CN114854089A - Application of aryl alcohol amine as epoxy resin diluent and epoxy resin composition - Google Patents
Application of aryl alcohol amine as epoxy resin diluent and epoxy resin composition Download PDFInfo
- Publication number
- CN114854089A CN114854089A CN202210471762.4A CN202210471762A CN114854089A CN 114854089 A CN114854089 A CN 114854089A CN 202210471762 A CN202210471762 A CN 202210471762A CN 114854089 A CN114854089 A CN 114854089A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- amine
- alkyl
- resin composition
- halogen
- 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.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 80
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 80
- -1 aryl alcohol amine Chemical class 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000003085 diluting agent Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000524 functional group Chemical group 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 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 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000010425 asbestos Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical group OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002990 reinforced plastic Substances 0.000 claims description 2
- 229910052895 riebeckite Inorganic materials 0.000 claims description 2
- 239000013008 thixotropic agent Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 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 claims 2
- 238000000465 moulding Methods 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000007865 diluting Methods 0.000 abstract description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000012264 purified product Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000012855 volatile organic compound Substances 0.000 description 8
- 235000019445 benzyl alcohol Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QAWJAMQTRGCJMH-UHFFFAOYSA-N 2-(4-methylphenyl)oxirane Chemical compound C1=CC(C)=CC=C1C1OC1 QAWJAMQTRGCJMH-UHFFFAOYSA-N 0.000 description 3
- MRXPNWXSFCODDY-UHFFFAOYSA-N 2-methyl-2-phenyloxirane Chemical compound C=1C=CC=CC=1C1(C)CO1 MRXPNWXSFCODDY-UHFFFAOYSA-N 0.000 description 3
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 150000003975 aryl alkyl amines Chemical class 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229960004889 salicylic acid Drugs 0.000 description 3
- 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 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 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 1
- YVMKRPGFBQGEBF-UHFFFAOYSA-N 2-(3-chlorophenyl)oxirane Chemical compound ClC1=CC=CC(C2OC2)=C1 YVMKRPGFBQGEBF-UHFFFAOYSA-N 0.000 description 1
- ICVNPQMUUHPPOK-UHFFFAOYSA-N 2-(4-fluorophenyl)oxirane Chemical compound C1=CC(F)=CC=C1C1OC1 ICVNPQMUUHPPOK-UHFFFAOYSA-N 0.000 description 1
- ARHIWOBUUAPVTB-UHFFFAOYSA-N 2-(4-methoxyphenyl)oxirane Chemical compound C1=CC(OC)=CC=C1C1OC1 ARHIWOBUUAPVTB-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 description 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 description 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- 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
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention discloses an application of aryl alcohol amine as an epoxy resin diluent and an epoxy resin composition. The application of the aryl alcohol amine as an epoxy resin diluent is characterized in that the aryl alcohol amine has a structural general formula shown as the following formula. When the aryl alcohol amine compound is applied to the epoxy resin composition to play a role in diluting, the cross-linking and curing of the composition can be promoted, the curing time is shortened, the mechanical property of the epoxy resin composition is enhanced, and the aryl alcohol amine compound has the advantage of particularly low VOC and is suitable for preparing environment-friendly epoxy resin products.
Description
Technical Field
The present invention relates to the use of arylalkylamines as diluents for epoxy resins and to epoxy resin compositions comprising such diluents.
Background
The epoxy resin is a thermosetting resin, has excellent chemical resistance, good paint film adhesion, good heat resistance, electrical insulation performance and the like, and is widely applied to the fields of coatings, adhesives and composite materials.
In the epoxy resin composition, benzyl alcohol is used as a diluent of epoxy resin, has the advantages of low viscosity, good diluting effect, certain promotion effect on curing of the epoxy resin and the like, and is widely used in the epoxy resin industry. However, the disadvantages of benzyl alcohol are also very obvious, and the boiling point is low, and the saturated vapor pressure is high, so that the trend that benzyl alcohol is regarded as VOC in the industry and is forbidden or used less in the industry is more and more obvious. However, although there are many types of epoxy resin diluents available on the market, no environmentally friendly diluent capable of replacing benzyl alcohol has been developed, and the reason for this is mainly that benzyl alcohol can play a role in diluting the epoxy resin and also can obviously promote the curing and crosslinking of the epoxy resin. The lack of substances which can replace benzyl alcohol and are found in the market also greatly limits the development of environmental protection of epoxy resin materials.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide an application of arylalkylamines as a diluent for epoxy resins. When the aryl alcohol amine compound is applied to the epoxy resin composition to play a role in diluting, the cross-linking and curing of the composition can be promoted, the curing time is shortened, the mechanical property of the epoxy resin composition is enhanced, and the aryl alcohol amine compound has the advantage of particularly low VOC and is suitable for preparing environment-friendly epoxy resin products.
