CN114773579A - Solvent-free epoxy curing agent and preparation method thereof - Google Patents
Solvent-free epoxy curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN114773579A CN114773579A CN202210619814.8A CN202210619814A CN114773579A CN 114773579 A CN114773579 A CN 114773579A CN 202210619814 A CN202210619814 A CN 202210619814A CN 114773579 A CN114773579 A CN 114773579A
- Authority
- CN
- China
- Prior art keywords
- polyamine
- mass ratio
- curing agent
- accelerator
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 73
- 239000004593 Epoxy Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims description 34
- 229920000768 polyamine Polymers 0.000 claims abstract description 46
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000012745 toughening agent Substances 0.000 claims description 58
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 44
- 239000004200 microcrystalline wax Substances 0.000 claims description 38
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000010451 perlite Substances 0.000 claims description 35
- 235000019362 perlite Nutrition 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 239000004033 plastic Substances 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 22
- 239000003093 cationic surfactant Substances 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 17
- 229930195729 fatty acid Natural products 0.000 claims description 17
- 239000000194 fatty acid Substances 0.000 claims description 17
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 14
- 239000012188 paraffin wax Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000004203 carnauba wax Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920001732 Lignosulfonate Polymers 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- JPIJQSOTBSSVTP-UHFFFAOYSA-N 2,3,4-trihydroxybutanoic acid Chemical compound OCC(O)C(O)C(O)=O JPIJQSOTBSSVTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 239000012966 redox initiator Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000012874 anionic emulsifier Substances 0.000 claims description 9
- 230000001804 emulsifying effect Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 229920005610 lignin Polymers 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000012875 nonionic emulsifier Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 40
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 alicyclic amine Chemical class 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004848 polyfunctional curative Substances 0.000 description 5
- BYQADQLDVPAGSR-UHFFFAOYSA-N toluene;hydrobromide Chemical compound Br.CC1=CC=CC=C1 BYQADQLDVPAGSR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000007942 carboxylates Chemical group 0.000 description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RLUJQBLWUQZMDG-UHFFFAOYSA-N toluene;hydrochloride Chemical group Cl.CC1=CC=CC=C1 RLUJQBLWUQZMDG-UHFFFAOYSA-N 0.000 description 3
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229920006334 epoxy coating Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
- C08G59/5033—Amines aromatic
-
- 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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
-
- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a solventless epoxy curing agent, which comprises 50-100 parts of benzyl polyamine, 20-50 parts of polyamine-epoxy adduct and 0-20 parts of accelerator. The solvent-free epoxy curing agent provided by the invention effectively improves the comprehensive performance of the curing agent by combining the amine curing main body and other auxiliary components in the curing agent.
Description
Technical Field
The invention belongs to the technical field of chemical coatings, and particularly relates to a solvent-free epoxy curing agent and a preparation method thereof.
Background
Epoxy resin is a linear thermoplastic high molecular polymer, and uncured epoxy resin has no good mechanical property, chemical resistance and heat resistance. However, good performance can be obtained by reacting a linear epoxy resin with a suitable curing agent to form a three-dimensionally crosslinked thermoset structure, a process commonly referred to as curing or gelling of the epoxy resin, and thus the curing agent is critical to the practical utility of the epoxy resin.
Epoxy curing agents can be classified into solvent-based and solventless types. The solvent type epoxy curing agent is mainly insoluble in water due to the structure of epoxy resin, and organic solvents such as benzene, ketone, aromatic hydrocarbon and the like are required to be added as diluents, so that the solvent type epoxy curing agent has a strong smell and is easy to volatilize, and the solvent type epoxy curing agent causes great pollution to the surrounding environment. With the increasing environmental protection requirement, the solvation-free, high solid content and water-based performances of the epoxy curing agent are more and more emphasized.
At present, the research aiming at the solvent-free epoxy curing agent mainly focuses on the modification of the main curing amine, but neglects the influence of other components in the curing agent on the performance of the curing agent. For example, the flexibilizer can effectively improve the flexibility of the cured product, and the accelerator can not only reduce the reaction temperature and shorten the reaction time, but also improve the mechanical property of the cured product.
In summary, how to provide a solventless epoxy curing agent and a preparation method thereof, which effectively improve the comprehensive performance of the curing agent by combining an amine curing main body and other auxiliary components in the curing agent, is a problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the technical problems and provides a solvent-free epoxy curing agent and a preparation method thereof, wherein an amine curing main body, a toughening agent and an accelerator in the curing agent are respectively designed, so that the comprehensive performance of the curing agent can be effectively improved.
The invention achieves the above objects by the following technical means,
a solvent-free epoxy curing agent comprises the following raw materials in parts by weight: 50-100 parts of benzyl polyamine, 20-50 parts of polyamine-epoxy adduct and 0-20 parts of accelerator.
The preparation method of the benzyl polyamine comprises the following steps: adding polyamine, water, metal hydroxide and fatty alcohol into a four-mouth reaction bottle, slowly dropwise adding toluene monohalide in the nitrogen atmosphere, heating to 40-80 ℃ for reaction for 1-10h, filtering after the reaction is finished, performing oil-water separation, and performing reduced pressure distillation to obtain the benzyl polyamine.
Wherein the metal hydroxide is one of potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide and barium hydroxide.
The fatty alcohol is one of methanol, ethanol, propanol, isopropanol, n-butanol, and isobutanol.
The toluene monohalide is toluene monochloride or toluene monobromide.
Further, the accelerator is selected from one of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, triethylamine, triethanolamine and o-hydroxybenzyldimethylamine, and the molar ratio of the polyamine, the metal hydroxide, the fatty alcohol and the toluene monohalide is 1: (0.8-1.2): (2-6): (0.7-0.9), wherein the mass ratio of the metal hydroxide to the water is 1: (3-5).
