CN114316274A - POSS (polyhedral oligomeric silsesquioxane) modified urea derivative, preparation method thereof and epoxy resin composition - Google Patents
POSS (polyhedral oligomeric silsesquioxane) modified urea derivative, preparation method thereof and epoxy resin composition Download PDFInfo
- Publication number
- CN114316274A CN114316274A CN202111665206.2A CN202111665206A CN114316274A CN 114316274 A CN114316274 A CN 114316274A CN 202111665206 A CN202111665206 A CN 202111665206A CN 114316274 A CN114316274 A CN 114316274A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- type epoxy
- poss
- modified urea
- urea derivative
- 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 168
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 168
- 150000003672 ureas Chemical class 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000011521 glass Substances 0.000 claims description 38
- 229920003986 novolac Polymers 0.000 claims description 15
- 230000002787 reinforcement Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- -1 aralkyl phenol Chemical compound 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 10
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000174 eucryptite Inorganic materials 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000002557 mineral fiber Substances 0.000 claims description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 3
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 claims description 3
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 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 4
- 239000011247 coating layer Substances 0.000 claims 1
- 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 1
- 238000001879 gelation Methods 0.000 abstract description 10
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004202 carbamide Substances 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011342 resin composition Substances 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000010125 resin casting Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 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 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08G59/18—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
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- 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
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- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- 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
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention relates to the field of organic synthesis, in particular to a POSS modified urea derivative, a preparation method thereof and an epoxy resin composition. According to the invention, a polyhedral oligomeric silsesquioxane (POSS) framework is connected with urea with a certain chain length to prepare the POSS modified urea derivative shown in the formula I, and the derivative can be used as a curing agent of epoxy resin. By adopting the curing agent, the epoxy resin can be cured at a high speed at a moderate temperature of about 150 ℃ and can be cured at a speed of about 2.5min, and compared with the curing time in hours at the temperature in the prior art, the efficiency is greatly improved; in addition, the gelation time before curing can be kept not too short, the maximum time can reach 3.2min, and enough operation time is reserved. Meanwhile, the product obtained by the rapid curing also has higher performance, and has the advantages of high impact strength, high bending modulus, good heat-resistant stability and the like.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a POSS modified urea derivative, a preparation method thereof and an epoxy resin composition.
Background
The epoxy resin condensate has excellent bonding strength and high and low temperature resistance, good dielectric property and easy processing and forming, so the epoxy resin condensate is widely applied to the fields of aerospace, construction, machinery and the like. However, epoxy resins have problems of incomplete reaction and long curing time when cured at medium temperature (about 150 ℃); if the curing rate is artificially increased at a medium temperature, the resultant cured product will have high brittleness and low impact strength, and thus, toughening and modification are required. In the conventional technology, a toughening agent such as polyamide, polyetheramine, polyurethane or rubber is usually added to improve the toughness of an epoxy resin cured product, but the toughness and the heat resistance stability of the material are also reduced.
Disclosure of Invention
Based on the above, it is necessary to provide a POSS modified urea derivative and a preparation method thereof, wherein the POSS modified urea derivative can be used as a curing agent for epoxy resin, so that the epoxy resin can be rapidly cured at a medium temperature, and the cured product has the advantages of high impact strength, high bending modulus and good heat resistance stability.
In one aspect of the present invention, a POSS modified urea derivative is provided having a structure represented by formula I:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2～R5each occurrence is independently selected from-H, -D, -F, -Cl, -Br, methyl, methoxy or ethyl;
are attachment sites.
In some embodiments, a POSS modified urea derivative has the structure shown in formula II:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or 1, 4-phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2、R4、R5each occurrence is independently selected from-H, methyl or ethyl;
are attachment sites.