It is a second object of the present invention to provide an epoxy resin composition comprising the above diluent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention firstly provides an application of aryl alcohol amine as an epoxy resin diluent, wherein the aryl alcohol amine has a structural general formula shown as the following formula I:
wherein R is 1 Selected from H, halogen, C 1 ～C 20 Alkyl or alkoxy or aralkyl of (a), preferably selected from H, halogen, methyl, methoxy;
R 4 selected from H, C 1 ～C 5 Alkyl of (3), preferably H, methyl;
R 2 、R 3 each independently selected from H, optionally substituted or unsubstituted alkyl or cycloalkyl or aralkyl, preferably from C 1 ～C 20 More preferably selected from C 1 ～C 10 Unsubstituted or hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted alkyl, cycloalkyl and C 6 ～C 20 Unsubstituted or hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted aralkyl.
In a preferred embodiment, in formula I, R 2 、R 3 Each independently selected from H, cyclohexyl, phenyl, benzyl, C 1 -C 6 Alcoholic hydroxyl group of (2), C 1 -C 10 Alkyl of (C) 1 -C 6 Methylamino and alkyl piperazine.
In a preferred embodiment, the application is particularly suitable for use in the fields of paper processing, the manufacture of cured epoxy resins, the manufacture of coatings, adhesives, reinforced or non-reinforced plastics, elastomers, molded parts, and the like.
The source of the aryl alcohol amine compound is not limited, and the aryl alcohol amine compound can be directly purchased through a market way, and can also be customized by a chemical customization service. In order to save the cost of raw materials, the invention adopts the following process to synthesize the aryl alcohol amine compound:
mixing a compound shown as a formula II with a compound shown as a formula III in the presence of a catalyst for reaction to prepare an aryl alcohol amine compound shown as a formula I;
wherein R is 1 -R 4 The definitions of (a) are the same as above.
The compound of formula II is preferably selected from styrene oxide and derivatives thereof, and may be, for example, but not limited to, styrene oxide, 2-phenyl propylene oxide, (4-fluorophenyl) ethylene oxide, 4-bromostyrene epoxide, 3-chlorostyrene oxide, 2- (4-methylphenyl) ethylene oxide, 2- (4-methoxyphenyl) ethylene oxide, and the like.
The compound of formula III is preferably selected from amines such as aliphatic, alicyclic or aromatic amines with or without functional groups, wherein the amines without functional groups may be, for example, but not limited to, aniline, benzylamine, N-methylaniline, cyclohexylamine, N-methylcyclohexylamine, dimethylamine, diethylamine, N-propylamine, etc.; the functional group in the amine group having a functional group is preferably a hydroxyl group, an amino group, an imino group, a vinyl group, an alkoxy group, a halogen group, or a carboxyl group, and examples of the amine group include, but are not limited to, ethanolamine, diethanolamine, N-aminoethylpiperazine, 3-dimethylaminopropylamine, vinylamine, and the like.
The catalyst is selected from phenols and tertiary amine catalysts, preferably one or more selected from salicylic acid, phenol, cardanol, nonylphenol, triethanolamine, 2,4, 6-tris (dimethylaminomethyl) phenol.
In the above reaction raw materials, the suggested molar ratio of the compound shown in formula II to the compound shown in formula III is 1 (0.8-3), preferably 1 (0.9-1.5).
The amount of the catalyst added to the reaction raw materials is 0 to 2%, preferably 0.1 to 1%, for example, 0.5%, 0.8%, 1% or the like, based on the total mass of the compound represented by the formula II and the compound represented by the formula III.
The reaction conditions of the above-mentioned mixing reaction are: the reaction temperature is 50-100 ℃, and the reaction time is 1-6 h. After the reaction is finished, the obtained product is purified in vacuum to obtain the target product.
