agent and preparation method thereof - Google Patents
Petroleum resin modified polyamine epoxy resin curing agent and preparation method thereof Download PDFInfo
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- CN115010832A CN115010832A CN202210883997.4A CN202210883997A CN115010832A CN 115010832 A CN115010832 A CN 115010832A CN 202210883997 A CN202210883997 A CN 202210883997A CN 115010832 A CN115010832 A CN 115010832A
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- 229920005989 resin Polymers 0.000 title claims abstract description 141
- 239000011347 resin Substances 0.000 title claims abstract description 141
- 239000003208 petroleum Substances 0.000 title claims abstract description 138
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 90
- 229920000768 polyamine Polymers 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 24
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 9
- 238000005336 cracking Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- 238000001833 catalytic reforming Methods 0.000 claims description 5
- 238000005504 petroleum refining Methods 0.000 claims description 5
- NKVCYHYQKKNFJI-UHFFFAOYSA-N 2-(hexacosan-13-yloxymethyl)oxirane Chemical compound CCCCCCCCCCCCCC(CCCCCCCCCCCC)OCC1CO1 NKVCYHYQKKNFJI-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 28
- 239000002131 composite material Substances 0.000 abstract description 9
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 238000007385 chemical modification Methods 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000010426 asphalt Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- 238000012986 modification Methods 0.000 description 12
- 230000004048 modification Effects 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- 239000004593 Epoxy Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011384 asphalt concrete Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000002464 physical blending Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- NVKSMKFBUGBIGE-UHFFFAOYSA-N 2-(tetradecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCCCOCC1CO1 NVKSMKFBUGBIGE-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- -1 alicyclic amine Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 1
- OKTJSMMVPCPJKN-BJUDXGSMSA-N carbon-11 Chemical compound [11C] OKTJSMMVPCPJKN-BJUDXGSMSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F240/00—Copolymers of hydrocarbons and mineral oils, e.g. petroleum resins
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Epoxy Resins (AREA)
Abstract
A preparation of petroleum resin modified polyamine epoxy resin curing agent, using raw material carbon 5 or carbon 9 fraction of carbon 5 or carbon 9 petroleum resin as main body, adding allyl glycidyl ether in the process of preparing petroleum resin, using the reaction of double bond on the allyl glycidyl ether and active substance containing double bond in the carbon 5 or carbon 9 fraction, making the allyl glycidyl ether participate in the synthesis of petroleum resin, further introducing epoxy group on the molecule of petroleum resin, generating allyl glycidyl ether modified petroleum resin; epoxy groups on allyl glycidyl ether modified petroleum resin molecules can react with amino groups on polyamine end-capping substances to generate the petroleum resin modified polyamine epoxy resin curing agent. The petroleum resin modified polyamine epoxy resin curing agent can perform curing reaction with epoxy resin to form a petroleum resin modified epoxy resin composite material, and the toughness of the epoxy resin material and the adhesion of the epoxy resin material with various base materials are improved in a chemical modification mode.
Description
Technical Field
The invention belongs to the technical field of epoxy resin modification, and relates to a petroleum resin modified polyamine epoxy resin curing agent and a preparation method thereof.
Background
Petroleum resin is an amorphous thermoplastic material generated by a byproduct of ethylene cracking through a certain polymerization reaction. Because the components of the cracked products are changed due to the changes of the depth, the process and the parameters of the ethylene cracking, the generated by-products comprise aromatic hydrocarbons, alkanes, alkenes and the like, and various components are more than 160. The petroleum resins can be classified into types of carbon 4, carbon 5, carbon 6, carbon 7, carbon 8, carbon 9, carbon 10, carbon 11, carbon 12, carbon 5/carbon 9 and the like according to the carbon number of the monomer, and the two types which are most widely applied are the petroleum resins of carbon 5 and carbon 9 respectively. Carbon 5 petroleum resins are commonly used in the fields of tackifiers, adhesives, road marking coatings, and the like; the carbon 9 petroleum resin is mainly applied to the fields of paint, coating, rubber modification and the like.