Further, the preparation method of the polyamine-epoxy resin adduct comprises the following steps: adding polyamine into a four-mouth reaction bottle, slowly dropwise adding epoxy resin in the nitrogen atmosphere, heating to 40-80 ℃, reacting for 1-6h, and obtaining polyamine-epoxy resin addition product after the reaction is finished; the mass ratio of the polyamine to the epoxy resin is 1: (0.8-1.8).
The epoxy resin is selected from one of bisphenol A type glycidyl ether, bisphenol F type glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, C12-C14 glycidyl ether and cardanol glycidyl ether.
All the polyamines are one or more of aliphatic amine, alicyclic amine and aromatic amine compounds containing two primary amine groups.
The invention also provides a pretreatment method of the accelerator in the solvent-free epoxy curing agent, which comprises the following steps:
(1) adding paraffin and palm wax into a solvent (40-50 ℃) and uniformly mixing, then adding a cationic surfactant and uniformly mixing to obtain an oil phase for later use;
(2) preheating an accelerant (50-60 ℃), and then dropwise adding the accelerant into the oil phase obtained in the step (1) under the condition of stirring (2000-3000 r/min) to obtain an emulsion;
(3) and (3) dispersing the emulsion in a dispersion machine (400-600 r/min), and simultaneously heating (65-75 ℃) to evaporate the solvent to dryness, thereby completing the pretreatment of the accelerator.
Further, in the step (1), the melting point of the paraffin is 50-60 ℃, the solvent is petroleum ether (the boiling point is 60-70 ℃) or trichloromethane, and the mass ratio of the paraffin, the palm wax, the solvent and the cationic surfactant is 1: (2-3): (4-8): (0.6-1.6); in the step (2), the mass ratio of the accelerator to the oil phase is 1: (2-4).
Further, the preparation method of the cationic surfactant comprises the following steps: uniformly mixing fatty acid, benzene and concentrated sulfuric acid in a reaction kettle, then dripping 2,3, 4-trihydroxy butyric acid, reacting for 8-16h under the condition of heating (80-90 ℃) and stirring, then dripping mixed solution of anhydrous citric acid and thionyl chloride, reacting for 6-10h under the condition of heating (80-90 ℃) and stirring, adding 3-6 times of deionized water into the obtained product, adding ammonium bicarbonate after uniformly mixing for neutralization reaction, and filtering and removing impurities to obtain the cationic surfactant; wherein the molar ratio of the fatty acid, the 2,3, 4-trihydroxy butyric acid and the anhydrous citric acid is (3-3.3): 1: (1-1.4), the adding amount of concentrated sulfuric acid is 2-3% of fatty acid, the adding amount of thionyl chloride is 0.5-1.5% of anhydrous citric acid, and the fatty acid is long-chain fatty acid.
The invention also provides a toughening agent used in the solvent-free epoxy curing agent, the mass part of the toughening agent in the curing agent is 10-20 parts, the toughening agent is of a core-shell structure and sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, and the mass ratio of the toughening agent to the plastic layer is 1: (1-2): (3-5): (1-3).
Further, the perlite micro powder core is prepared from the following raw materials in a mass ratio of 1: (0.1-0.3) perlite micropowder and silane coupling agent; the microcrystalline wax layer is prepared from the following raw materials in a mass ratio of 1: (0.15-0.3) microcrystalline wax, an anionic emulsifier; the rubber layer is prepared from the following raw materials in mass ratio of 1: (0.4-0.6): (0.2-0.4): (0.06-0.1) styrene, butadiene, diallylamine, azobisisobutyramidine hydrochloride; the plastic layer is prepared from the following raw materials in a mass ratio of 1: (0.3-0.5): (1-1.6): (0.05-0.1) styrene, 3, 4-epoxy-1-butylene, methyl methacrylate and a redox initiator.
Further, the preparation method of the toughening agent comprises the following steps:
s1, adding 5-10 times of water and a silane coupling agent into the perlite micro powder, stirring and soaking for 30-60min, and evaporating water to obtain perlite micro powder kernels;
s2, uniformly stirring the microcrystalline wax and the anionic emulsifier, putting the mixture into an emulsifying machine (the emulsifying temperature is 85-95 ℃, and the stirring speed is 2500-3500 r/min), and adding 10-20 times of deionized water for emulsification to obtain microcrystalline wax emulsion;
s3, placing the perlite micro powder core and the microcrystalline wax emulsion in a dispersion machine at the temperature of 110-120 ℃ for dispersion until water is volatilized, and obtaining a microcrystalline wax layer;
s4, adding a nonionic emulsifier (the addition amount is 10-16% of deionized water), deionized water (the addition amount is 10-20 times of all raw materials) and the material obtained in the step S3 into a reaction kettle, uniformly stirring, adding monomer styrene, butadiene and diallylamine, stirring to emulsify the monomer, adding a cationic initiator azobisisobutyramidine hydrochloride ATNA, and reacting at 60-65 ℃ for 8-12 hours to obtain a rubber layer;
s5, adding monomer styrene, 3, 4-epoxy-1-butylene and methyl methacrylate into the material obtained in the step S4, stirring to emulsify the monomer, adding a redox initiator, and reacting at 50-60 ℃ for 3-5h to obtain a plastic layer;
s6, freezing and demulsifying the material obtained in the step S5, washing, filtering, and drying in vacuum to obtain the finished product of the toughening agent.
In step S1, the perlite micropowder has a particle size of 5-10 μm and a bulk density of 40-70kg/m3。
In step S2, the melting point of the microcrystalline wax is 65-75 ℃, and the anionic emulsifier is carboxylate or sulfonate.
In step S4, the nonionic emulsifier is a fatty alcohol polyoxyethylene ether series, an isomeric tridecanol polyoxyethylene ether series, or an alkylphenol polyoxyethylene ether series.
