CN113861383B - Epoxy resin containing naphthalene ring structure and preparation method thereof - Google Patents
Epoxy resin containing naphthalene ring structure and preparation method thereof Download PDFInfo
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- CN113861383B CN113861383B CN202111213609.3A CN202111213609A CN113861383B CN 113861383 B CN113861383 B CN 113861383B CN 202111213609 A CN202111213609 A CN 202111213609A CN 113861383 B CN113861383 B CN 113861383B
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- epoxy resin
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 94
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 94
- 125000001624 naphthyl group Chemical group 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 125000003277 amino group Chemical group 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 9
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims description 7
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 claims description 5
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 claims description 5
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical group NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 claims description 3
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 claims description 3
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical class C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims description 3
- MCVKPZKRJSXROY-UHFFFAOYSA-N cyclobutane;oxirane Chemical compound C1CO1.C1CCC1 MCVKPZKRJSXROY-UHFFFAOYSA-N 0.000 claims description 3
- ZKTCOEWQIXZOCZ-UHFFFAOYSA-N cyclopropane oxirane Chemical compound O1CC1.C1CC1 ZKTCOEWQIXZOCZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000007530 organic bases Chemical class 0.000 claims description 3
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical class C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 238000006798 ring closing metathesis reaction Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 150000001350 alkyl halides Chemical class 0.000 description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- -1 glycerol amine Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- OKBVMLGZPNDWJK-UHFFFAOYSA-N naphthalene-1,4-diamine Chemical compound C1=CC=C2C(N)=CC=C(N)C2=C1 OKBVMLGZPNDWJK-UHFFFAOYSA-N 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- LIUKLAQDPKYBCP-UHFFFAOYSA-N 4-bromonaphthalen-1-amine Chemical compound C1=CC=C2C(N)=CC=C(Br)C2=C1 LIUKLAQDPKYBCP-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
-
- 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
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
A high-temperature-resistant high-modulus epoxy resin and a preparation method thereof. An epoxy resin containing naphthalene ring structure is provided, and the epoxy resin is prepared by reacting the following components: (a) a naphthalene derivative represented by the following formula 1, wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is the reaction product of an amine group and (b) an epoxy-terminated compound; 4, 4-diaminodiphenyl sulfone as curing agent.
Description
Technical Field
The invention relates to a high-modulus high-temperature-resistant condensed water glycerol amine type epoxy resin containing naphthalene ring structure and a preparation method thereof.
Background
Epoxy resins refer to a generic term for a class of polymers containing two or more epoxy groups in the molecule. As an important thermosetting resin, epoxy resin can be subjected to crosslinking reaction with amine or anhydride curing agents to form an insoluble and infusible polymer with a three-dimensional network structure, and the epoxy resin is widely applied to the fields of coating, adhesives, electronic and electrical appliance packaging materials, composite material matrix resins and the like.
However, with the rapid development of aerospace, electronic and electric industries and the continuous expansion of application fields of composite materials, common epoxy resins cannot meet the use requirements, and epoxy resins face the problem of high performance, wherein the synthesis of high-modulus high-temperature-resistant epoxy resins has become one of the research hot spots.
For example, patent CN112694597a discloses a method for preparing a high modulus heterocyclic epoxy resin, which is prepared by the examples, and after curing with a curing agent, the flexural modulus is 3.2GPa. CN109422867B discloses a high-modulus low-viscosity epoxy resin and a preparation method, the tensile modulus of the epoxy resin prepared by the example is between 3.4 and 3.6GPa after curing with a curing agent. CN101831051a discloses a high temperature resistant epoxy resin containing naphthalene ring, dicyclopentadiene ring and imide structure and its preparation method, and the epoxy resin prepared in the embodiment thereof and curing agent are cured, and the glass transition temperature (Tg) is between 226.1-232.1 ℃. CN103059265A discloses a halogen-free flame-retardant epoxy resin containing naphthalene ring structure and a preparation method thereof, after the epoxy resin prepared by the embodiment is cured with a curing agent, tg is 211.7 ℃, tensile modulus is 3.57GPa, and flexural modulus is 3.01GPa. CN109651596a discloses an epoxy resin containing a naphthalene ring structure, which is prepared by reacting naphthalene ring phenol a with epichlorohydrin.
However, the epoxy resins synthesized by the prior art represented by the above-mentioned documents still cannot satisfy the high performance requirements of modulus > 4GPa and Tg > 250 ℃ after curing at the same time. Therefore, there is an urgent need to develop a high modulus, high temperature resistant epoxy resin that meets both of the above two requirements.