C 5 Or C 9 The fraction is a by-product of cracking to ethylene and catalytic reforming in petroleum refining, C 5 The fraction is a mixture of a plurality of substances containing four to six carbon atoms, generally comprising active components such as isoprene, cyclopentadiene, 1, 3-pentadiene, 1, 4-pentadiene and various types of monoolefins and other inactive components, and is synthesized C 5 Raw materials for petroleum resins; c 9 The distillate is a mixture of a plurality of substances containing eight to ten carbon atoms, generally comprises active components such as dimethyl styrene, dicyclopentadiene, methyl indene, styrene, indene and the like and other inactive components, and is a synthetic C 9 Raw materials for petroleum resins.
The products prepared by using the byproducts as raw materials can obtain various series of petroleum resins with different softening points, molecular weights and colors according to different synthesis methods. The polarity of the petroleum resin can be changed or the appearance of the petroleum resin can be improved by introducing a new functional group through chemical modification, so that byproducts are more effectively utilized, the additional value of the petroleum resin is increased, and an industrial chain is extended. Petroleum resin has properties similar to asphalt, is a thermoplastic resin of a complex mixture, is widely applied to the fields of coatings, tackifiers, printing ink rubber and the like, and is widely applied to the field of highway construction and maintenance, and because the petroleum resin is brown or brown, a cementing material formed by blending and modifying petroleum resin and chemical materials such as SBS modifiers is called 'colored asphalt' on the market, and the asphalt-like material is not colored or colorless per se, but is dark brown, so that the asphalt-like material is easier to dye compared with a black asphalt material. The colored asphalt concrete pavement can be prepared by matching with graded stone after dyeing, but the colored pavement is easy to fade and has poor high-temperature resistance, and the colored asphalt concrete pavement cannot be widely applied.
In the field of coatings, the petroleum resin can greatly improve the performance of the coatings, such as accelerating the drying rate of a coating film, improving the water resistance, acid resistance and alkali resistance of the coating film, and enhancing the surface hardness and gloss. In the field of tackifiers, petroleum resins have a very good tackifying effect, which is intended to provide adhesion. The addition of petroleum resin can improve the heat resistance and stability of the main components in the tackifier such as synthetic rubber, polyolefin, etc. In the field of printing ink, the petroleum resin has high softening point, good stability and good intermiscibility, and is applied to the preparation of printing ink.
Epoxy resin belongs to thermosetting polymer materials, and is widely applied to the fields of machinery, aerospace, automobiles and the like due to excellent chemical stability, heat resistance, corrosion resistance, electrical insulation and adhesion. However, epoxy resins have the disadvantages of high brittleness and poor impact resistance, and are prone to cracking, so that the application range of the epoxy resins is greatly limited, and thus the toughening modification of the epoxy resins becomes a research hotspot. The toughening of epoxy resin generally adopts the toughening of rubber elastomers, the toughening of nano inorganic fillers, the toughening of thermoplastic resin and the toughening of liquid crystal polymers, and the more common thermoplastic resin generally adopts materials such as polysulfone polymers, polyurethane and the like. The toughening modification method mainly adopts physical blending, and needs to form a stable uniform system by technical means such as high-speed stirring, shearing and the like for the epoxy resin and the toughening agent (toughening resin) to play a role in toughening modification.
Studies on modification of epoxy resins by chemical modification using petroleum resins as modifiers, Zheng Hao, in "preparation and modification of epoxy resins based on Petroleum resins", an active functional group-phenolic hydroxyl group was introduced into carbon 9 petroleum resins, and BF was used by cationic polymerization method 3 O(C 2 H 5 ) 2 The modified epoxy resin based on the carbon 9 petroleum resin is prepared by using epoxy chloropropane as a modifier to react with phenolic hydroxyl under the action of a catalyst to epoxidize the phenolic hydroxyl modified petroleum resin. The cured product has excellent mechanical properties including impact property, bending property, thermal stability and the like, but the preparation process is complex and the technological requirements are strict, and strictly speaking, the modification only introduces epoxy groups capable of reacting with the epoxy curing agent on the petroleum resin and is not epoxy resin in the real sense, and the physical and chemical properties of the whole epoxy resin can not be achieved by only depending on individual epoxy groups.