In step S5, the redox initiator is benzoyl peroxide/N, N-dimethylaniline, ammonium persulfate/sodium bisulfite, cumene hydroperoxide/tetraethylene imine or tert-butyl hydroperoxide/sodium metabisulfite.
The invention also provides a preparation method of the solvent-free epoxy curing agent, which comprises the following steps:
A. placing the pretreated accelerator and the nano lignin powder in a disperser at 30-40 ℃ for dispersing for 1-2 hours to obtain a first material;
B. uniformly mixing lignosulfonate, sodium silicate and water, adding a toughening agent in an amount which is 0.2-0.4 times that of the lignosulfonate, soaking for 30-50min, heating and volatilizing to obtain a second material;
C. uniformly mixing benzyl polyamine and polyamine-epoxy adduct according to the mass parts, and then adding the material I and the material II to obtain a curing agent;
wherein the mass ratio of the accelerator pretreated in the step A to the nano lignin powder is 1: (0.03-0.06), wherein the mass ratio of the lignosulfonate, the sodium silicate and the water in the step B is 1: (0.1-0.4): (3-5).
The invention has the beneficial effects that:
(1) in the preparation process of the curing agent, benzyl polyamine is selected to introduce benzene ring groups, so that the temperature resistance and the chemical resistance of the product can be improved.
(2) The accelerator is added, and is pretreated by paraffin and palm wax, so that the stability of the accelerator can be improved, the accelerator can exert the accelerating effect only during heating and curing, the dispersion effect of the accelerator in the curing agent is improved, and the curing performance of the curing agent is improved.
(3) The cationic surfactant with the multiple lipophilic branched chains is prepared, and can promote the aggregation of paraffin and palm wax in emulsion on the surfaces of accelerator droplets, so that the pretreatment of the accelerator is completed.
(4) The toughening agent disclosed by the invention adopts a core-shell structure, sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, wherein the perlite micro powder core is a hard core and can be expanded in a heat absorption manner, the microcrystalline wax layer is low in softening point and has ductility, and the rubber layer and the plastic layer are combined, so that the toughening effect can be comprehensively improved.
(5) The perlite micro powder core can be well combined with the organic microcrystalline wax layer after being treated by the silane coupling agent, and then the anionic emulsifier is added in the preparation of the microcrystalline wax layer, so that the perlite micro powder core can be adsorbed by the cationic initiator, and the formation of the rubber layer on the surface of the microcrystalline wax layer is promoted.
(6) The raw material for preparing the rubber layer of the toughening agent comprises diallyl amine, the raw material for preparing the plastic layer comprises 3, 4-epoxy-1-butylene, so that the combination of the rubber layer and the plastic layer is promoted, the shell plastic with epoxy groups is formed, and the compatibility of the toughening agent and a toughened matrix (epoxy resin) is improved.
(7) Because the surface of the toughening agent is a hard shell, the pretreated accelerator is easy to damage due to violent collision, and the toughening agent and the pretreated accelerator are respectively subjected to surface treatment, so that the toughening agent and the pretreated accelerator are charged the same to generate repulsion, thereby avoiding mutual influence of the toughening agent and the pretreated accelerator and being beneficial to dispersion.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
This example provides a solventless epoxy curing agent, which comprises 50 parts by weight of benzyl polyamine and 20 parts by weight of polyamine-epoxy adduct. The curing agent is prepared by directly mixing the raw materials.
The preparation method of the benzyl polyamine comprises the following steps: adding polyamine, water, potassium hydroxide and methanol into a four-mouth reaction bottle, slowly dropwise adding toluene monochloride in the nitrogen atmosphere, heating to 40 ℃ for reaction for 1h, filtering after the reaction is finished, carrying out oil-water separation, and carrying out reduced pressure distillation to obtain the benzyl polyamine. The molar ratio of polyamine, potassium hydroxide, fatty alcohol and toluene monochloride is 1: 0.8: 2: 0.7, wherein the mass ratio of potassium hydroxide to water is 1: 3.
the preparation method of the polyamine-epoxy resin adduct comprises the following steps: adding polyamine into a four-mouth reaction bottle, slowly dropwise adding bisphenol A type glycidyl ether in the nitrogen atmosphere, heating to 40 ℃, reacting for 1h, and obtaining polyamine-epoxy resin addition product after the reaction is finished; the mass ratio of polyamine to bisphenol A glycidyl ether is 1: 0.8.
all the polyamines are one or more of aliphatic amine, alicyclic amine and aromatic amine compounds containing two primary amine groups.
Example 2
On the basis of embodiment 1, the embodiment also provides a toughening agent for a solvent-free epoxy curing agent, wherein the toughening agent comprises 10 parts by mass of the curing agent, the toughening agent sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, and the mass ratio of the toughening agent to the plastic layer is 1: 1: 3: 1.
