KR20180104295A - Aromatic polyamide surface modifier of silica sol - Google Patents
Aromatic polyamide surface modifier of silica sol Download PDFInfo
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- KR20180104295A KR20180104295A KR1020187020528A KR20187020528A KR20180104295A KR 20180104295 A KR20180104295 A KR 20180104295A KR 1020187020528 A KR1020187020528 A KR 1020187020528A KR 20187020528 A KR20187020528 A KR 20187020528A KR 20180104295 A KR20180104295 A KR 20180104295A
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- aromatic polyamide
- group
- alkyl group
- formula
- Prior art date
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- 239000004760 aramid Substances 0.000 title claims abstract description 34
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 34
- 239000003607 modifier Substances 0.000 title abstract description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 239000010419 fine particle Substances 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- -1 methylene, ethylene, methylethylene, trimethylene, propylene, methylpropylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene Chemical group 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 125000005370 alkoxysilyl group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 238000010550 living polymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YVFMGBISSJHIRW-UHFFFAOYSA-N methyl 4-prop-2-enoxybenzoate Chemical compound COC(=O)C1=CC=C(OCC=C)C=C1 YVFMGBISSJHIRW-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ILUWJNMEDRWSHF-UHFFFAOYSA-N ethyl 3-(ethylamino)benzoate Chemical compound CCNC1=CC=CC(C(=O)OCC)=C1 ILUWJNMEDRWSHF-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BYRPTKZOXNFFDB-UHFFFAOYSA-N lithium;bis(trimethylsilyl)azanide;oxolane Chemical compound [Li+].C1CCOC1.C[Si](C)(C)[N-][Si](C)(C)C BYRPTKZOXNFFDB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/12—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids with both amino and carboxylic groups aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
식(1)으로 표시되는 것을 특징으로 하는 방향족 폴리아마이드는 무기 미립자 표면의 수식제로서 이용 가능하다. (식 중, X는 탄소수 1~10의 알킬렌기를 나타내고, R'는 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, R3은 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, n은 2 이상의 정수를 나타내고, k는 1~3의 정수를 나타낸다.)
Description
본 발명은 방향족 폴리아마이드에 관한 것으로, 더욱 상세하게 서술하면 무기 미립자의 표면 수식 등에 이용 가능한 방향족 폴리아마이드에 관한 것이다.The present invention relates to aromatic polyamides, and more particularly relates to aromatic polyamides which can be used for surface modification of inorganic microfine particles and the like.
유기 재료의 내열성이나 역학 특성 및 전기적 특성을 향상시키기 위해서, 실리카 겔이나 산화타이타늄 등의 무기 미립자를 유기 고분자와 섞은 하이브리드 재료(나노 컴퍼지트)가 자주 연구되고 있다.Hybrid materials (nanocomposites) in which inorganic fine particles such as silica gel or titanium oxide are mixed with organic polymers are frequently studied to improve heat resistance, mechanical properties, and electrical properties of organic materials.
그러나 유기 재료와 무기 재료는 애초부터 성질이 크게 상이하므로, 첨가할 수 있는 무기 미립자의 양이 한정된다는 문제가 있고, 첨가한 무기 미립자를 유기 재료 중에서 분산시키는 것이 어려울 뿐만아니라, 시간이 지나면 첨가한 무기 미립자가 유기 재료 중에서 응집해버리는 등의 문제가 있다.However, since the properties of the organic material and the inorganic material differ greatly from the beginning, there is a problem that the amount of the inorganic fine particles to be added is limited, and it is difficult to disperse the added inorganic fine particles in the organic material. There is a problem that the inorganic fine particles aggregate in the organic material.
그래서 이러한 문제들을 해결하기 위해서 무기 미립자 표면을 유기 저분자 화합물이나 유기 고분자로 수식하는 것이 행해져오고 있다.Therefore, in order to solve these problems, the surface of the inorganic fine particles is modified with an organic low molecular compound or an organic polymer.
특히 유기 고분자로 수식하는 경우는 (1) 무기 표면에 개시 부위를 도입하여 거기서부터 리빙 중합을 행하거나, 또는 (2) 리빙 폴리머 말단에 무기물과 결합할 수 있는 관능기(-Si(OR)3, -PO3H, -CO2H, -SH 등)를 도입하고, 무기 미립자 표면에 반응시킨다는 2가지의 방법이 주로 행해지고 있다.Particularly, in the case of modifying with an organic polymer, (1) introducing the initiation site on the inorganic surface and performing living polymerization therefrom, or (2) introducing a functional group (-Si (OR) 3 , -PO 3 H, -CO 2 H, -SH, etc.) is introduced into the reaction system and reacted on the surface of the inorganic fine particles.