In another aspect of the present invention, a method for preparing the POSS modified urea derivative is provided, which comprises the following steps:
reacting a compound shown in a formula III, a compound shown in a formula IV and carbonyldiimidazole under the protection of nitrogen or argon at the temperature of 20-35 ℃ to prepare the POSS modified urea derivative;
in another aspect of the present invention, an epoxy resin composition is also provided, which comprises the following components by mass:
100 parts of epoxy resin,
5-53 parts of POSS modified urea derivative,
0-150 parts of a filler and a solvent;
wherein the POSS modified urea derivative is the POSS modified urea derivative.
In some embodiments, the epoxy resin is selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, phenol type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, dicyclopentadiene type epoxy resin, phenol type epoxy resin, anthracene type epoxy resin, phenol type epoxy resin, norbornene type epoxy resin, and the like, One or more of an aralkyl phenol type epoxy resin, an epoxy resin having an arylene ether structure in a molecule, an alicyclic epoxy resin, a polyhydric alcohol type epoxy resin, a silicon-containing epoxy resin, a nitrogen-containing epoxy resin, a phosphorus-containing epoxy resin, a glycidyl amine epoxy resin, and a glycidyl ester epoxy resin.
In some embodiments, the filler is selected from one or more of silica, silica glass frit, mica powder, hollow glass beads, microcrystalline glass, eucryptite, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, clay, kaolin, composite silica fume, E glass frit, D glass frit, L glass frit, M glass frit, S glass frit, T glass frit, NE glass frit, and Q glass frit.
The invention also provides an epoxy resin coating which is formed by curing the epoxy resin composition of any one of the embodiments.
The present invention also provides a prepreg comprising a reinforcement and the epoxy resin composition of any one of the preceding embodiments adhered to a surface of the reinforcement; or, the coating comprises a reinforcement body and the epoxy resin coating arranged on the surface of the reinforcement body.
In some embodiments, the reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.
The invention also provides a laminate comprising one or more sheets of a prepreg according to any one of the preceding embodiments.
The invention also provides a metal foil-clad laminate which comprises the laminate and metal foils arranged on one side or two sides of the laminate.
The invention also provides a printed wiring board which comprises the laminated board and/or the metal foil-clad laminated board.
The POSS modified urea derivative shown in the formula I is prepared by connecting a polyhedral oligomeric silsesquioxane (POSS) framework with urea with a certain chain length, and can be used as a curing agent of epoxy resin, so that the epoxy resin can be cured at a high speed at a medium temperature of about 150 ℃ and can be cured at the fastest speed of about 2.5min, and compared with the curing time of taking hours as a unit at the temperature in the prior art, the efficiency is greatly improved; in addition, the gelation time before curing can be kept not too short, the maximum time can reach 3.2min, and enough operation time is reserved. Meanwhile, the product obtained by the rapid curing also has higher performance, and has the advantages of high impact strength, high bending modulus, good heat-resistant stability and the like.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the accompanying examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise. In the description of the present invention, "a plurality" means at least one, e.g., one, two, etc., unless specifically limited otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, the numerical intervals are regarded as continuous, and include the minimum and maximum values of the range and each value between the minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
The percentage contents referred to in the present invention mean, unless otherwise specified, mass percentages for solid-liquid mixing and solid-solid phase mixing, and volume percentages for liquid-liquid phase mixing.
The percentage concentrations referred to in the present invention refer to the final concentrations unless otherwise specified. The final concentration refers to the ratio of the additive component in the system to which the component is added.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a certain temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In one aspect of the present invention, a POSS modified urea derivative is provided having a structure represented by formula I:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2～R5each occurrence is independently selected from-H, -D, -F, -Cl, -Br, methyl, methoxy or ethyl;
are attachment sites.