the preparation method of the toughening agent comprises the following steps:
s1, taking perlite micropowder (the granularity is 5 mu m, and the bulk density is 40 kg/m)3) Adding 5 times of water and a silane coupling agent, stirring and soaking for 30min, and then evaporating water to obtain perlite micro powder kernels; wherein the mass ratio of the perlite micropowder to the silane coupling agent is 1: 0.1;
s2, mixing the raw materials according to the mass ratio of 1: 0.15, uniformly stirring the microcrystalline wax (the melting point is 65 ℃) and the carboxylate anionic emulsifier, putting the mixture into an emulsifying machine (the emulsifying temperature is 85 ℃, and the stirring speed is 2500 r/min), and adding 10 times of deionized water for emulsification to obtain microcrystalline wax emulsion;
s3, placing the perlite micro powder core and the microcrystalline wax emulsion in a dispersion machine at 110 ℃ for dispersion until water is volatilized, and obtaining a microcrystalline wax layer;
s4, adding a nonionic emulsifier (fatty alcohol-polyoxyethylene ether series, the addition amount of which is 10 percent of that of deionized water), deionized water (the addition amount of which is 10 times of that of all raw materials) and the material obtained in the step S3 into a reaction kettle, uniformly stirring, and then mixing according to a mass ratio of 1: 0.4: 0.2 adding monomers of styrene, butadiene and diallylamine, stirring to emulsify the monomers, adding a cationic initiator of azodiisobutyl amidine hydrochloride (the addition amount is 0.06 time of that of the styrene), and reacting for 8 hours at 60 ℃ to obtain a rubber layer;
s5, adding the raw materials obtained in the step S4 into the mixture according to the mass ratio of 1: 0.3: 1 adding monomer styrene, 3, 4-epoxy-1-butylene and methyl methacrylate, stirring to emulsify the monomer, adding a redox initiator (benzoyl peroxide/N, N-dimethylaniline, the addition amount is 0.05 time of the styrene), and reacting for 3 hours at 50 ℃ to obtain a plastic layer;
s6, freezing and demulsifying the material obtained in the step S5, washing, filtering, and drying in vacuum to obtain the finished product of the toughening agent.
The rest is the same as in example 1.
Example 3
This example provides a solventless epoxy curing agent, which comprises 75 parts by weight of benzyl polyamine, 35 parts by weight of polyamine-epoxy adduct, and 10 parts by weight of 2,4, 6-tris (dimethylaminomethyl) phenol.
The preparation method of the benzyl polyamine comprises the following steps: adding polyamine, water, sodium hydroxide and ethanol into a four-mouth reaction bottle, slowly dropwise adding toluene monobromide under the nitrogen atmosphere, heating to 60 ℃ for reaction for 5 hours, filtering after the reaction is finished, carrying out oil-water separation, and carrying out reduced pressure distillation to obtain the benzyl polyamine. The molar ratio of polyamine, sodium hydroxide, fatty alcohol and toluene monobromide is 1: 1: 4: 0.8, the mass ratio of sodium hydroxide to water is 1: 4.
the preparation method of the polyamine-epoxy resin adduct comprises the following steps: adding polyamine into a four-mouth reaction bottle, slowly dropwise adding bisphenol F type glycidyl ether in the nitrogen atmosphere, heating to 60 ℃, reacting for 3 hours, and obtaining polyamine-epoxy resin addition product after the reaction is finished; the mass ratio of the polyamine to the bisphenol F type glycidyl ether is 1: 1.3.
example 4
On the basis of embodiment 3, the present embodiment further provides a pretreatment method of an accelerator, which specifically includes the following steps:
(1) according to the mass ratio of 1: 2.5: 6: 1.1, adding paraffin (the melting point is 54 ℃) and palm wax into petroleum ether at the temperature of 45 ℃ for uniform mixing, then adding a cationic surfactant, and uniformly mixing to obtain an oil phase for later use;
(2) preheating an accelerant to 55 ℃, and dropwise adding the accelerant into 3 times of the oil phase obtained in the step (1) under the stirring condition (2500 r/min) to obtain emulsion;
(3) and (3) dispersing the emulsion in a dispersion machine (500 r/min), and simultaneously heating (70 ℃) to evaporate the solvent to dryness to finish the pretreatment of the accelerator.
The preparation method of the cationic surfactant comprises the following steps: uniformly mixing fatty acid, benzene and concentrated sulfuric acid in a reaction kettle, then dripping 2,3, 4-trihydroxy butyric acid, reacting for 12 hours under the condition of heating (85 ℃) and stirring, then dripping mixed solution of anhydrous citric acid and thionyl chloride, reacting for 8 hours under the condition of heating (85 ℃) and stirring, adding 4.5 times of deionized water into the obtained product, uniformly mixing, then adding ammonium bicarbonate for neutralization reaction, and filtering to remove impurities to obtain a cationic surfactant; wherein the molar ratio of the fatty acid, the 2,3, 4-trihydroxy butyric acid and the anhydrous citric acid is (3-3.3): 1: (1-1.4), the adding amount of concentrated sulfuric acid is 2-3% of fatty acid, the adding amount of thionyl chloride is 0.5-1.5% of anhydrous citric acid, and the fatty acid is long-chain fatty acid.
The rest was the same as in example 3.
Example 5
On the basis of embodiment 3, the embodiment also provides a toughening agent for the solvent-free epoxy curing agent, wherein the toughening agent comprises 15 parts by mass of the curing agent, the toughening agent sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, and the mass ratio of the perlite micro powder core to the microcrystalline wax layer is 1: 1.5: 4: 2.
the plastic layer is prepared from the following raw materials in a mass ratio of 1: 0.4: 1.3: 0.08 parts of styrene, 3, 4-epoxy-1-butene, methyl methacrylate and a redox initiator.
The preparation method of the toughening agent comprises the following steps:
S1、taking perlite micropowder (with particle size of 7 μm and bulk density of 55 kg/m)3) Adding 7.5 times of water and silane coupling agent, stirring and soaking for 45min, and evaporating water to obtain perlite micropowder core; the mass ratio of the perlite micro powder to the silane coupling agent is 1: 0.2;
s2, mixing the raw materials according to the mass ratio of 1: 0.22, uniformly stirring the microcrystalline wax (the melting point is 70 ℃) and the sulfonate anionic emulsifier, putting the mixture into an emulsifying machine (the emulsifying temperature is 90 ℃, and the stirring speed is 3000 r/min), and adding (15 times of) deionized water for emulsification to obtain microcrystalline wax emulsion;
s3, placing the perlite micro powder core and the microcrystalline wax emulsion in a dispersing machine at 115 ℃ for dispersing until water is volatilized, and obtaining a microcrystalline wax layer;
s4, adding a nonionic emulsifier (isomeric tridecanol polyoxyethylether series, the addition amount of which is 13 percent of that of deionized water), deionized water (the addition amount of which is 15 times that of all raw materials) and the material obtained in the step S3 into the reaction kettle, uniformly stirring, and then mixing according to a mass ratio of 1: 0.5: 0.3 adding monomers of styrene, butadiene and diallylamine, stirring to emulsify the monomers, adding azodiisobutyramidine hydrochloride (the addition is 0.08 time of the styrene), and reacting for 10 hours at 62 ℃ to obtain a rubber layer;
s5, adding the raw materials obtained in the step S4 into the mixture according to the mass ratio of 1: 0.4: 1.3 adding monomer styrene, 3, 4-epoxy-1-butylene and methyl methacrylate, stirring to emulsify the monomers, adding redox initiator (ammonium persulfate/sodium bisulfite, the addition is 0.08 times of the styrene), and reacting for 4h at 55 ℃ to obtain a plastic layer;
s6, freezing and demulsifying the material obtained in the step S5, washing, filtering, and drying in vacuum to obtain the finished product of the toughening agent.