Disclosure of Invention
The application provides the high-modulus high-temperature-resistant condensed water glycerinum type epoxy resin containing naphthalene ring structure, which aims to overcome the defects of the prior art and meet the requirement that the high performance of the epoxy resin condensate can reach the modulus (tensile modulus, flexural modulus and the like) of more than 4GPa and Tg of more than 250 ℃.
The second purpose of the application is to provide a preparation method of the high-modulus high-temperature-resistant condensed water glycerol amine type epoxy resin containing naphthalene ring structure.
In one aspect, the application provides an epoxy resin containing a naphthalene ring structure, wherein the epoxy resin is prepared by reacting the following components:
(1) The reaction product of (a) and (b) below:
(a) Naphthalene derivatives represented by the following formula 1:
Wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is an amine group;
(b) An epoxy-terminated compound, and
(2) Curing agent 4, 4-diaminodiphenyl sulfone.
In one embodiment of the application, R 1-R8 each independently represents H, an amine group, a C1-C10 alkyl group, or a halogen; preferably, R 1-R8 each independently represents H, an amine group, a C1-C8 alkyl group, or a halogen; more preferably, R 1-R8 each independently represents H, an amine group, a C1-C4 alkyl group, or a halogen; most preferably, R 1-R8 each independently represents H, an amine group, a methyl group, an ethyl group, a propyl group, a butyl group, or a halogen.
In one embodiment of the application, at least one of R 1-R8 is an amine group; preferably, at least two (e.g., one to four, i.e., one, two, three, or four) of R 1-R8 are amine groups.
In one example of the present application, the naphthalene derivative represented by formula 1 is selected from one or more of 1, 8-naphthalene diamine, 1, 5-naphthalene diamine, 2, 3-naphthalene diamine, 2, 6-naphthalene diamine, 1-naphthalene amine, and 4-bromo-1-naphthalene cyclic amine.
In one embodiment of the application, the epoxy-terminated compound is a compound containing one or more structures I
Preferably, the epoxy-terminated compound is a C1-C20 alkane, C1-C20 haloalkane, hydroxy-substituted C1-C20 alkane, C3-C20 cycloalkane, C3-C20 halocycloalkane or hydroxy-substituted C3-C20 cycloalkane containing one or more of the above structures I; more preferably, the epoxy-terminated compound is selected from the group consisting of propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, halogenated propylene oxide, halogenated butylene oxide, halogenated pentylene oxide, halogenated hexylene oxide, ethylene oxide cyclopropane, ethylene oxide cyclobutane, and combinations thereof; most preferably, the epoxy-terminated compound is selected from the group consisting of propylene oxide, epichlorohydrin, and combinations thereof.
In one example of the present application, the epoxy resin comprises a structure represented by the following formula (2):
wherein, in the formula: R1-R8 each independently represent H, C-C20 alkyl or halogen, provided that at least one of R1-R8 is a glycidylamine structure represented by the formula:
in another aspect, the present application provides a method for preparing the epoxy resin of the present application, comprising the steps of:
(1) The naphthalene derivative shown in the formula (1), the epoxy group end-capped compound and the catalyst are subjected to ring opening reaction,
Wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is an amine group;
(2) Adding alkali into the product obtained in the step (1), and performing ring closure reaction to obtain a reaction product; and
(3) And (3) reacting the reaction product obtained in the step (2) with a curing agent 4, 4-diaminodiphenyl sulfone to obtain the epoxy resin.
In one example of the present application, the catalyst comprises one or more of water, ethanol, propanol, ethylene glycol, isopropanol.
In one example of the present application, in the above step (1), the molar ratio of the naphthalene derivative represented by formula (1), the epoxy-terminated compound and the catalyst is 1: (4-20): (2-6), preferably 1: (8-16): (2-6).
In one example of the present application, in the above step (2), the base includes an inorganic base and/or an organic base, such as sodium hydroxide or potassium hydroxide; preferably, the molar ratio of hydroxyl groups contained in the base in the step (2) to active hydrogen in the naphthalene derivative represented by the formula (1) is (1-2): 1, preferably (1.2-1.6): 1.
From the molecular design point of view, the naphthalene ring with a large-volume rigid structure is introduced into the epoxy skeleton. The naphthalene ring molecules are more easily closely stacked due to steric hindrance effect and the planar structure, so that the bond rotation capability is reduced, the movement of the epoxy resin chain segment is weakened, the rigidity of the whole polymer chain segment is increased, and the heat resistance and the modulus of the epoxy condensate are greatly improved. In addition, the polyfunctional epoxy groups contained in the molecules enable the epoxy resin to have higher crosslinking density in curing, and the synergistic effect of the polyfunctional epoxy groups and the epoxy resin enables the epoxy resin to have high modulus and high temperature resistance after curing. The epoxy resin can meet the requirements of high performance with modulus more than 4GPa and Tg more than 250 ℃ after being cured.