Polyhedral oligomeric silsesquioxane (POSS) is a high-performance organic-inorganic hybrid material, POSS is used as an inorganic component, an organic substituent group connected to a silicon atom is used as an organic component, an inorganic phase and an organic phase are combined through a strong chemical bond, the problems of inorganic particle aggregation and weak bonding force of two-phase interfaces are solved, and the POSS is a hybrid material with excellent performance, so that the POSS is easily compounded with a polymer matrix in copolymerization, grafting or blending modes to improve the performances of the polymer matrix such as temperature resistance, flame retardance, toughening and the like. Based on this, in order to solve the problems of large brittleness and low impact strength of the epoxy resin after being rapidly cured at a moderate temperature of about 150 ℃ in the conventional technology, researchers try to introduce a POSS skeleton into the epoxy resin curing agent, for example, the POSS skeleton is combined with amino to improve the performance of the epoxy resin after being cured at a moderate temperature by an amine curing agent.
The inventor of the invention discovers through a great deal of research that if POSS is combined with urea with a certain chain length, the POSS modified urea derivative shown in the formula I can be used as an epoxy resin curing agent, so that the epoxy resin can be cured at a medium temperature of about 150 ℃ at a higher speed, and can be cured within about 2.5min at the fastest speed, and compared with the curing time in the traditional technology which takes hours as a unit at the temperature, the efficiency is greatly improved; in addition, the gelation time before curing can be kept not too short, the maximum time can reach 3.2min, and enough operation time is reserved. Meanwhile, the product obtained by the rapid curing also has higher performance, and has the advantages of high impact strength, high bending modulus, good heat-resistant stability and the like.
In the structure of the POSS modified urea derivative shown in the formula I, a main chain has a certain length and does not contain a branched chain or only contains a short branched chain (methyl, methoxy or ethyl), so that the steric hindrance around the reactive urea group is small, the POSS modified urea derivative can better react with epoxy resin, and the POSS modified urea derivative can have high crosslinking density in a short time, so that the epoxy resin can be quickly cured under a medium-temperature condition, and the cured epoxy resin can have high impact strength; meanwhile, the flexural modulus of the cured epoxy resin is not affected by the reduction of the structural rigidity caused by the overlong length of the main chain.
In some embodiments, the POSS modified urea-based derivatives have the structure shown in formula II:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or 1, 4-phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2、R4、R5each occurrence is independently selected from-H, methyl or ethyl;
are attachment sites.
In another aspect of the present invention, a method for preparing the POSS modified urea derivative is provided, which comprises the following steps:
reacting a compound shown in a formula III, a compound shown in a formula IV and carbonyldiimidazole under the protection of nitrogen or argon at the temperature of 20-35 ℃ to prepare the POSS modified urea derivative;
in some embodiments, the method comprises the following steps:
mixing a compound shown in a formula III, triethylamine and a solvent to prepare a solution; under the protection of nitrogen or argon and at the temperature of 20-35 ℃, adding Carbonyl Diimidazole (CDI) into the solution, stirring for 0.5-1.5 h, adding the solution of the compound shown in the formula IV, continuously stirring for 9-11 h, pouring the reaction system into water, extracting with an organic solvent, washing, drying, concentrating, separating and purifying.
Preferably, the compound shown in the formula III, triethylamine and a solvent are mixed to prepare a solution; under the protection of nitrogen or argon and at the temperature of 25 ℃, Carbonyl Diimidazole (CDI) is added into the solution, after stirring for 1h, the solution of the compound shown in the formula IV is added, stirring is continued for 10h, then the reaction system is poured into water, extracted by an organic solvent, washed, dried, concentrated, separated and purified.
In some embodiments, the ratio of the amounts of the compound of formula III, triethylamine, CDI, and the compound of formula IV is 1 (8-10) to (8-10), preferably 1:8:8: 8.1.
In some embodiments, the compound of formula III and triethylamine are dissolved using anhydrous tetrahydrofuran.
In some embodiments, the compound of formula IV is dissolved using N, N-dimethylformamide.
In some embodiments, the extraction is performed with dichloromethane.
In another aspect of the present invention, an epoxy resin composition is also provided, which comprises the following components by mass:
100 parts of epoxy resin,
5-53 parts of POSS modified urea derivative,
0-150 parts of a filler and a solvent;
wherein the POSS modified urea derivative is represented by the formula I or the formula II.