The invention patent of reactive normal temperature color asphalt and a preparation method and application thereof (201810921193.2) discloses reactive normal temperature color asphalt and a preparation method and application thereof, comprising petroleum resin, a reactive solvent, a coupling agent, water-based epoxy resin and pigment. In the patent, petroleum resin and waterborne epoxy resin are modified mutually, but only on the basis of physical blending modification of two materials. The reaction type solvent in the invention has the main function of liquefying the petroleum resin, so that the petroleum resin has fluidity at normal temperature, and simultaneously, the petroleum resin can be better mixed with other components such as water-based epoxy resin and the like. The coupling agent can combine inorganic substances and organic substances to generate molecular chains with an integral structure. The petroleum resin and the epoxy resin do not have chemical reaction, and the coupling agent has the possibility of forming relevant connection between the resins or reactive solvents, but is also a technology for blending and modifying the petroleum resin and the epoxy resin. The performances of the material disclosed by the invention depend on the blending uniformity of the material, and because no corresponding stable chemical bond connection exists between the epoxy resin and the petroleum resin, the material is easy to be layered or separated out, and the overall performance of the material is influenced.
The invention patent of cold-mixing type colorful epoxy asphalt, compatilizer and preparation method (201910701563.6) discloses cold-mixing type colorful epoxy asphalt, compatilizer and preparation method. The cold-mixing type colored epoxy asphalt comprises a component A: colored asphalt, cold-mixing type colored asphalt compatilizer and modified epoxy resin; and B component: the cold mixing type epoxy asphalt composite curing agent. The cold-mixing type color asphalt compatilizer is prepared from base oil, a functional grafting agent and an initiator, and the cold-mixing type epoxy asphalt composite curing agent is prepared from at least two of aliphatic polyamine curing agent, polythiol curing agent, polyisocyanate curing agent, alicyclic amine curing agent, aromatic amine curing agent, low-molecular polyamide curing agent, tertiary amine curing agent, modified aromatic amine curing agent and resin curing agent. Although the invention patent synthesizes a compatilizer by utilizing base oil, a functional grafting agent and an initiator, the compatilizer only simply increases the compatibility between the petroleum resin and the epoxy resin on the basis of physical blending modification on the modification of the petroleum resin and the epoxy resin, and the three are not chemically connected. The cold-mixing type epoxy asphalt composite curing agent disclosed in the patent only lists the conventional epoxy resin curing agent, and only can perform curing reaction with epoxy resin, and the epoxy resin and petroleum resin are physically blended and modified integrally.
The epoxy resin and the petroleum resin are modified into a whole in a chemical modification mode, so that the defect of physical blending modification on material compatibility can be avoided, the materials can be prevented from being separated out and isolated due to the connection of chemical bonds, the manufacturing cost of the epoxy resin composite material is effectively reduced, the toughness of the modified epoxy resin composite material and the cohesiveness of the modified epoxy resin composite material to various base materials are greatly improved, and the modified epoxy resin composite material can be widely applied to the fields of building exterior wall coatings, pavement marking coatings, colored pavement anti-skid coatings and the like.
Disclosure of Invention
In order to make up the defects of the existing petroleum resin and epoxy resin materials, the invention provides a petroleum resin modified polyamine epoxy resin curing agent.
The technical scheme adopted by the invention is as follows: a petroleum resin modified polyamine epoxy resin curing agent comprises the following components in parts by mass: prepared by the reaction of modified petroleum resin and polyamine end-capping compound;
wherein: modified petroleum resin consisting of 5 Fraction or C 9 38-62 parts of fraction, 25 parts of solvent, 0.5-0.6 part of azodiisobutyronitrile and 3-12 parts of allyl glycidyl ether;
the polyamine end-capping material is prepared by reacting 3-11 parts of diethylenetriamine, 3-13 parts of triethylenetetramine, 3-13 parts of m-xylylenediamine, 5-15 parts of butyl glycidyl ether or 7-20 parts of dodecyl-tetradecyl glycidyl ether.