Detailed Description
In the present invention, unless otherwise specified, the percentage (%) or the part means a weight percentage or a part by weight with respect to the composition.
In the present invention, the components involved or preferred components thereof may be combined with each other to form a new technical solution, unless otherwise specified.
In the present invention, all the embodiments mentioned herein and the preferred embodiments may be combined with each other to form new technical solutions, if not specifically described.
In the present invention, all technical features mentioned herein and preferred features may be combined with each other to form new technical solutions, if not specifically stated.
In the present invention, the sum of the contents of the respective components in the composition is 100% unless otherwise specified.
In the present invention, the sum of the parts of the components in the composition may be 100 parts by weight, if not stated to the contrary.
In the present invention, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values.
In the present invention, unless otherwise indicated, the integer numerical range "a-b" represents a shorthand representation of any combination of integers between a and b, where a and b are integers. For example, the integer numerical range "1-N" represents 1,2 … … N, where N is an integer.
In the present invention, unless otherwise indicated, "a combination thereof" means a multicomponent mixture of the elements, e.g., two, three, four, and up to the maximum possible multicomponent mixture.
The term "a" as used in this specification means "at least one" unless specifically indicated.
The percentages stated in the present invention (including weight percent) are based on the total weight of the composition, unless otherwise indicated.
"Range" is disclosed herein in the form of lower and upper limits. There may be one or more lower limits and one or more upper limits, respectively. The given range is defined by selecting a lower limit and an upper limit. The selected lower and upper limits define the boundaries of the particular ranges. All ranges that can be defined in this way are inclusive and combinable, i.e., any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for specific parameters, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5.
In this context, unless otherwise indicated, each reaction is carried out at ambient temperature and pressure.
In this context, the individual reaction steps may or may not be carried out sequentially, unless otherwise indicated. For example, other steps may be included between the respective reaction steps, and the order may be exchanged between the reaction steps. Preferably, the reaction processes herein are performed sequentially.
In this document, unless otherwise indicated, the terms "comprising," "including," and the like mean that any other applicable component/monomer may be included in addition to the listed components/monomers.
In one aspect, the application provides an epoxy resin containing a naphthalene ring structure, wherein the epoxy resin is prepared by reacting the following components:
(1) The reaction product of (a) and (b) below:
(a) Naphthalene derivatives represented by the following formula 1:
Wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is an amine group;
(b) An epoxy-terminated compound, and
(2) Curing agent 4, 4-diaminodiphenyl sulfone.
In the above formula (1), R 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or halogen. In a preferred embodiment, R 1-R8 each independently represents H, an amine group, a C1-C10 alkyl group, or a halogen. In another embodiment of the application, R 1-R8 each independently represents H, an amine group, a C1-C8 alkyl group, or a halogen. In another preferred embodiment of the application, R 1-R8 each independently represents H, an amine group, a C1-C4 alkyl group or a halogen. In another preferred embodiment of the application, R 1-R8 each independently represents H, amino, methyl, ethyl, propyl, butyl or halogen. Herein, the halogen represents fluorine, chlorine, bromine or iodine. As used herein, the term "amine group" may be an amine group substituted with-NH 2 or a C1-C20 alkyl (preferably C1-C10 alkyl, more preferably C1-C4 alkyl, most preferably methyl, ethyl, propyl or butyl) group.
In the above formula (1), at least one of R 1-R8 is an amine group. In a preferred embodiment of the application, at least two (e.g., one to four, i.e., one, two, three, or four) of R 1-R8 are amine groups.
In a preferred embodiment of the present application, the naphthalene derivative represented by formula 1 is selected from one or more of 1, 8-naphthalene diamine, 1, 5-naphthalene diamine, 2, 3-naphthalene diamine, 2, 6-naphthalene diamine, 1-naphthalene amine, and 4-bromo-1-naphthalene cyclic amine.