The epoxy resin composition composed of the POSS modified urea derivative shown in the formula I and the epoxy resin has longer gelation time at a moderate temperature of about 150 ℃ and reserves more operable time; the curing speed is high, and the performance of a cured product is good.
In some embodiments, the POSS-modified urea derivative may be used in the epoxy resin composition in an amount of, for example, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, or 50 parts. The amount of the POSS-modified urea derivative in the epoxy resin composition is directly related to the degree of reaction between the POSS-modified urea derivative and the epoxy resin composition, so that the gelation and curing speed of the epoxy resin and the performance of a cured product are influenced. Controlling the amount within a reasonable range allows for a better balance of gelation and cure speed, and conflicting properties such as impact strength and flexural modulus.
In some embodiments, the amount of filler in the epoxy resin composition may be, for example, 25 parts, 50 parts, 75 parts, 100 parts, or 125 parts.
In some embodiments, the solvent is selected from N, N-dimethylformamide.
In some embodiments, the epoxy resin is selected from the group consisting of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, tetramethyl bisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene novolac type epoxy resin, aralkyl type epoxy resin, One or more of an aralkyl phenol type epoxy resin, an epoxy resin having an arylene ether structure in a molecule, an alicyclic epoxy resin, a polyhydric alcohol type epoxy resin, a silicon-containing epoxy resin, a nitrogen-containing epoxy resin, a phosphorus-containing epoxy resin, a glycidyl amine epoxy resin, and a glycidyl ester epoxy resin.
In some embodiments, the filler is selected from one or more of silica, silica glass frit, mica powder, hollow glass beads, microcrystalline glass, eucryptite, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, clay, kaolin, composite silica fume, E glass frit, D glass frit, L glass frit, M glass frit, S glass frit, T glass frit, NE glass frit, and Q glass frit.
It is understood that the epoxy resin composition may further include additives commonly used in the art, such as one or more of other thermosetting resins, thermoplastic resins, curing agents, curing accelerators, toughening agents, flame retardants, coupling agents, and defoaming agents, without impairing the original properties of the resin composition.
The invention also provides an epoxy resin coating which is formed by curing the epoxy resin composition of any one of the embodiments.
The present invention also provides a prepreg comprising a reinforcement and the epoxy resin composition of any of the preceding embodiments attached to a surface of the reinforcement; or, the coating comprises a reinforcement body and the epoxy resin coating arranged on the surface of the reinforcement body.
In some embodiments, the reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.
In some embodiments, the reinforcement can be, for example, one or more of wood pulp paper, glass cloth, glass nonwoven, aramid paper, aramid cloth, glass felt, and glass roving cloth.
The present invention also provides a laminate comprising one or more sheets of the prepreg of any of the preceding embodiments.
The invention also provides a preparation method of the laminated board, which comprises the following steps:
soaking the flaky reinforcement in the epoxy resin composition, taking out, and drying at 145-155 ℃ for 2-5 min to obtain a laminated board raw material layer; if a multilayer laminate is to be produced, a plurality of laminate stock layers are laminated.
The invention also provides a metal foil-clad laminate which comprises the laminate and metal foils arranged on one side or two sides of the laminate.
In some embodiments, the metal foil is a copper foil, further an electrolytic copper foil.
The invention also provides a preparation method of the metal-clad laminate, which comprises the following steps:
the laminate is covered on one or both sides with a metal foil and then treated in a vacuum hot press.
In some embodiments, the process condition parameters in the vacuum thermocompressor are as follows:
the temperature is 150 ℃, the vacuum degree is 10-20 mBar, and the pressure is 20kg/cm2And the time is 10 min.
The invention also provides a printed wiring board which comprises the laminated board and/or the metal foil-clad laminated board.
The present invention will be described in further detail with reference to specific examples and comparative examples. Experimental parameters not described in the following specific examples are preferably referred to the guidelines given in the present application, and may be referred to experimental manuals in the art or other experimental methods known in the art, or to experimental conditions recommended by the manufacturer. It is understood that the following examples are more specific to the apparatus and materials used, and in other embodiments, are not limited thereto.