The preparation method of the aryl alcohol amine compound is provided as a preferable, convenient and feasible synthesis process only for the smooth implementation of the scheme of the invention, but it should be noted that the synthesis process does not have any limitation on the functions of the obtained aryl alcohol amine compound, and the functions of the aryl alcohol amine compound are only related to the product structure and physical properties. The arylalkylamines compounds are not limited in this invention and can be prepared by any feasible scheme.
The invention also provides an epoxy resin composition, which comprises a compound shown in the formula I or a mixture formed by the compounds shown in the formula I and at least one polymer capable of being crosslinked;
wherein R is 1 Selected from H, halogen, C 1 ～C 20 Alkyl or alkoxy or aralkyl of (a), preferably selected from H, halogen, methyl, methoxy;
R 4 selected from H, C 1 ～C 5 The alkyl group of (1) is preferably H or methyl.
R 2 、R 3 Each independently selected from H, optionally substituted or unsubstituted alkyl or cycloalkyl or aralkyl, preferably from C 1 ～C 20 More preferably selected from C 1 ～C 10 Unsubstituted alkyl, cycloalkyl and C 6 ～C 20 Unsubstituted aralkyl and C 1 ～C 10 Hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxyl-substituted alkyl, cycloalkylAnd C 6 ～C 20 Any of methyl, ethyl, hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted aralkyl
In a preferred embodiment, the mass ratio of the compound of the formula I or the mixture of compounds of the formula I to the polymer capable of crosslinking is from 1:99 to 60:40, preferably from 5:95 to 30: 70, more preferably 10:90 to 20: 80.
in a preferred embodiment, the polymer capable of being crosslinked comprises:
a) an epoxy resin;
b) a curing agent;
c) optionally an additive.
In a preferred embodiment, the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, glycidyl ether type epoxy resin.
In a preferred embodiment, the curing agent is selected from amine-based curing agents, anhydride-based curing agents;
preferably, the amine curing agent is one or more of aliphatic amine, polyether amine, alicyclic amine, aromatic amine, polyamide and modified substances thereof, wherein the aliphatic amine, polyether amine, alicyclic amine, aromatic amine and polyamide at least contain two amino functional groups;
preferably, the acid anhydride curing agent is one or more of fatty acid anhydride containing at least one acid anhydride functional group, aromatic acid anhydride and modified product thereof.
In a preferred embodiment, the additives include optionally fillers, functional aids, non-reactive diluents;
preferably, the filler is one or more of calcium carbonate, titanium dioxide, mica powder, talcum powder, montmorillonite, wollastonite powder, barium sulfate, asbestos powder and argil;
preferably, the functional auxiliary agent is one or more of a dispersing agent, a defoaming agent, a leveling agent, a thixotropic agent, a wetting dispersing agent, an accelerator, a toughening agent and a plasticizer;
preferably, the non-reactive diluent is one or more of xylene, benzyl alcohol, toluene, benzene, dibutyl phthalate, dioctyl phthalate and acetone.
In a preferred embodiment, the content of each component in the crosslinkable polymer is, in parts by weight:
10-70 parts by weight of epoxy resin,
10-40 parts by weight of a curing agent,
0-30 parts of additive.
The epoxy resin composition may be prepared by any method known in the art, for example, by mixing the compound of formula I or a mixture of compounds of formula I with an epoxy resin to form the agent A, and then blending with the agent B; or the compound shown in the formula I or the mixture formed by the compound shown in the formula I is firstly mixed with a curing agent to form an agent B, and then is mixed with an epoxy resin agent A; or respectively mixing the compound shown in the formula I or a mixture composed of the compound shown in the formula I, an epoxy resin agent A and a curing agent B to obtain the epoxy resin composition. The additive can be added in any preparation process and is uniformly mixed with related components.