In one embodiment of the application, the epoxy-terminated compound is a compound containing one or more structures I
In another example of the application, the epoxy-terminated compound is a C1-C20 alkane (preferably a C1-C10 alkane, more preferably a C1-C6 alkane, most preferably a C1-C4 alkane), a C1-C20 haloalkane (preferably a C1-C10 haloalkane, more preferably a C1-C6 haloalkane, most preferably a C1-C4 haloalkane), a hydroxy-substituted C1-C20 alkane (preferably a hydroxy-substituted C1-C10 alkane, more preferably a hydroxy-substituted C1-C6 alkane, most preferably a hydroxy-substituted C1-C4 alkane), a C3-C20 cycloalkane (preferably a C3-C10 cycloalkane, more preferably a C3-C8 cycloalkane, most preferably a C3-C6 alkane), a C3-C20 haloalkane (preferably a C3-C10 haloalkane, more preferably a C3-C8 haloalkane, most preferably a C3-C6 haloalkane) or a hydroxy-substituted C3-C20 cycloalkane (preferably a hydroxy-substituted C3-C10 cycloalkane, most preferably a hydroxy-substituted C3-C8 cycloalkane). In another example of the present application, the epoxy-terminated compound is selected from the group consisting of propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, halogenated propylene oxide, halogenated butylene oxide, halogenated pentylene oxide, halogenated hexylene oxide, ethylene oxide cyclopropane, ethylene oxide cyclobutane, and combinations thereof. In a preferred embodiment of the present application, the epoxy-terminated compound is selected from the group consisting of propylene oxide, epichlorohydrin, and combinations thereof. In yet another preferred embodiment of the present application, the epoxy-terminated compound is epichlorohydrin.
In the present application, the amounts of the naphthalene derivative and the epoxy-terminated compound are not particularly limited. In one example of the application, the molar ratio of naphthalene derivative to epoxy-terminated compound is 1: (4-20), preferably 1: (8-16).
The epoxy resins of the present application can also be prepared by adding additional materials (e.g., branching agents) if desired. For the purposes of the present application, branching agents are polyhydric alcohol or polyamine compounds having a molecular weight of up to 599, preferably from 50 to 500, and having at least three hydroxyl, primary amino and/or secondary amino groups per molecule. If used, the branching agent generally comprises no more than 10%, preferably no more than 5% and still more preferably no more than 2% of the total weight of the reactants. Examples of branching agents include polyols such as trimethylol propane, glycerol, trimethylol ethane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, sucrose, sorbitol, pentaerythritol, triethanolamine, diethanolamine, etc., and alkoxylates having a number average molecular weight of up to 599, in particular up to 500.
In one example of the present application, the epoxy resin comprises a structure represented by the following formula (2) or a structure derived from the following formula (2):
wherein, in the formula: R1-R8 each independently represent H, C-C20 alkyl or halogen, provided that at least one of R1-R8 is a glycidylamine structure represented by the formula:
In the above formula (2), R 1-R8 each independently represents H, C-C20 alkyl or halogen. In a preferred embodiment, R 1-R8 each independently represents H, an amine group, a C1-C10 alkyl group, or a halogen. In another embodiment of the application, R 1-R8 each independently represents H, C-C8 alkyl or halogen. In another preferred embodiment of the application, R 1-R8 each independently represents H, C-C4 alkyl or halogen. In another preferred embodiment of the application, R 1-R8 each independently represents H, methyl, ethyl, propyl, butyl or halogen. Herein, the halogen represents fluorine, chlorine, bromine or iodine.
In the above formula (1), at least one of R 1-R8 is a glycidylamine structure represented by the above formula. In a preferred embodiment of the application, at least two (e.g., one to four, i.e., one, two, three or four) of R 1-R8 are glycidylamine structures represented by the above formula.
In another aspect, the present application provides a method for preparing the epoxy resin of the present application, comprising the steps of:
(1) Performing ring opening reaction on naphthalene derivatives shown in the formula (1), epoxy group end-capped compounds and catalysts;
(2) Adding alkali into the product obtained in the step (1), and performing ring closure reaction to obtain a reaction product; and
(3) And (3) reacting the reaction product obtained in the step (2) with a curing agent 4, 4-diaminodiphenyl sulfone to obtain the epoxy resin.
In the step (1), the definition of the naphthalene derivative and the epoxy-terminated compound represented by the formula (1) is the same as that of the above-mentioned part.
In the step (1), the catalyst is a catalyst commonly used in the art, including but not limited to one or more of water, ethanol, propanol, ethylene glycol and isopropanol, preferably one or more of ethanol, water and ethylene glycol.
In the above step (1), the amounts of the naphthalene derivative represented by the formula (1), the epoxy-terminated compound and the catalyst are not particularly limited. In one example of the present application, the molar ratio of naphthalene derivative, epoxy-terminated compound, and catalyst represented by formula (1) is 1: (4-20): (2-6), preferably 1: (8-16): (2-6).
In the above step (1), the temperature of the reaction is not particularly limited. In one embodiment of the application, the reaction temperature is 60-115 ℃, preferably 80-110 ℃.
In the above step (1), the time of the reaction is not particularly limited. In one embodiment of the application, the reaction time is 1 to 16 hours, preferably 4 to 10 hours.