The raw material sources are as follows:
eight-p-aminophenyl POSS: xian Qiyue Biotechnology Ltd;
octaaminopropyl POSS: xian Qiyue Biotechnology Ltd;
bisphenol a type epoxy resin: NPEL-128, south Asia plastics industries, Inc.;
o-cresol novolac epoxy resin: NPCN-704, south Asia plastics industries, Inc.;
dicyandiamide: dicy, a group of industries, nabobism;
organic urea accelerator UR 500: DYHARD UR500, Germany winning Industrial shares company;
silicon dioxide: silverbond 706, Silbike (Shanghai) mining, Inc.
POSS-A (X ═ 1, 4-phenylene, R)2～R3all-H) preparation:
1mol of octa-aminophenyl POSS and 8mol of triethylamine (Et) were added to the vessel at room temperature3N), anhydrous Tetrahydrofuran (THF), mixing into a solution; in N2Adding 8mol Carbonyl Diimidazole (CDI) into the solution under the atmosphere, and stirring for 1 hour at constant temperature; then 8.1mol of aniline in N, N-Dimethylformamide (DMF) was added thereto, and after stirring for another 10 hours, the reaction mixture was poured into water, extracted with dichloromethane, and the organic phase was washed with saturated brine and then with anhydrous Na2SO4Drying and filtering, concentrating the filtrate to obtain A crude product, and performing column chromatography separation to obtain A POSS modified ureA derivative product which is named as POSS-A.
POSS-B(X＝-CH2CH2CH2-，R2～R3all-H) preparation:
consistent with the preparation of POSS-A, the difference is that octaaminophenyl POSS is replaced with an equal amount of octaaminopropyl POSS.
Example 1
Adding 100 parts of bisphenol A epoxy resin, 25 parts of POSS-A, 50 parts of silicon dioxide and a proper amount of N, N-Dimethylformamide (DMF) into a container, and uniformly stirring to obtain a resin composition containing POSS modified urea derivatives;
1 piece of 2116-type glass fiber cloth is soaked in the resin composition and dried in a drying oven at 150 ℃ for 3min to obtain a prepreg with the thickness of 0.1 mm; combining 4 pieces of prepreg into a laminated body, covering 1 piece of electrolytic copper foil with the thickness of 18 mu m on each side of the laminated body, sending the laminated body into a hot press with the temperature of 150 ℃, vacuumizing to ensure that the vacuum degree is always kept between 10 and 20mBar, and increasing the pressure to 20kg/cm2After constant temperature and pressure are kept for 10min, the temperature is reduced to be below 40 ℃, pressure is released, vacuum is released, and materials are taken to obtain a copper-clad laminate with the thickness of 0.4 mm; completely removing the copper surface of the copper clad laminate to obtain a laminate;
further, the resin composition is poured into a mold coated with an epoxy resin mold release agent preheated to 150 ℃, vacuum is drawn to maintain the degree of vacuum at 10 to 20mBar all the time, and the pressure is increased to 20kg/cm2And after constant temperature and pressure are kept for 10min, cooling to below 40 ℃, releasing pressure and vacuum, and then taking the material to obtain the epoxy resin casting body for preparing the impact strength test sample.
The laminate and the epoxy resin cast in the other examples and comparative examples were prepared in the same manner as in example 1, and the resin compositions in the examples and comparative examples were formulated as shown in Table 1 (the amounts of the components are in parts by mass):
TABLE 1
The laminates and epoxy resin castings obtained in the examples and comparative examples were subjected to the following performance tests, and the test results are shown in table 2:
(1) tg/. degree.C. (glass transition temperature): the samples were prepared according to Differential Scanning Calorimetry (DSC) using IPC TM-6502.4.25D standards using laminates.
(2) Td/. degree.C. (thermal decomposition temperature): the samples were prepared according to thermogravimetric analysis (TGA) using the laminate according to the IPC TM-6502.4.24.6 standard.