The application has the following technical advantages:
(1) the aryl alcohol amine compound is used as an epoxy resin diluent, has low saturated vapor pressure and extremely low VOC, and can be used for preparing environment-friendly epoxy adhesives or coatings and the like;
(2) the aryl alcohol amine compound serving as an epoxy resin diluent can remarkably promote the crosslinking and curing of resin, and has the advantage of shortening the curing time compared with a conventional reactive or non-reactive diluent;
(3) the aryl alcohol amine compound is used as an epoxy resin diluent, so that the mechanical property of the obtained epoxy resin cured product is obviously improved, especially when the aryl alcohol amine compound contains functional groups such as primary amino group and the like, the primary amino group can be used as a reactive functional group to participate in curing and crosslinking of resin, the mechanical property of the cured product can be further improved, and the toughening effect on materials is achieved;
(4) the aryl alcohol amine compound has higher structure adjustability and wider operation window, and can be suitable for epoxy resin compositions with wider performance requirements;
(5) the epoxy resin diluent can be used independently or matched with other epoxy resin diluents, and has important significance for expanding the type selection of the diluent.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The names, abbreviations and sources of the main chemicals used in the examples of the present invention are shown in the following table. The reagents used are all chemically pure unless otherwise indicated.
The information on the main raw materials involved in the following embodiments is shown in table 1:
TABLE 1 information on the main raw materials
| Chemical name | Source |
| Styrene oxide | Wanhua chemistry |
| Phenol and its preparation | Aladdin |
| Aniline | Wanhua chemistry |
| Diethylamine | Beijing yinuoqiao technology |
| 2- (4-methylphenyl) oxirane | Shanghai Kedi |
| N-methylaniline | Beijing yinuoqiao technology |
| N-methylcyclohexylamine | Beijing yinuoqiao technology |
| Salicylic acid | Beijing yinuoqiao technology |
| Benzylamine | Beijing yinuoqiao technology |
| N-propylamine | Beijing yinuoqiao technology |
| Ethanolamine | Beijing yinuoqiao technology |
| N-aminoethylpiperazines | Beijing yinuoqiao technology |
| 3-Chlorochlorinated styrene | Hebeizhou Kun medicine |
| 3-dimethylaminopropylamine | Beijing yinuoqiao technology |
| 2-phenyl propylene oxide | Microphone forest |
| 4-Bromobenzeneepoxide | Sigma-Aldrich |
| Wanamine2110 | Wanhua chemistry |
| Epoxy resin E51 | Sanmu resin |
The main test method adopted by the invention is as follows:
(1) and (3) viscosity testing: the viscosity of the material was measured at 25 ℃ using a U.S. Bohler fly viscometer.
(1) VOC testing: VOC testing is carried out by a testing method in the limit of the adhesive volatile organic compound of GB 33372-2020;
(2) gel time test: weighing 100g of a mixture of resin and a curing agent, and carrying out a hectogram gel time test at 25 ℃;
(3) and (3) testing the mechanical property of a condensate: tensile strength and tensile modulus performance tests were performed by methods in the general rules of the test methods for mechanical Properties of plastics, GBT 1039-1992.
Preparation of examples 1 to 9: preparation of arylalkylamines
[ PREPARATION EXAMPLE 1 ]
Adding 27.9g (0.3mol) of aniline and 0.2g of salicylic acid into a three-opening reaction container, heating to 80 ℃, slowly dropwise adding 12g (0.1mol) of styrene oxide under the stirring state, and after dropwise adding, carrying out heat preservation reaction for 4 hours to obtain a crude product; removing unreacted raw materials in vacuum to obtain a purified product A.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.42(s,2H),7.34(d,2H),7.24(d,H),7.06(d,2H),6.65(d,H),6.57(s,2H),5.15(s,H),4.86(t,H),3.7(d,H),3.53(d,2H).
[ PREPARATION EXAMPLE 2 ]
Adding 21.4g (0.2mol) of N-methylaniline and 0.3g of phenol into a three-opening reaction vessel, heating to 100 ℃, slowly dropwise adding 12g (0.1mol) of styrene oxide under the stirring state, and after dropwise adding, carrying out heat preservation reaction for 6 hours to obtain a crude product; removing unreacted raw materials in vacuum to obtain a purified product B.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.44(s,2H),7.36(d,2H),7.25(d,H),7.21(d,2H),6.95(s,2H),6.8(d,H),5.17(s,H),4.86(t,H),3.73(s,2H),2.73(s,3H).