In the above step (2), the base is not particularly limited. In a preferred embodiment of the application, the alkaline solution comprises, but is not limited to, an inorganic and/or organic base, such as sodium hydroxide or potassium hydroxide (which may be a solid or a solution such as an aqueous solution, at a concentration of, for example, 20-100wt%, preferably 30-50 wt%). Preferably, the molar ratio of hydroxyl groups contained in the base described in the above step (2) to active hydrogen (i.e., hydrogen atoms capable of undergoing a ring-opening reaction with the epoxy-terminated compound) in the naphthalene derivative represented by the formula (1) is (1-2): 1, preferably (1.2-1.6): 1.
In the above step (2), the temperature of the reaction is not particularly limited. In one embodiment of the application, the reaction temperature is 20-100 ℃, preferably 40-80 ℃.
In the above step (2), the time of the reaction is not particularly limited. In one embodiment of the application, the reaction time is 1 to 6 hours, preferably 2 to 4 hours.
In the method of the present application, a step of purification may be further included. For example, the epoxy resin obtained in the step (2) is washed with deionized water and is subjected to extraction delamination by using an inert solvent until the water phase is neutral, and then the solvent is removed to obtain the epoxy resin containing the naphthalene ring structure. Preferably, the inert solvent includes, but is not limited to, one or more of toluene, benzene, xylene, methylene chloride, dichloroethane, preferably toluene and/or dichloroethane.
Examples
The invention is further illustrated by the following examples. The examples of the present invention are for better understanding of the present invention, but do not limit the present invention in any way.
Synthesis example 1
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 925g (10 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 1, 8-naphthalene diamine (in formula (1), R 1 and R 8 were each substituted with amino-NH 2, the same applies hereinafter) and 18g (1 mol) of water. The temperature was raised while stirring, and the reaction was continued at 60℃for 16 hours.
After cooling to 20℃160g (4 mol OH-, 100wt% strength) of sodium hydroxide solid were added and the ring closure was maintained for 6 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and then dichloroethane is added into the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The lower oil phase was taken and dichloroethane was distilled off to give 162.4g of 1, 8-naphthalene diamine epoxy resin.
Synthesis example 2
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 740g (8 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 1, 4-naphthalene diamine (in formula (1), R 1 and R 4 were each substituted with amino-NH 2, the same applies hereinafter) and 180g (3 mol) of isopropyl alcohol. The temperature was raised while stirring, and the reaction was carried out at 80℃for 12 hours.
After cooling to 40℃400g of sodium hydroxide solution (2 mol of OH -, concentration 20 wt%) were added and the ring closure reaction was maintained for 1 hour.
The epichlorohydrin is recovered by reduced pressure distillation, and then the crude epoxy resin is extracted by adding dimethylbenzene into the material. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The upper oil phase was taken and xylene was distilled off to obtain 152.8g of 1, 4-naphthalenediamine epoxy resin.
Synthesis example 3
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 555g (6 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 1, 5-naphthalene diamine (in formula (1), R 1 and R 5 were each substituted with amino-NH 2, the same applies hereinafter) and 115g (2.5 mol) of ethanol. The temperature was raised while stirring, and the reaction was carried out at 90℃for 10 hours.
After cooling to 60℃192g (2.4 mol OH -, 50 wt%) of sodium hydroxide solution were added and the ring closure was maintained for 4 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and toluene is added to the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The upper oil phase was taken and toluene was distilled off to obtain 181.5g of 1, 5-naphthalene diamine epoxy resin.
Synthesis example 4
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 462.5g (5 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) and 168g (2.8 mol) of propanol, 2, 3-naphthalene diamine (in formula (1), R 2 and R 3 were each substituted with amino-NH 2, the same applies below). The temperature was raised while stirring, and the reaction was carried out at 100℃for 8 hours.
After cooling to 80℃373g (2.8 mol OH -, 30wt% strength) of sodium hydroxide solution was added and the ring closure was maintained for 3 hours.
And (3) distilling under reduced pressure to recover epichlorohydrin, and then adding benzene into the material to extract crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The upper oil phase was taken and benzene was distilled off to obtain 172g of 2, 3-naphthalene diamine epoxy resin.
Synthesis example 5
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 370g (4 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 2, 6-naphthalene diamine (in formula (1), R 2 and R 6 were each substituted with amino-NH 2, the same applies hereinafter) and 74.4g (1.2 mol) of ethylene glycol. The temperature was raised while stirring, and the reaction was carried out at 110℃for 6 hours.
After cooling to 90℃800g (2 mol OH -, 10wt% strength) of sodium hydroxide solution was added and the ring closure reaction was maintained for 6 hours.
The epichlorohydrin is recovered by distillation under reduced pressure, and then methylene chloride is added into the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The lower oil phase was taken and the methylene chloride was distilled off to obtain 143.3g of 2, 6-naphthalene diamine epoxy resin.