The rest is the same as in example 3.
Example 6
This example is a combination of examples 4 and 5.
Example 7
On the basis of embodiment 6, this embodiment also provides a preparation method of the solvent-free epoxy curing agent, which specifically includes the following steps:
A. according to the mass ratio of 1: 0.045, placing the pretreated accelerator and the nano lignin powder in a dispersing machine at 35 ℃ together for dispersing for 1.5 hours to obtain a first material;
B. according to the mass ratio of 1: 0.25: 4, uniformly mixing lignosulfonate, sodium silicate and water, adding a toughening agent in an amount which is 0.3 times that of the lignosulfonate, soaking for 40min, heating and volatilizing to obtain a material II;
C. and uniformly mixing benzyl polyamine and polyamine-epoxy adduct according to the mass parts, and then adding the material I and the material II to obtain the curing agent.
The rest is the same as in example 6.
Example 8
The embodiment provides a solvent-free epoxy curing agent, which consists of 55 parts by weight of benzyl polyamine, 25 parts by weight of polyamine-epoxy adduct, 2 parts by weight of benzyl dimethylamine and 10 parts by weight of toughening agent.
The preparation method of benzyl polyamine and polyamine-epoxy resin addition product is the same as that of example 1, and the preparation method of toughening agent is the same as that of example 2.
The embodiment also provides a pretreatment method of the accelerator, which specifically comprises the following steps:
(1) according to the mass ratio of 1: 2: 4: 0.6, adding paraffin (the melting point is 50 ℃) and palm wax into chloroform at 40 ℃ for uniform mixing, then adding a cationic surfactant, and uniformly mixing to obtain an oil phase for later use;
(2) preheating an accelerant to 50 ℃, and dropwise adding the accelerant into 2 times of the oil phase obtained in the step (1) under the stirring condition (2000 r/min) to obtain emulsion;
(3) and (3) dispersing the emulsion in a dispersion machine (400 r/min), and simultaneously heating (65 ℃) to evaporate the solvent to dryness to finish the pretreatment of the accelerator.
The preparation method of the cationic surfactant comprises the following steps: uniformly mixing fatty acid, benzene and concentrated sulfuric acid in a reaction kettle, then dripping 2,3, 4-trihydroxy butyric acid, reacting for 8 hours under the condition of heating (80 ℃) and stirring, then dripping mixed solution of anhydrous citric acid and thionyl chloride, reacting for 6 hours under the condition of heating (80 ℃) and stirring, adding 3-6 times of deionized water into the obtained product, uniformly mixing, then adding ammonium bicarbonate for neutralization reaction, and filtering to remove impurities to obtain a cationic surfactant; wherein the molar ratio of the fatty acid, the 2,3, 4-trihydroxybutyric acid and the anhydrous citric acid is 3: 1: 1, the adding amount of concentrated sulfuric acid is 2 percent of that of fatty acid, and the adding amount of thionyl chloride is 0.5 percent of that of anhydrous citric acid.
The embodiment also provides a preparation method of the solvent-free epoxy curing agent, which specifically comprises the following steps:
A. according to the mass ratio of 1: 0.03, placing the pretreated accelerant and the nano lignin powder in a dispersing machine at 30 ℃ for dispersing for 1h to obtain a first material;
B. according to the mass ratio of 1: 0.1: 3, uniformly mixing lignosulfonate, sodium silicate and water, adding a toughening agent in an amount which is 0.2 times that of the lignosulfonate, soaking for 30min, heating and volatilizing to obtain a second material;
C. and uniformly mixing benzyl polyamine and polyamine-epoxy adduct according to the mass parts, and then adding the material I and the material II to obtain the curing agent.
Example 9
The embodiment provides a solvent-free epoxy curing agent, which consists of 100 parts by weight of benzyl polyamine, 50 parts by weight of polyamine-epoxy adduct, 20 parts by weight of o-hydroxybenzyl dimethylamine and 20 parts by weight of toughening agent.
The preparation method of the benzyl polyamine comprises the following steps: adding polyamine, water, lithium hydroxide and isopropanol into a four-mouth reaction bottle, slowly dropwise adding toluene monobromide under the nitrogen atmosphere, heating to 80 ℃ for reaction for 10 hours, filtering after the reaction is finished, carrying out oil-water separation, and carrying out reduced pressure distillation to obtain the benzyl polyamine. The molar ratio of polyamine, lithium hydroxide, isopropanol and toluene monobromide is 1: 1.2: 6: 0.7, the mass ratio of the lithium hydroxide to the water is 1: 5.
the preparation method of the polyamine-epoxy resin adduct comprises the following steps: adding polyamine into a four-mouth reaction bottle, slowly dropwise adding cardanol glycidyl ether in the nitrogen atmosphere, heating to 80 ℃, reacting for 6 hours, and obtaining polyamine-epoxy resin addition product after the reaction is finished; the mass ratio of polyamine to cardanol glycidyl ether is 1: (0.8-1.8).