[ PREPARATION EXAMPLE 3 ]
Adding 11.3g (0.1mol) of N-methylcyclohexylamine and 0.02g of 2,4, 6-tris (dimethylaminomethyl) phenol into a three-opening reaction container, heating to 70 ℃, slowly dropwise adding 12g (0.1mol) of styrene oxide under the stirring state, and after dropwise adding, keeping the temperature for reaction for 3 hours to obtain a crude product; removing unreacted raw materials in vacuum to obtain a purified product C.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.45(s,2H),7.32(d,2H),7.25(d,H),5.25(s,H),4.83(t,H),2.86(s,2H),2.56(m,H),2.25(s,3H),1.57(t,2H),1.45(m,2H),1.35(t,2H),1.20(m,2H),1.1(m,2H).
[ PREPARATION EXAMPLE 4 ]
Adding 10.9g (0.15mol) of diethylamine into a three-port reaction vessel, heating to 50 ℃, slowly dropwise adding 12g (0.1mol) of styrene oxide under the stirring reflux state, and after dropwise adding, keeping the temperature and reacting for 5 hours to obtain a crude product; and removing unreacted raw materials in vacuum to obtain a purified product D.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.2(s,2H),7.04(s,2H),5.35(s,H),4.86(t,H),2.86(s,2H),2.4(t,4H),2.2(s,3H),1.17(d,6H).
[ PREPARATION EXAMPLE 5 ]
Adding 8.5g (0.08mol) of benzylamine into a three-port reaction container, heating to 60 ℃, slowly dropwise adding 12g (0.1mol) of styrene oxide under the stirring state, and after dropwise adding, keeping the temperature and reacting for 1h to obtain a crude product; and removing unreacted raw materials in vacuum to obtain a purified product E.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.35(s,2H),7.31(d,2H),7.28(d,H),7.26(s,2H),6.85(s,2H),5.15(s,H),4.86(t,H),3.82(s,5H),3.1(d,2H)，2.1(m,H).
[ PREPARATION EXAMPLE 6 ]
Adding 5g (0.085mol) of n-propylamine into a three-port reaction vessel, heating to 50 ℃, slowly dropwise adding 15.4g (0.1mol) of 3-styrene oxychloride under the stirring reflux state, and after dropwise adding, keeping the temperature and reacting for 2 hours to obtain a crude product; and removing unreacted raw materials in vacuum to obtain a purified product F.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.45(s,H),7.34(d,2H),7.22(s,H),5.23(s,H),4.86(t,H),3.1(t,2H),2.52(d,2H),1.9(m,H),1.45(m,2H),0.85(d,3H).
[ PREPARATION EXAMPLE 7 ]
Adding 7.3g (0.12mol) of ethanolamine into a three-port reaction vessel, heating to 60 ℃, slowly dropwise adding 19.9g (0.1mol) of 4-bromostyrene epoxide under stirring, and after dropwise adding, keeping the temperature and reacting for 1h to obtain a crude product; and removing unreacted raw materials in vacuum to obtain a purified product G.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.85(s,2H),7.15(s,2H),5.35(s,H),4.86(t,H),3.47(t,2H),3.15(d,2H),2.73(t,2H)，1.85(m,H)，1.65(d,H).
[ PREPARATION EXAMPLE 8 ]
Adding 20.4g (0.2mol) of 3-dimethylaminopropylamine into a three-opening reaction container, heating to 60 ℃, slowly dropwise adding 13.4g (0.1mol) of 2-phenyl propylene oxide under stirring, and after dropwise adding, keeping the temperature and reacting for 3 hours to obtain a crude product; and removing unreacted raw materials in vacuum to obtain a purified product H.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.55(s,2H),7.3(d,2H),7.2(s,H),5.2(s,H),3.65(m,H),3.07(s,2H),2.52(d,2H),2.37(d,2H),2.17(s,6H),1.57(m,2H),1.4(s,3H).
[ PREPARATION EXAMPLE 9 ]
Adding 15.5g (0.12mol) of N-aminoethyl piperazine into a three-port reaction container, heating to 70 ℃, slowly dropwise adding 13.4g (0.1mol) of 2- (4-methylphenyl) ethylene oxide under the stirring state, and after dropwise adding, keeping the temperature and reacting for 4 hours to obtain a crude product; removing unreacted raw materials in vacuum to obtain a purified product I.
Nuclear magnetic hydrogen spectrum: 1 H NMR(CDCl 3 ,400MHz,TMS):δ7.25(s,2H),7.1(s,2H),5.16(s,H),4.87(t,H),3.7(m,H),3.1(d,2H),2.65(m,6H),2.4(d,2H),2.35(d,4H),2.17(s,3H)，1.06(m,H).