Synthesis example 6
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively charged 740g (8 mol) of epichlorohydrin, 71.5g (0.5 mol, 1mol of active hydrogen therein) of 1-naphthylamine (in formula (1), R 1 was substituted with amino-NH 2, the same applies hereinafter) and 124g (2 mol) of ethylene glycol. The temperature was raised while stirring, and the reaction was carried out at 115℃for 8 hours.
After cooling to 100℃120g (1.5 mol OH -, 50 wt%) of sodium hydroxide solution was added and the ring closure was maintained for 2 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and toluene is added to the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The upper oil phase was taken and toluene was distilled off to obtain 105g of 1-naphthalenyl amine epoxy resin.
Synthesis example 7
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively charged 925g (10 mol) of epichlorohydrin, 4-bromo-1-naphthylamine (in formula (1), R 1 was substituted with amino-NH 2, R 4 was substituted with bromine atom, the same shall apply hereinafter) 111g (0.5 mol, active hydrogen 1 mol) and 124g (2 mol) of ethylene glycol. The temperature was raised while stirring, and the reaction was carried out at 100℃for 6 hours.
After cooling to 50℃173g (1.3 mol OH -, 30 wt%) of sodium hydroxide solution were added and the ring closure was maintained for 4 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and then dichloroethane is added into the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The lower oil phase was taken and dichloroethane was distilled off to obtain 142g of 4-bromo-1-naphthalen-cyclic amine epoxy resin.
Synthesis example 8
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively charged 555g (6 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 1, 5-naphthalene diamine (in the formula (1), R 1 and R 5 were each substituted with amino-NH 2, the same applies hereinafter) and 74.4g (1.2 mol) of ethylene glycol. The temperature was raised while stirring, and the reaction was carried out at 100℃for 6 hours.
After cooling to 70℃192g (2.4 mol OH -, 50 wt%) of sodium hydroxide solution were added and the ring closure was maintained for 6 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and then the crude epoxy resin is extracted by adding dimethylbenzene into the material. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The upper oil phase was taken and xylene was distilled off to obtain 184g of 1, 5-naphthalene diamine epoxy resin.
Synthesis example 9
To a 2L four port round bottom flask equipped with a stirrer, thermometer and reflux condenser were successively added 925g (10 mol) of epichlorohydrin, 79g (0.5 mol, 2mol of active hydrogen) of 1, 8-naphthalene diamine (in formula (1), R 1 and R 8 were each substituted with amino-NH 2, the same applies hereinafter) and 115g (2.5 mol) of ethanol. The temperature was raised while stirring, and the reaction was carried out at 90℃for 10 hours.
After cooling to 40℃160g (4 mol OH-, 100wt% strength) of sodium hydroxide solid were added and the ring closure was maintained for 6 hours.
The epichlorohydrin is recovered by reduced pressure distillation, and then dichloroethane is added into the material to extract the crude epoxy resin. Deionized water is continuously added, and the mixture is washed for a plurality of times until the pH value of the water phase is neutral. The lower oil phase was taken and the dichloroethane was distilled off to obtain 165g of 1, 8-naphthalene diamine epoxy resin.
Synthesis of comparative example 1
As described in CN109651596A, in a 1000ml four-necked round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel and a condenser were placed 135g of epichlorohydrin, 78g of 1, 6-dihydroxynaphthalene and 0.78g of tetrabutylammonium bromide as catalyst, and the temperature was raised under stirring to react at 120℃for 1 hour. Then cooling to 30 ℃, dropwise adding 59g of sodium hydroxide, maintaining the ring-closure reaction for 5 hours, then steaming out epichlorohydrin, adding methyl ethyl ketone into the reaction liquid to extract epoxy resin, taking an oil phase, and steaming out methyl ethyl ketone after water washing to obtain 90g of 1, 6-dihydroxynaphthalene epoxy resin.
Application example 1
The epoxy resins prepared in synthetic examples 1 to 9 and comparative synthetic example 1 and commercial bisphenol a epoxy resin (E51) were uniformly mixed with the epoxy resin in an equimolar ratio of the curing dose to the epoxy value using 4, 4-diaminodiphenyl sulfone (DDS) as a curing agent, added to a sample model, and then cured in an oven according to a curing procedure of 150 ℃ +2h+180 ℃ +4h+200 ℃ +2h. The cured samples obtained were tested to obtain Tg according to ASTM D7028, tensile and flexural modulus according to GB/T2567 method. The specific data are shown in Table 1.
Comparative example 1 was used
The epoxy resins prepared in synthetic examples 1 to 9 and comparative synthetic example 1 and commercial bisphenol a epoxy resin (E51) were uniformly mixed with the epoxy resin in an equimolar ratio of the curing dose to the epoxy value, added to a sample model, and then cured in an oven according to a curing procedure of 120 ℃ 2h +150 ℃ 4h +180 ℃ 2 h. The cured samples obtained were tested to obtain Tg according to ASTM D7028, tensile and flexural modulus according to GB/T2567 method. The specific data are shown in Table 2.