(3) Impact strength/(kJ/m)2): and (4) preparing a sample by using an epoxy resin casting body according to the GB/T1843-2008 standard, and testing the cantilever beam impact strength of the notch sample at room temperature.
(4) Flexural modulus/GPa: the specimens were prepared according to ASTM D882 using a laminate, and the specimens were tested for flexural strength at room temperature at a thickness of 0.8 mm.
(5) Initial reaction temperature/° c: the test results were "3.5 extrapolated onset temperature" in the standard, performed according to GB/T22232-2008 standard.
(6)150 ℃ gelation time/sec: the test temperature was changed from 180 ℃ to 150 ℃ in accordance with GB/T1699-1997 standard.
(7) Curing time/min: the resin compositions provided in examples and comparative examples were impregnated with 1 sheet of 2116-size glass cloth, and dried in an oven at 200 ℃ for X sec to obtain samples. According to Differential Scanning Calorimetry (DSC), a reaction enthalpy test is carried out on a test sample, the test sample is carried out according to ISO 11357-5-2013 standard, the reaction enthalpy result within the range of 50-250 ℃ is less than 2J/g, namely the curing is finished, and X sec is recorded as the curing time result.
TABLE 2
| Group of | Tg | Td | Impact strength | Flexural modulus | Initial reaction temperature | Gelation time at 150 deg.C | Curing time |
| Example 1 | 145 | 358 | 25 | 22.0 | 147 | 153 | 160 |
| Example 2 | 136 | 349 | 21 | 19.2 | 153 | 188 | 220 |
| Example 3 | 151 | 364 | 28 | 23.5 | 143 | 136 | 150 |
| Example 4 | 148 | 368 | 24 | 23.8 | 148 | 158 | 160 |
| Example 5 | 138 | 350 | 26 | 21.6 | 153 | 190 | 230 |
| Example 6 | 152 | 345 | 22 | 19.0 | 146 | 140 | 150 |
| Example 7 | 178 | 357 | 29 | 23.1 | 150 | 168 | 180 |
| Comparative example 1 | 126 | 335 | 15 | 15.3 | 165 | 254 | 480 |
| Comparative example 2 | 141 | 368 | 29 | 18.7 | 141 | 117 | 130 |
| Comparative example 3 | 121 | 323 | 12 | 13.8 | 168 | 287 | 1080 |
| Comparative example 4 | 124 | 328 | 9 | 15.2 | 141 | 152 | 180 |
| Comparative example 5 | 142 | 348 | 18 | 19.6 | 168 | 562 | 1500 |
As is apparent from tables 1 and 2, when a urea derivative having a POSS structure is selected for use in combination with an epoxy resin within the range of the amount preset in the present invention, a resin composition having excellent properties can be obtained. The resin composition has more excellent performance than a similar medium-temperature quick-curing epoxy resin composition, specifically, the Tg (glass transition temperature) of a laminated board is more than 140 ℃, the Td (thermal decomposition temperature) is more than 346 ℃, the flexural modulus is more than 19GPa, and the impact strength of a resin casting body is more than 18kJ/m2。
The addition amount of POSS-B in the comparative example 1 is less than the preset lower limit of the resin composition, the performance improvement effect on a cured product is limited, Tg, Td, impact strength and flexural modulus are low, and medium-temperature rapid curing cannot be realized; the POSS-B addition amount of comparative example 2 is larger than the upper limit defined by the resin composition, which results in a decrease in Tg and flexural modulus, and excessively fast gelation time at 150 ℃ which is not favorable for operation and construction; from comparative example 3, it can be seen that the resin composition without POSS-B exhibited the worst overall performance; comparative example 4 and example 5 compared with each other, it can be seen that the use of organic urea accelerator instead of POSS-B, the resin composition can achieve medium temperature fast curing, but the Tg, Td, impact strength and flexural modulus are all low, and the properties provided by the examples cannot be achieved; comparative example 5 compares with example 4 and shows that the equivalent of octaaminopropyl POSS instead of POSS-B has acceptable Tg, Td, impact strength and flexural modulus of the laminate, but the initial reaction temperature of the resin composition is too high, the gelation time at 150 ℃ is too long, the curing time is too long, and the resin composition cannot be applied to medium-temperature fast curing scenes.