The preparation method of the petroleum resin modified polyamine epoxy resin curing agent comprises the following steps:
the first step is as follows: preparation of modified petroleum resin
38 to 62 portions of C 5 Fraction or C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, and controlling the temperature of the reaction kettleThe temperature is 70-80 ℃, the aromatic hydrocarbon fraction is completely dissolved by stirring, then 0.5-0.6 part of azodiisobutyronitrile is added at the reaction temperature of 70-80 ℃, 3-12 parts of allyl glycidyl ether is dripped after the reaction is controlled to be finished within 3 hours, and then the reaction is continued for 1 hour to prepare the modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 3-11 parts of diethylenetriamine or 3-13 parts of triethylene tetramine or 3-13 parts of m-xylylenediamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dripping 5-15 parts of butyl glycidyl ether or 7-20 parts of dodecyl-to-tetradecyl glycidyl ether into the reaction kettle in a dripping mode while stirring, controlling the dripping within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.05-0.32 mol/100 g.
Preferably, said C 5 The fraction is a mixture of several substances containing four to six carbon atoms, and is a by-product of cracking to prepare ethylene and catalytic reforming process in petroleum refining, and is synthetic C 5 Raw materials for petroleum resins.
Preferably, said C 9 The fraction is a mixture of several substances containing eight to ten carbon atoms, and is a by-product of cracking to prepare ethylene and catalytic reforming process in petroleum refining, and is synthesized C 9 Raw materials for petroleum resins.
Preferably, the solvent refers to an organic solvent having a boiling point higher than 80 ℃ under normal pressure.
Preferably, said C 5 The petroleum resin is C 5 The fraction is polymerized to produce a thermoplastic resin with an amorphous structure.
Preferably, the first and second electrodes are formed of a metal,said C is 9 The petroleum resin is C 9 The fraction is polymerized to produce a thermoplastic resin with an amorphous structure.
The invention has the following advantages and positive effects:
the method takes raw material carbon 5 or carbon 9 fraction of synthetic carbon 5 or carbon 9 petroleum resin as a main body, allyl glycidyl ether is added in the process of preparing the petroleum resin, the allyl glycidyl ether participates in the synthesis of the petroleum resin by utilizing the reaction of double bonds on the allyl glycidyl ether and active substances containing double bonds in the carbon 5 or carbon 9 fraction, and then epoxy groups are introduced into the molecules of the petroleum resin to generate allyl glycidyl ether modified petroleum resin; epoxy groups on allyl glycidyl ether modified petroleum resin molecules can react with amino groups on polyamine end-capping substances to generate the petroleum resin modified polyamine epoxy resin curing agent. The modification method is simple, has low requirements on process conditions, and is suitable for mass production.
The petroleum resin modified polyamine epoxy resin curing agent can perform curing reaction with epoxy resin, and petroleum resin is introduced into an epoxy resin system in a chemical modification mode to form a uniform and stable petroleum resin modified epoxy resin composite material which has excellent toughness and cohesiveness to various base materials.
Application performance comparison
The petroleum resin modified polyamine epoxy resin curing agent can effectively improve the toughness and weather resistance of an epoxy resin material after curing, and the cohesiveness of the epoxy resin material with an asphalt base material and a cement base material, and can be widely applied to the fields of building exterior wall coatings, pavement marking coatings, color pavement anti-skid coatings and the like.
Bitumen has been used for over a century in the highway field and has been the primary road-building adhesive to date. The adhesion performance of asphalt and gravel is one of the key factors affecting the application performance and the service life of asphalt concrete pavements. The judgment of the adhesion of the asphalt and the aggregate uses a T0616-1993 adhesion test of the asphalt and the coarse aggregate, and the method is used for testing the adhesion of the asphalt and the surface of the coarse aggregate and evaluating the water stripping resistance of the coarse aggregate. After the color adhesive is paved on a road surface, the mechanical property is reduced along with the prolonging of the service time under the influence of natural light, damp and hot weather, ultraviolet irradiation and the like. Therefore, the change of the bonding performance of the cementing material under the action of environmental factors, particularly rain, high temperature and the like, is directly related to the road performance and the service life of the pavement layer, and has very important practical significance.
With reference to this method, adhesion tests can be carried out on road markings, coatings of the anti-slip type, to judge their adhesion performance under particular conditions.