The embodiment also provides a pretreatment method of the accelerator, which specifically comprises the following steps:
(1) according to the mass ratio of 1: 3: 8: 1.6, adding paraffin (with the melting point of 60 ℃) and palm wax into petroleum ether with the temperature of 50 ℃ for uniform mixing, then adding a cationic surfactant, and uniformly mixing to obtain an oil phase for later use;
(2) preheating an accelerator to 60 ℃, and dropwise adding the accelerator into 4 times of the oil phase obtained in the step (1) under the stirring condition (3000 r/min) to obtain emulsion;
(3) and (3) dispersing the emulsion in a dispersion machine (600 r/min), and simultaneously heating (75 ℃) to evaporate the solvent to dryness to complete the pretreatment of the accelerator.
The preparation method of the cationic surfactant comprises the following steps: uniformly mixing fatty acid, benzene and concentrated sulfuric acid in a reaction kettle, then dripping 2,3, 4-trihydroxy butyric acid, reacting for 16 hours under the condition of heating (90 ℃) and stirring, then dripping mixed solution of anhydrous citric acid and thionyl chloride, reacting for 10 hours under the condition of heating (90 ℃) and stirring, adding 3-6 times of deionized water into the obtained product, uniformly mixing, then adding ammonium bicarbonate for neutralization reaction, and filtering to remove impurities to obtain a cationic surfactant; wherein the molar ratio of the fatty acid, the 2,3, 4-trihydroxybutyric acid to the anhydrous citric acid is 3.3: 1: 1.4, the adding amount of concentrated sulfuric acid is 3 percent of that of fatty acid, and the adding amount of thionyl chloride is 1.5 percent of that of anhydrous citric acid.
The embodiment also provides a toughening agent used in the solvent-free epoxy curing agent, which sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, wherein the mass ratio of the perlite micro powder core to the microcrystalline wax layer is 1: 2: 5: 3.
the plastic layer is prepared from the following raw materials in a mass ratio of 1: 0.5: 1.6: 0.1 of styrene, 3, 4-epoxy-1-butylene, methyl methacrylate and a redox initiator.
The preparation method of the toughening agent comprises the following steps:
s1, collecting perlite micropowder (with particle size of 10 μm and bulk density of 70 kg/m)3) Adding 10 times of water and silane coupling agent, stirring and soaking for 60min, and evaporating water to obtain perlite micropowder core; perlite micropowder and silane coupling agentThe quantity ratio is 1: 0.3;
s2, mixing the raw materials according to the mass ratio of 1: 0.3, uniformly stirring the microcrystalline wax (the melting point is 75 ℃) and the carboxylate anionic emulsifier, putting the mixture into an emulsifying machine (the emulsifying temperature is 95 ℃ and the stirring speed is 3500 r/min), and adding (20 times of) deionized water for emulsification to obtain microcrystalline wax emulsion;
s3, placing the perlite micro powder core and the microcrystalline wax emulsion in a dispersing machine at 120 ℃ for dispersing until water is volatilized, and obtaining a microcrystalline wax layer;
s4, adding a nonionic emulsifier (alkylphenol ethoxylates series with the addition amount of 16 percent of deionized water), deionized water (with the addition amount of 20 times of all the raw materials) and the material obtained in the step S3 into the reaction kettle, uniformly stirring, and then mixing according to the mass ratio of 1: 0.6: 0.4 adding monomers of styrene, butadiene and diallylamine, stirring to emulsify the monomers, adding azodiisobutyl amidine hydrochloride (the addition amount is 0.1 time of that of the styrene), and reacting for 12 hours at 65 ℃ to obtain a rubber layer;
s5, adding the materials obtained in the step S4 according to the mass ratio of 1: 0.5: 1.6 adding monomer styrene, 3, 4-epoxy-1-butylene and methyl methacrylate, stirring to emulsify the monomer, adding redox initiator (cumene hydroperoxide/tetraethylene imine, the addition is 0.1 time of styrene), and reacting for 5h at 60 ℃ to obtain a plastic layer;
s6, freezing and demulsifying the material obtained in the step S5, washing, filtering, and drying in vacuum to obtain the finished product of the toughening agent.
The embodiment also provides a preparation method of the solvent-free epoxy curing agent, which specifically comprises the following steps:
A. according to the mass ratio of 1: 0.06, placing the pretreated accelerant and the nano lignin powder in a dispersing machine at 40 ℃ for dispersing for 1-2 hours to obtain a first material;
B. according to the mass ratio of 1: 0.4: 5, uniformly mixing lignosulfonate, sodium silicate and water, adding 0.4 times of toughening agent, soaking for 50min, heating and volatilizing to obtain a material II;
C. and uniformly mixing benzyl polyamine and polyamine-epoxy adduct according to the mass parts, and then adding the material I and the material II to obtain the curing agent.
Comparative example 1
This comparative example differs from example 7 in that the oil phase of step (1) of the accelerator pretreatment process does not include paraffin wax.
Comparative example 2
This comparative example differs from example 7 in that no palm wax is included in the oil phase of step (1) of the accelerator pretreatment process.
Comparative example 3
This comparative example differs from example 7 in that in step (1) of the pretreatment method of the accelerator, petroleum ether was replaced with benzene.
Comparative example 4
The present comparative example is different from example 7 in that in step (1) of the pretreatment method of the accelerator, the mass ratio of paraffin wax to carnauba wax is 1: 1.5.
comparative example 5
The comparative example differs from example 7 in that in step (1) of the accelerator pretreatment method, the mass ratio of paraffin wax to palm wax is 1: 3.5.
comparative example 6
This comparative example differs from example 7 in that the oil phase of step (1) of the accelerator pretreatment process does not include a cationic surfactant.