Comparative example 2 was used
The epoxy resins prepared in synthetic examples 1 to 9 and comparative synthetic example 1 and commercial bisphenol a epoxy resin (E51) were uniformly mixed with the epoxy resin in an equimolar ratio of the curing dose to the epoxy value, added to a sample model, and then cured in an oven according to a curing procedure of 120 ℃ 2h+150 ℃ 4h+180 ℃ 2h. The cured samples obtained were tested to obtain Tg according to ASTM D7028, tensile and flexural modulus according to GB/T2567 method. The specific data are shown in Table 3.
Comparative example 3 was used
The epoxy resins prepared in synthetic examples 1 to 9 and comparative synthetic example 1 and commercial bisphenol a epoxy resin (E51) were uniformly mixed with the epoxy resin in an equimolar ratio of the curing dose to the epoxy value, added to a sample model, and then cured in an oven according to a curing procedure of 140 ℃ +2h+170 ℃ +4h+200 ℃ +2h. The cured samples obtained were tested to obtain Tg according to ASTM D7028, tensile and flexural modulus according to GB/T2567 method. The specific data are shown in Table 4.
Comparative example 4 was used
The epoxy resins prepared in synthetic examples 1 to 9 and comparative synthetic example 1 and commercial bisphenol a epoxy resin (E51) were uniformly mixed with the epoxy resin in an equimolar ratio of the curing dose to the epoxy value using 4, 4-diaminodiphenylmethane (DDM) as a curing agent, added to a sample model, and then cured in an oven according to a curing procedure of 150 ℃ 2h+180 ℃ 4h+200 ℃ 2h. The cured samples obtained were tested to obtain Tg according to ASTM D7028, tensile and flexural modulus according to GB/T2567 method. The specific data are shown in Table 5.
Table 1 application example 1 data
Table 2 application of comparative example 1 data
Table 3 application of comparative example 2 data
Table 4 application of comparative example 3 data
Table 5 application of comparative example 4 data
In the data of application example 1 and application comparisons 1-4, the Tg and modulus of the cured casting of the epoxy resins prepared in Synthesis examples 1-9 were significantly higher than those of comparative examples 1 and E51 epoxy resins;
Compared with the data of comparative examples 1-4, the Tg and modulus of the casting body after curing by using the epoxy resin prepared in synthetic examples 1-9 in example 1 reach the expected requirements of high performance of modulus > 4GPa and Tg > 250 ℃, which shows that the naphthalene ring-containing epoxy resin prepared in the invention under a specific curing agent has excellent heat resistance and high modulus.
Claims (22)
1. An epoxy resin containing naphthalene ring structure, which is prepared by reacting the following components:
(1) The reaction product of (a) and (b) below:
(a) Naphthalene derivatives represented by the following formula 1:
Wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is an amine group;
(b) An epoxy-terminated compound, and
(2) Curing agent 4, 4-diaminodiphenyl sulfone.
2. The epoxy resin of claim 1, wherein each R 1-R8 independently represents H, an amine group, a C1-C10 alkyl group, or a halogen.
3. The epoxy resin of claim 1, wherein each R 1-R8 independently represents H, an amine group, a C1-C8 alkyl group, or a halogen.
4. The epoxy resin of claim 1, wherein each R 1-R8 independently represents H, an amine group, a C1-C4 alkyl group, or a halogen.
5. The epoxy resin of claim 1, wherein each R 1-R8 independently represents H, an amine group, a methyl group, an ethyl group, a propyl group, a butyl group, or a halogen.
6. The epoxy resin of claim 1, wherein at least one of R 1-R8 is an amine group.
7. The epoxy resin of claim 1, wherein at least two of R 1-R8 are amine groups.
8. The epoxy resin of claim 1, wherein one, two, three, or four of R 1-R8 are amine groups.
9. The epoxy resin according to claim 1, wherein the naphthalene derivative represented by formula 1 is selected from one or more of 1, 8-naphthalene diamine, 1, 5-naphthalene diamine, 2, 3-naphthalene diamine, 2, 6-naphthalene diamine, 1-naphthalene amine and 4-bromo-1-naphthalene cyclic amine.
10. The epoxy resin of claim 1 wherein the epoxy-terminated compound is a compound containing one or more structures I
11. The epoxy resin of claim 1, wherein the epoxy-terminated compound is a C1-C20 alkane, C1-C20 haloalkane, hydroxy-substituted C1-C20 alkane, C3-C20 cycloalkane, C3-C20 halocycloalkane, or hydroxy-substituted C3-C20 cycloalkane containing one or more of structure I above.