Polyurethane road surface anti-skid paint (hereinafter referred to as paint A), epoxy resin road surface anti-skid paint (hereinafter referred to as paint B) and acrylic road surface anti-skid paint (hereinafter referred to as paint C) are used as a comparison group, and compared with petroleum resin modified epoxy resin road surface anti-skid paint (hereinafter referred to as paint D) formed by curing petroleum resin modified polyamine epoxy resin curing agent and epoxy resin, the results are as follows:
table 1: performance test meter for various road surface anti-skid coatings
From the above data analysis, it is found that the epoxy resin material (D coating material) after the modification with the petroleum resin has a low tensile strength to the asphalt concrete base material and a high adhesive strength to the cement concrete base material, but has a significant improvement in the adhesive property to the asphalt base material, though the adhesive strength to the cement concrete base material is reduced. According to an adhesion test, the D coating shows higher adhesion performance and has higher water stripping resistance. The paint A, the paint B and the paint D have good ultraviolet resistance, while the paint C has obvious apparent cracking and decoloration. And (4) evaluating modes such as various data, indexes and the like in the comprehensive table D are optimized for comprehensive application performance of the coating. The data in the comprehensive table show that the D coating has relatively excellent comprehensive application performance.
The curing agent can effectively improve the toughness and weather resistance of the cured epoxy resin material and the cohesiveness of the cured epoxy resin material with asphalt base materials and cement base materials, and can be widely applied to the fields of building exterior wall coatings, pavement marking coatings, colored pavement anti-skid coatings and the like.
Detailed Description
The following describes a specific embodiment of the present invention.
Example 1
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
38 parts of C 5 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.5 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 12 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 11 parts of diethylenetriamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dripping 15 parts of butyl glycidyl ether into the reaction kettle in a dripping mode while stirring, controlling the dripping to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.32mol/100 g.
Example 2
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
43 parts of C 5 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, and stirring to distill the aromatic hydrocarbonCompletely dissolving, adding 0.5 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then dropwise adding 10 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuously reacting for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 10 parts of diethylenetriamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dripping 13 parts of butyl glycidyl ether into the reaction kettle in a dripping mode while stirring, controlling the dripping to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.29mol/100 g.
Example 3
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
Mixing 48 parts of C 5 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.5 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 8 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 8 parts of diethylenetriamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dripping 11 parts of butyl glycidyl ether into the reaction kettle in a dripping mode while stirring, controlling the dripping to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.23mol/100 g.
Example 4
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
50 portions of C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.6 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 5 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 6 parts of triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding 14 parts of carbon-dodecyl-carbon-tetradecyl glycidyl ether into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.16mol/100 g.
Example 5
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
54 parts of C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.6 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 4 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 5 parts of triethylene tetramine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding 12 parts of carbon-dodecyl-carbon-tetradecyl glycidyl ether into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.14mol/100 g.
Example 6
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
Mixing 58 parts of C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.6 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 4 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 4 parts of m-xylylenediamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding 9 parts of C-dodecyl-C-tetradecyl glycidyl ether into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.06mol/100 g.
Example 7
Preparation of petroleum resin modified polyamine epoxy resin curing agent
The first step is as follows: preparation of modified petroleum resin
62 portions of C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.6 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 3 parts of allyl glycidyl ether, controlling the time for dripping to be 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step: preparation of polyamine end-caps
Adding 3 parts of m-xylylenediamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding 7 parts of carbon dodecyl to carbon tetradecyl glycidyl ether into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.05mol/100 g.
Claims (7)
1. A petroleum resin modified polyamine epoxy resin curing agent is characterized in that: the composition comprises the following components in parts by mass: prepared by the reaction of modified petroleum resin and polyamine end capping compound;
wherein: modified petroleum resin consisting of 5 Fraction or C 9 38-62 parts of fraction, 25 parts of solvent, 0.5-0.6 part of azodiisobutyronitrile and 3-12 parts of allyl glycidyl ether;
the polyamine end-capping material is prepared by reacting 3-11 parts of diethylenetriamine, 3-13 parts of triethylenetetramine, 3-13 parts of m-xylylenediamine, 5-15 parts of butyl glycidyl ether or 7-20 parts of dodecyl-tetradecyl glycidyl ether.