Comparative example 7
This comparative example differs from example 7 in that the cationic surfactant in the pretreatment method of the accelerator is a conventional quaternary ammonium salt type cationic surfactant containing a C10-C18 long chain alkyl group.
Comparative example 8
This comparative example differs from example 8 in that the toughening agent is a conventional toughening agent polyimide.
Comparative example 9
This comparative example differs from example 8 in that the toughening agent comprises, in order from the inside to the outside, a rubber layer and a plastic layer.
Comparative example 10
This comparative example differs from example 8 in that the toughening agent does not include a microcrystalline wax layer.
Comparative example 11
The comparative example differs from example 8 in that the toughening agent was prepared by replacing perlite fines with silica fines in step S1.
Comparative example 12
This comparative example differs from example 8 in that the toughening agent was prepared in step S1 without the addition of a silane coupling agent.
Comparative example 13
This comparative example differs from example 8 in that the toughener is prepared by the process step S4 without the addition of the monomer diallylamine.
Comparative example 14
This comparative example differs from example 8 in that the toughening agent was prepared in step S5 without the addition of the monomer 3, 4-epoxy-1-butene.
Comparative example 15
This comparative example is different from example 9 in that the temperature of the disperser in step A of the method for preparing a solventless epoxy curing agent is 25 ℃.
Comparative example 16
This comparative example is different from example 9 in that the temperature of the disperser in step A of the method for preparing a solventless epoxy curing agent is 45 ℃.
Comparative example 17
The comparative example differs from example 9 in that no nano-lignin powder was added in step a of the preparation method of the solvent-free epoxy hardener.
Comparative example 18
This comparative example differs from example 9 in that no lignosulfonate was added in step B of the solvent-free epoxy hardener preparation process.
Comparative example 19
This comparative example differs from example 9 in that no sodium silicate was added in step B of the process for preparing a solventless epoxy hardener.
Curing performance parameters of the solvent-free epoxy curing agent prepared by the invention
Curing agents prepared in examples 1 to 9 of the present invention and comparative examples 1 to 19, and a commercially available solventless epoxy curing agent were compounded with a bisphenol A type epoxy resin (epoxy value of 0.4) to prepare a two-component epoxy coating according to n (epoxy group)/n (amino active hydrogen) =1/1, and the results of curing properties were measured by preparing a coating film product according to GB/T1727-.
TABLE 1
As can be seen from the above Table 1, the solventless epoxy hardener prepared by the invention has excellent performance indexes, most of which are superior to those of products sold in the market, especially in examples 7-9, the hardness is 6H, the adhesion is grade 1, the flexibility is less than or equal to 1mm, the impact resistance is between 70-74cm, the water resistance is excellent, the curing surface drying time is 2H, and the solventless epoxy hardener shows good curing performance.
On the basis of the embodiment 3, the embodiment 4 pretreats the accelerator, so that the curing surface drying time of the curing agent is shortened, and other curing performances are improved; example 5 with the addition of a toughening agent, flexibility and other curing properties were improved.
Example 6 combines the solutions of examples 4 and 5, but since the pre-treated accelerator is easily affected by the toughening agent, the final curing tack-free time and other curing properties are not significantly or even decreased. On the basis of the embodiment 6, in the embodiment 7, when the curing agent is prepared, the surface treatment is also simultaneously carried out on the toughening agent and the pretreated accelerator respectively, so that the comprehensive performance of the curing agent is improved.
Secondly, the toughening effect test of the epoxy curing agent prepared by the invention
The curing agents prepared in examples 3, 5, 7 to 9 and comparative examples 8 to 14 of the present invention, and the commercially available solventless epoxy curing agent were compounded with bisphenol A epoxy resin to prepare a two-component epoxy coating, and the results of the tests of impact strength, bending strength and elongation at break were measured according to the corresponding national standards, respectively, as shown in Table 2.
TABLE 2
As can be seen from Table 2, the solventless epoxy curing agents prepared in examples 3, 5, 7-9 of the present invention have better impact strength, bending strength and tensile strength than those of the commercially available products. On the basis of the embodiment 3, the toughening agent is prepared and added into the curing agent, and the impact strength, the bending strength and the tensile strength of the toughening agent are obviously improved.
In particular, examples 7, 8 and 9 are excellent in the impact strength of 35.8 kJ/m2The bending strength is more than 124.5 MPa, and the tensile strength is more than 139.2 MPa. The curing agent of the invention has good toughening effect.
The invention has the beneficial effects that: the solvent-free epoxy curing agent and the preparation method thereof provided by the invention are used for respectively designing the amine curing main body, the toughening agent and the accelerator in the curing agent, so that the comprehensive performance of the curing agent can be effectively improved.
Finally, it should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and not intended to limit the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or some technical features thereof can be replaced. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A solvent-free epoxy curing agent is characterized in that: the feed comprises the following raw materials in parts by weight: 50-100 parts of benzyl polyamine, 20-50 parts of polyamine-epoxy adduct and 0-20 parts of accelerator;
the benzyl polyamine is prepared by the following steps: adding polyamine, water, metal hydroxide and fatty alcohol into a four-mouth reaction bottle, slowly dropwise adding toluene monohalide in the nitrogen atmosphere, heating to 40-80 ℃ for reaction for 1-10h, filtering after the reaction is finished, performing oil-water separation, and performing reduced pressure distillation to obtain the benzyl polyamine.
2. The solventless epoxy curing agent of claim 1, wherein: the promoter is selected from one of 2,4, 6-tri (dimethylaminomethyl) phenol, benzyl dimethylamine, triethylamine, triethanolamine and o-hydroxybenzyl dimethylamine, and the molar ratio of polyamine, metal hydroxide, fatty alcohol and toluene monohalide is 1: (0.8-1.2): (2-6): (0.7-0.9), wherein the mass ratio of the metal hydroxide to the water is 1: (3-5).