[ examples 1 to 9 ]
With the arylalkylamines compounds prepared in the preparation examples as epoxy resin diluents, different epoxy resin compositions were prepared according to the following methods, respectively:
arylalkylolamines, 4-diaminodicyclohexylmethane (wanamine @2110), epoxy resin (E51), as 10: 22: 78 to obtain the epoxy resin composition. The VOC of the aromatic alkylamine compounds and the viscosity, gel time, tensile strength and tensile modulus of the resulting epoxy resin compositions were measured, respectively, and the results are shown in table 2.
Comparative examples 1 to 4
Epoxy resin compositions were prepared and tested for properties in the same manner as in examples without diluent and with conventional diluents such as benzyl alcohol, toluene and butyl glycidyl ether, respectively, and the test results are shown in table 2.
TABLE 2 Performance test results
Description of the drawings: the "blank" in table 2 refers to the control without any diluent added as a blank.
As can be seen from the test results in Table 2, the aryl alcohol amine compound provided by the invention has an obvious dilution effect on the epoxy resin composition, and can meet the application requirements of different dilution degrees; meanwhile, compared with the 25 ℃ gel time of 115min in the blank control of the comparative example 1, the test result shows that when the aryl alcohol amine compound provided by the invention is used as an epoxy resin diluent, the curing and crosslinking of the epoxy resin can be remarkably promoted, the gel time is shortened, the aryl alcohol amine compound can be used as a few promoting type epoxy diluents, and the aryl alcohol amine compound has the advantage of low VOC compared with a benzyl alcohol diluent and can be widely applied. In addition, the cured epoxy resin prepared by the method has obvious improvement on mechanical properties, especially when the aryl alcohol amine compound contains active hydrogen, the aryl alcohol amine compound can be used as a reactive epoxy diluent, and the crosslinking performance of the cured epoxy resin can be further improved, so that the aryl alcohol amine compound provided by the invention expands the types of the epoxy diluent, can show excellent applicability in various aspects, and is suitable for large-scale production and application.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (10)
1. The application of aryl alcohol amine as an epoxy resin diluent is characterized in that the aryl alcohol amine has a structural general formula shown as the following formula I:
wherein R is 1 Selected from H, halogen, C 1 ～C 20 Alkyl or alkoxy or aralkyl of (a), preferably selected from H, halogen, methyl, methoxy;
R 4 selected from H, C 1 ～C 5 Alkyl of (3), preferably H, methyl;
R 2 、R 3 each independently selected from H, optionally substituted or unsubstituted alkyl or cycloalkyl or aralkyl, preferably from C 1 ～C 20 Optionally substituted or unsubstituted alkyl or cycloalkyl or aralkyl, more preferably selected from C 1 ～C 10 Unsubstituted or hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted alkyl, cycloalkyl and C 6 ～C 20 Unsubstituted or hydroxy, amino, iminoAlkyl, vinyl, alkoxy, halogen, and aralkyl substituted with carboxyl.
2. The use according to claim 1, wherein in formula I, R is 2 、R 3 Each independently selected from H, cyclohexyl, phenyl, benzyl, C 1 -C 6 Alcoholic hydroxyl group of (2), C 1 -C 10 Alkyl of (C) 1 -C 6 Methylamino and alkyl piperazine.
3. Use according to claim 1 or 2, for paper processing, for the manufacture of cured epoxy resins, for the manufacture of coatings, adhesives, reinforced or non-reinforced plastics, elastomers, mouldings.
4. An epoxy resin composition, characterized in that the composition comprises a compound represented by formula I or a mixture composed of compounds represented by formula I and at least one polymer capable of being crosslinked;
wherein R is 1 Selected from H, halogen, C 1 ～C 20 Alkyl or alkoxy or aralkyl of (a), preferably selected from H, halogen, methyl, methoxy;
R 4 selected from H, C 1 ～C 5 The alkyl group of (1) is preferably H or methyl.
R 2 、R 3 Each independently selected from H, optionally substituted or unsubstituted alkyl or cycloalkyl or aralkyl, preferably from C 1 ～C 20 More preferably selected from C 1 ～C 10 Unsubstituted alkyl, cycloalkyl and C 6 ～C 20 Unsubstituted aralkyl and C 1 ～C 10 Hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted alkyl, cycloalkyl and C 6 ～C 20 Any of methyl, ethyl, hydroxy, amino, imino, vinyl, alkoxy, halogen, carboxy-substituted aralkyl.