2. The method for preparing a petroleum resin modified polyamine epoxy resin curing agent according to claim 1, wherein the curing agent comprises: comprises the following steps:
the first step is as follows: preparation of modified petroleum resin
38 to 62 portions of C 5 Fraction or C 9 Adding the distillate and 25 parts of solvent into a reaction kettle, controlling the temperature of the reaction kettle to be 70-80 ℃, stirring to completely dissolve the aromatic hydrocarbon distillate, adding 0.5-0.6 part of azodiisobutyronitrile at the reaction temperature of 70-80 ℃, then beginning to dropwise add 3-12 parts of allyl glycidyl ether, controlling the addition to be finished within 3 hours, and then continuing to react for 1 hour to prepare modified petroleum resin;
the second step is that: preparation of polyamine end-caps
Adding 3-11 parts of diethylenetriamine or 3-13 parts of triethylene tetramine or 3-13 parts of m-xylylenediamine into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dripping 5-15 parts of butyl glycidyl ether or 7-20 parts of dodecyl-to-tetradecyl glycidyl ether into the reaction kettle in a dripping mode while stirring, controlling the dripping within 1 hour, and then stirring for 2.5-3 hours to prepare a polyamine end-capping substance;
the third step: preparation of petroleum resin modified polyamine epoxy resin curing agent
And adding the polyamine end-capping material obtained in the second step into a reaction kettle, controlling the temperature of the reaction kettle to be 60-70 ℃, slowly dropwise adding the modified petroleum resin obtained in the first step into the reaction kettle in a dropwise adding mode while stirring, controlling the dropwise adding to be finished within 1 hour, and then stirring for 2.5-3 hours to prepare the petroleum resin modified polyamine epoxy resin curing agent with the amine value of 0.05-0.32 mol/100 g.
3. The petroleum resin modified polyamine epoxy resin curing agent according to claim 1, wherein: said C is 5 The fraction is a mixture of several substances containing four to six carbon atoms, and is a by-product of cracking to prepare ethylene and catalytic reforming process in petroleum refining, and is synthetic C 5 Raw materials for petroleum resins.
4. The petroleum resin modified polyamine epoxy resin curing agent according to claim 1, wherein: said C is 9 The fraction is a mixture of several substances containing eight to ten carbon atoms, is a by-product of cracking to prepare ethylene and catalytic reforming process in petroleum refining, and is synthetic C 9 Raw materials for petroleum resins.
5. The petroleum resin modified polyamine epoxy resin curing agent according to claim 1, wherein: the solvent is an organic solvent with the boiling point higher than 80 ℃ under normal pressure.
6. The petroleum resin modified polyamine epoxy resin curing agent according to claim 3, wherein: said C is 5 The petroleum resin means C 5 The fraction is polymerized to produce a thermoplastic resin with an amorphous structure.
7. The petroleum resin modified polyamine epoxy resin curing agent according to claim 4, wherein: said C is 9 The petroleum resin means C 9 The fraction is polymerized to produce a thermoplastic resin with an amorphous structure.
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| GB1403214A (en) * | 1971-07-24 | 1975-08-28 | Hoechst Ag | Telomers |
| CN102250320A (en) * | 2011-05-27 | 2011-11-23 | 天津大学 | Preparation method of modified epoxy resin curing agent and epoxy varnish paint |
| CN104877111A (en) * | 2015-04-28 | 2015-09-02 | 中科院广州化学有限公司 | Fluorine-containing epoxy curing agent capable of normal-temperature curing, and preparation and application thereof |
| CN113980248A (en) * | 2021-10-22 | 2022-01-28 | 江苏扬农锦湖化工有限公司 | Water-based epoxy curing agent and preparation method and application thereof |
-
2022
- 2022-07-26 CN CN202210883997.4A patent/CN115010832B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1403214A (en) * | 1971-07-24 | 1975-08-28 | Hoechst Ag | Telomers |
| CN102250320A (en) * | 2011-05-27 | 2011-11-23 | 天津大学 | Preparation method of modified epoxy resin curing agent and epoxy varnish paint |
| CN104877111A (en) * | 2015-04-28 | 2015-09-02 | 中科院广州化学有限公司 | Fluorine-containing epoxy curing agent capable of normal-temperature curing, and preparation and application thereof |
| CN113980248A (en) * | 2021-10-22 | 2022-01-28 | 江苏扬农锦湖化工有限公司 | Water-based epoxy curing agent and preparation method and application thereof |
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