12. The epoxy resin of claim 1, wherein the epoxy-terminated compound is selected from the group consisting of propylene oxide, butylene oxide, pentylene oxide, hexylene oxide, halogenated propylene oxide, halogenated butylene oxide, halogenated pentylene oxide, halogenated hexylene oxide, ethylene oxide cyclopropane, ethylene oxide cyclobutane, and combinations thereof.
13. The epoxy resin of claim 1, wherein the epoxy-terminated compound is selected from the group consisting of propylene oxide, epichlorohydrin, and combinations thereof.
14. The epoxy resin according to claim 1, wherein the epoxy resin comprises a structure represented by the following formula (2):
wherein, in the formula: R1-R8 each independently represent H, C-C20 alkyl or halogen, provided that at least one of R1-R8 is a glycidylamine structure represented by the formula:
15. A method of preparing the epoxy resin of claim 1, the method comprising the steps of:
(1) The naphthalene derivative shown in the formula (1), the epoxy group end-capped compound and the catalyst are subjected to ring opening reaction,
Wherein: r 1-R8 each independently represents H, an amine group, a C1-C20 alkyl group, or a halogen, provided that at least one of R 1-R8 is an amine group;
(2) Adding alkali into the product obtained in the step (1), and performing ring closure reaction to obtain a reaction product; and
(3) And (3) reacting the reaction product obtained in the step (2) with a curing agent 4, 4-diaminodiphenyl sulfone to obtain the epoxy resin.
16. The method of claim 15, wherein the catalyst comprises one or more of water, ethanol, propanol, ethylene glycol, isopropanol.
17. The method according to claim 15, wherein in the step (1), the molar ratio of the naphthalene derivative represented by the formula (1), the epoxy-terminated compound and the catalyst is 1: (4-20): (2-6).
18. The method according to claim 15, wherein in the step (1), the molar ratio of the naphthalene derivative represented by the formula (1), the epoxy-terminated compound and the catalyst is 1: (8-16): (2-6).
19. The method of claim 15, wherein in the step (2), the base comprises an inorganic base and/or an organic base.
20. The method of claim 15, wherein in the step (2), the alkali comprises sodium hydroxide or potassium hydroxide.
21. The process according to claim 15, wherein the molar ratio of hydroxyl groups contained in the base in the step (2) to active hydrogen in the naphthalene derivative represented by the formula (1) is (1-2): 1.
22. The process according to claim 15, wherein the molar ratio of hydroxyl groups contained in the base in the step (2) to active hydrogen in the naphthalene derivative represented by the formula (1) is 1.2 to 1.6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831051A (en) * | 2010-05-07 | 2010-09-15 | 黄山市善孚化工有限公司 | High-temperature-resistant epoxy resin containing naphthalene ring, dicyclopentadiene ring and imide structure and preparation method thereof |
| JP2012121962A (en) * | 2010-12-07 | 2012-06-28 | Nippon Kayaku Co Ltd | Epoxy resin composition, prepreg, and cured product of the same |
| CN109337066A (en) * | 2018-09-28 | 2019-02-15 | 浙江大学 | One kind having reactivity, diffluent rigid chain polymer and preparation method thereof and composition |
| CN109651596A (en) * | 2018-12-24 | 2019-04-19 | 上海华谊树脂有限公司 | A kind of epoxy resin and preparation method thereof containing naphthalene ring |
| CN111777741A (en) * | 2020-08-04 | 2020-10-16 | 上海华谊树脂有限公司 | Tetraglycidyl amine epoxy resin and preparation method thereof |
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| KR20120101096A (en) * | 2009-12-02 | 2012-09-12 | 다우 글로벌 테크놀로지스 엘엘씨 | Epoxy resin compositions |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831051A (en) * | 2010-05-07 | 2010-09-15 | 黄山市善孚化工有限公司 | High-temperature-resistant epoxy resin containing naphthalene ring, dicyclopentadiene ring and imide structure and preparation method thereof |
| JP2012121962A (en) * | 2010-12-07 | 2012-06-28 | Nippon Kayaku Co Ltd | Epoxy resin composition, prepreg, and cured product of the same |
| CN109337066A (en) * | 2018-09-28 | 2019-02-15 | 浙江大学 | One kind having reactivity, diffluent rigid chain polymer and preparation method thereof and composition |
| CN109651596A (en) * | 2018-12-24 | 2019-04-19 | 上海华谊树脂有限公司 | A kind of epoxy resin and preparation method thereof containing naphthalene ring |
| CN111777741A (en) * | 2020-08-04 | 2020-10-16 | 上海华谊树脂有限公司 | Tetraglycidyl amine epoxy resin and preparation method thereof |
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