3. The solventless epoxy curing agent of claim 1, wherein: the polyamine-epoxy resin adduct is prepared by the following steps: adding polyamine into a four-mouth reaction bottle, slowly dropwise adding epoxy resin in the nitrogen atmosphere, heating to 40-80 ℃, reacting for 1-6h, and obtaining polyamine-epoxy resin addition product after the reaction is finished; the mass ratio of the polyamine to the epoxy resin is 1: (0.8-1.8).
4. A method for pretreating an accelerator in a solventless epoxy curing agent according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) adding paraffin and palm wax into a solvent, uniformly mixing, then adding a cationic surfactant, and uniformly mixing to obtain an oil phase for later use;
(2) preheating an accelerant, and dropwise adding the accelerant into the oil phase obtained in the step (1) under the stirring condition to obtain emulsion;
(3) and (4) dispersing the emulsion in a dispersion machine, and simultaneously heating and evaporating the solvent to dryness to complete the pretreatment of the accelerator.
5. The method for pretreating an accelerator according to claim 4, wherein: in the step (1), the melting point of the paraffin is 50-60 ℃, the solvent is petroleum ether or trichloromethane, and the mass ratio of the paraffin, the palm wax, the solvent and the cationic surfactant is 1: (2-3): (4-8): (0.6-1.6); in the step (2), the mass ratio of the accelerator to the oil phase is 1: (2-4).
6. The pretreatment method of accelerator according to claim 4, wherein: the preparation method of the cationic surfactant comprises the following steps: uniformly mixing fatty acid, benzene and concentrated sulfuric acid in a reaction kettle, then dripping 2,3, 4-trihydroxy butyric acid, reacting for 8-16h under the condition of heating and stirring, then dripping mixed solution of anhydrous citric acid and thionyl chloride, reacting for 6-10h under the condition of heating and stirring, adding deionized water in an amount which is 3-6 times that of the obtained product, adding ammonium bicarbonate after uniformly mixing for neutralization reaction, and filtering and removing impurities to obtain a cationic surfactant; wherein the molar ratio of the fatty acid, the 2,3, 4-trihydroxy butyric acid and the anhydrous citric acid is (3-3.3): 1: (1-1.4), the adding amount of concentrated sulfuric acid is 2-3% of the fatty acid, and the adding amount of thionyl chloride is 0.5-1.5% of the anhydrous citric acid.
7. A toughening agent for use in the solventless epoxy curing agent of claim 1, wherein: the toughening agent is 10-20 parts by mass in the curing agent, the toughening agent sequentially comprises a perlite micro powder core, a microcrystalline wax layer, a rubber layer and a plastic layer from inside to outside, and the mass ratio of the toughening agent to the plastic layer is 1: (1-2): (3-5): (1-3).
8. The toughening agent of claim 7, wherein: the perlite micro powder core is prepared from the following raw materials in a mass ratio of 1: (0.1-0.3) perlite micropowder and silane coupling agent; the microcrystalline wax layer is prepared from the following raw materials in a mass ratio of 1: (0.15-0.3) a microcrystalline wax, an anionic emulsifier; the rubber layer is prepared from the following raw materials in a mass ratio of 1: (0.4-0.6): (0.2-0.4): (0.06-0.1) styrene, butadiene, diallylamine, azobisisobutyramidine hydrochloride; the plastic layer is prepared from the following raw materials in a mass ratio of 1: (0.3-0.5): (1-1.6): (0.05-0.1) styrene, 3, 4-epoxy-1-butylene, methyl methacrylate and a redox initiator.
9. The toughening agent of claim 8, wherein: the preparation method of the toughening agent comprises the following steps:
s1, adding water and a silane coupling agent into the perlite micro powder, stirring and soaking for 30-60min, and evaporating water to obtain perlite micro powder cores;
s2, uniformly stirring the microcrystalline wax and the anionic emulsifier, putting the mixture into an emulsifying machine, and adding deionized water for emulsification to obtain microcrystalline wax emulsion;
s3, placing the perlite micro powder core and the microcrystalline wax emulsion in a dispersion machine at the temperature of 110-120 ℃ for dispersion until water is volatilized, and obtaining a microcrystalline wax layer;
s4, adding a nonionic emulsifier, deionized water and the material obtained in the step S3 into a reaction kettle, uniformly stirring, adding monomers including styrene, butadiene and diallylamine, stirring to emulsify the monomers, adding azodiisobutyramidine hydrochloride, and reacting at 60-65 ℃ for 8-12h to obtain a rubber layer;
s5, adding monomer styrene, 3, 4-epoxy-1-butylene and methyl methacrylate into the material obtained in the step S4, stirring to emulsify the monomer, adding a redox initiator, and reacting at 50-60 ℃ for 3-5h to obtain a plastic layer;
s6, freezing and demulsifying the material obtained in the step S5, washing, filtering, and drying in vacuum to obtain the finished product of the toughening agent.
10. A method for preparing a solventless epoxy curing agent according to any one of claims 4-9, wherein: the method specifically comprises the following steps:
A. placing the pretreated accelerator and the nano lignin powder in a disperser at 30-40 ℃ for dispersing for 1-2 hours to obtain a first material;
B. uniformly mixing lignosulfonate, sodium silicate and water, adding 0.2-0.4 times of toughening agent, soaking for 30-50min, heating and volatilizing to obtain a material II;
C. uniformly mixing benzyl polyamine and polyamine-epoxy adduct according to the parts by weight, and then adding the material I and the material II to obtain a curing agent;
wherein the mass ratio of the accelerator pretreated in the step A to the nano lignin powder is 1: (0.03-0.06), wherein the mass ratio of the lignosulfonate, the sodium silicate and the water in the step B is 1: (0.1-0.4): (3-5).
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