5. The epoxy resin composition according to claim 4, wherein the mass ratio of the compound of formula I or the mixture of compounds of formula I to the crosslinkable polymer is from 1:99 to 60:40, preferably from 5:95 to 30: 70, more preferably 10:90 to 20: 80.
6. the epoxy resin composition according to claim 4 or 5, wherein the crosslinkable polymer comprises:
a) an epoxy resin;
b) a curing agent;
c) optionally an additive.
7. The epoxy resin composition according to claim 6, wherein the epoxy resin is one or more of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, and a glycidyl ether type epoxy resin.
8. The epoxy resin composition according to claim 6, wherein the curing agent is selected from the group consisting of amine-based curing agents, acid anhydride-based curing agents;
preferably, the amine curing agent is one or more of aliphatic amine, polyether amine, alicyclic amine, aromatic amine, polyamide and modified substances thereof, wherein the aliphatic amine, polyether amine, alicyclic amine, aromatic amine and polyamide at least contain two amino functional groups;
preferably, the acid anhydride curing agent is one or more of fatty acid anhydride containing at least one acid anhydride functional group, aromatic acid anhydride and modified substance thereof.
9. The epoxy resin composition of claim 6, wherein the additive comprises optionally a filler, a functional aid, a non-reactive diluent;
preferably, the filler is one or more of calcium carbonate, titanium dioxide, mica powder, talcum powder, montmorillonite, wollastonite powder, barium sulfate, asbestos powder and argil;
preferably, the functional auxiliary agent is one or more of a dispersing agent, an antifoaming agent, a leveling agent, a thixotropic agent, a wetting dispersing agent, an accelerator, a flexibilizer and a plasticizer;
preferably, the non-reactive diluent is one or more of xylene, benzyl alcohol, toluene, benzene, dibutyl phthalate, dioctyl phthalate and acetone.
10. The epoxy resin composition according to claim 6, wherein the crosslinkable polymer comprises the following components in parts by weight:
10-70 parts by weight of epoxy resin,
10-40 parts by weight of a curing agent,
0-30 parts of additive.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4130510A (en) * | 1976-04-14 | 1978-12-19 | Hitachi Chemical Co., Ltd. | Curing of epoxy resin systems using halfester compounds containing aliphatic tertiary amino groups |
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| WO2021152281A1 (en) * | 2020-01-28 | 2021-08-05 | Paul Jones | Mannich base epoxy curative, cured epoxy resins thereof and methods of preparing the same |
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2022
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| US4130510A (en) * | 1976-04-14 | 1978-12-19 | Hitachi Chemical Co., Ltd. | Curing of epoxy resin systems using halfester compounds containing aliphatic tertiary amino groups |
| US4767805A (en) * | 1984-08-07 | 1988-08-30 | Mitsubishi Rayon Co., Ltd. | Intermediate for composite materials |
| WO2003043973A2 (en) * | 2001-11-23 | 2003-05-30 | Sigma Coatings B.V. | Amine phenolic compounds and their use as hardeners and/or accelerators in epoxy coatings |
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| US20110118469A1 (en) * | 2009-11-04 | 2011-05-19 | Massachusetts Institute Of Technology | Continuous flow synthesis of amino alcohols using microreactors |
| CN110099944A (en) * | 2016-12-19 | 2019-08-06 | 赢创德固赛有限公司 | Multiamide and amidoamines derived from hydroxy alkyl polyamines: the epoxy hardener having improved properties |
| CN109868037A (en) * | 2019-02-20 | 2019-06-11 | 常州菲胜图自动化仪器有限公司 | A kind of preparation method of epoxy conductive paint |
| CN110157297A (en) * | 2019-05-30 | 2019-08-23 | 陈理抗 | A kind of metal surface anticorrosive paint |
| CN110229310A (en) * | 2019-07-16 | 2019-09-13 | 上海骁鹏新材料科技有限公司 | Modified aqueous epoxy resin curing agent and preparation method thereof |
| WO2021152281A1 (en) * | 2020-01-28 | 2021-08-05 | Paul Jones | Mannich base epoxy curative, cured epoxy resins thereof and methods of preparing the same |
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