In conclusion, the POSS modified urea derivative provided by the invention can be used as a medium-temperature fast-curing resin composition, the reaction temperature can be reduced, the curing time can be shortened, and meanwhile, a cured product of the POSS modified urea derivative has excellent heat resistance, flexural modulus, toughness and impact strength, is more tough than a common medium-temperature curing agent, and has more excellent heat resistance and flexural modulus than a common toughening agent.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the patent of the invention is subject to the appended claims, and the description can be used for explaining the contents of the claims.
Claims (11)
1. A POSS-modified urea derivative having the structure of formula I:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2～R5each occurrence is independently selected from-H, -D, -F, -Cl, -Br, methyl, methoxy or ethyl;
are attachment sites.
2. The POSS-modified urea derivative of claim 1 having the structure of formula II:
wherein each occurrence of X is independently selected from- (CR)4R5)n-or 1, 4-phenylene;
n is independently selected from 1, 2, 3, 4, 5 or 6 for each occurrence;
R2、R4、R5each occurrence is independently selected from-H, methyl or ethyl;
are attachment sites.
3. A method of preparing POSS modified urea derivatives as claimed in claim 1 or 2 comprising the steps of:
reacting a compound shown in a formula III, a compound shown in a formula IV and carbonyldiimidazole under the protection of nitrogen or argon at the temperature of 20-35 ℃ to prepare the POSS modified urea derivative;
4. the epoxy resin composition is characterized by comprising the following components in parts by mass:
100 parts of epoxy resin,
5-53 parts of POSS modified urea derivative,
0-150 parts of a filler and a solvent;
wherein the POSS-modified urea derivative is the POSS-modified urea derivative of claim 1 or 2.
5. The epoxy resin composition according to claim 4, wherein the epoxy resin is selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, tetramethylbisphenol F type epoxy resin, bisphenol M type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol P type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, naphthol novolac type epoxy resin, anthracene type epoxy resin, phenolphthalein type epoxy resin, phenoxy type epoxy resin, norbornene type epoxy resin, adamantane type epoxy resin, fluorene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene novolac type epoxy resin, anthracene type epoxy resin, phenol type epoxy resin, and the like, One or more of an aralkyl type epoxy resin, an aralkyl phenol type epoxy resin, an epoxy resin containing an arylene ether structure in a molecule, an alicyclic epoxy resin, a polyhydric alcohol type epoxy resin, a silicon-containing epoxy resin, a nitrogen-containing epoxy resin, a phosphorus-containing epoxy resin, a glycidyl amine epoxy resin, and a glycidyl ester epoxy resin; and/or
The filler is selected from one or more of silicon dioxide, quartz glass powder, mica powder, hollow glass beads, microcrystalline glass, eucryptite, titanium dioxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talcum powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, eucryptite, clay, kaolin, composite silicon micro powder, E glass powder, D glass powder, L glass powder, M glass powder, S glass powder, T glass powder, NE glass powder and Q glass powder.
6. An epoxy resin coating layer, which is obtained by curing the epoxy resin composition according to claim 4 or 5.
7. A prepreg comprising a reinforcement and the epoxy resin composition of claim 4 or 5 adhered to a surface of the reinforcement.
8. The prepreg of claim 7, in which the reinforcement is made from one or more of plant fibers, animal fibers, mineral fibers, and synthetic fibers.
9. A laminate comprising one or more sheets of the prepreg of claim 7 or 8.
10. A metal-clad laminate comprising the laminate of claim 9 and a metal foil disposed on one or both sides of the laminate.
11. A printed wiring board comprising the laminate of claim 9 and/or the metal-foil-clad laminate of claim 10.
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