그러나 리빙 중합은 부가 중합과 개환 중합에 한정되므로, 얻어지는 폴리머는 그다지 내열성이 없는 지방족 폴리머이다. 이 경우, 무기 미립자를 유기 재료에 섞어 내열성을 높이고자 해도 표면 수식한 지방족 폴리머가 먼저 열분해하여, 표면 수식하지 않은 무기 미립자를 섞은 재료와 동일한 문제를 안게 된다. 또 애초부터 수식한 지방족 폴리머가 내열성이 높은 축합계 방향족 폴리머와 섞이기 어려운 것도 큰 문제가 된다.However, since living polymerization is limited to addition polymerization and ring-opening polymerization, the obtained polymer is an aliphatic polymer having little heat resistance. In this case, even if the inorganic fine particles are mixed with the organic material to increase the heat resistance, the surface-modified aliphatic polymer is thermally decomposed first, which causes the same problem as the material containing the inorganic fine particles not surface-modified. It is also a big problem that the aliphatic polymer modified from the beginning is difficult to mix with the condensed aromatic polymer having high heat resistance.
이러한 문제들을 해결하기 위해서는 내열성이 우수한 축합계 방향족 고분자로 무기 미립자 표면을 수식하면 된다. 그러나 축합계 방향족 고분자는 중축합으로 밖에 얻어지지 않기 때문에, 리빙 중합의 특성을 살린 상기 (1)과 (2)의 어프로치는 불가능했다.In order to solve these problems, it is sufficient to modify the surface of the inorganic fine particles with a condensed aromatic polymer having excellent heat resistance. However, since the condensed aromatic polymer can be obtained only by polycondensation, the approach of (1) and (2) above, taking advantage of the characteristics of living polymerization, was impossible.
본 발명은 이와 같은 사정을 감안하여 이루어진 것으로, 무기 미립자의 표면 수식 등에 이용 가능한 방향족 폴리아마이드를 제공하는 것을 목적으로 한다.The present invention has been made in view of such circumstances, and an object thereof is to provide an aromatic polyamide that can be used for surface modification of inorganic microfine particles.
본 발명자들은 지금까지 개발해온 중축합의 리빙 중합인 연쇄 축합 중합(CGCP)에 의한 방향족 폴리아마이드 중합법(비특허문헌 1 참조)에 있어서, 불포화 결합을 가지는 개시제를 사용하여 얻어진 불포화 말단을 이용함으로써, 무기물 표면과 반응하는 -Si(OR)3 등을 도입할 수 있는 결과, 무기 미립자 표면의 수식제로서 이용 가능한 방향족 폴리아마이드가 얻어지는 것을 알아내어 본 발명을 완성했다.The present inventors have found that by using an unsaturated terminal obtained by using an initiator having an unsaturated bond in an aromatic polyamide polymerization method (see Non-Patent Document 1) by chain condensation polymerization (CGCP) which is a living polymerization of polycondensation that has been developed so far, -Si (OR) 3 reacting with the surface of the inorganic material can be introduced. As a result, an aromatic polyamide that can be used as a modifier for the surface of the inorganic fine particles can be obtained.
즉, 본 발명은That is,
1. 식(1)으로 표시되는 것을 특징으로 하는 방향족 폴리아마이드,1. An aromatic polyamide characterized by the formula (1)
(식 중, X는 탄소수 1~10의 알킬렌기를 나타내고, R'는 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, R3은 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, n은 2 이상의 정수를 나타내고, k는 1~3의 정수를 나타낸다.)(Wherein X represents an alkylene group having 1 to 10 carbon atoms, R 'independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 1 and R 2 independently represent an alkyl group having 1 to 10 carbon atoms, 10 shows an alkyl group, R 3 independently represent an aryl group having 1 to 10 carbon atoms or an alkyl group having from 6 to 20 carbon atoms, n is an integer of 2 or, k represents an integer of 1 to 3.)
2. 식(2)으로 표시되는 1의 방향족 폴리아마이드,2. An aromatic polyamide represented by the formula (2)
(식 중, R', R1, R2 및 n은 상기와 동일하다.)(Wherein R ', R 1 , R 2 and n are as defined above)
3. 식(3)으로 표시되는 것을 특징으로 하는 방향족 폴리아마이드,3. An aromatic polyamide characterized by the formula (3)
(식 중, R은 불포화 결합 함유기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, n은 2 이상의 정수를 나타낸다.)(Wherein R represents an unsaturated bond-containing group, R 1 and R 2 independently represent an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 2 or more).
4. 식(4)으로 표시되는 3의 방향족 폴리아마이드,4. An aromatic polyamide represented by the formula (4)
(식 중, R1, R2 및 n은 상기와 동일하다.)(Wherein R 1 , R 2 and n are the same as above)
5. 상기 R1 및 R2가 서로 독립적으로 메틸기 또는 에틸기인 1 내지 4 중 어느 하나의 방향족 폴리아마이드,5. The R 1 and R 2 have any of the aromatic polyamide of the independently a methyl group or an ethyl group of from 1 to 4 to each other,
6. 1 내지 5 중 어느 하나의 방향족 폴리아마이드로 표면 수식되어 있는 무기 미립자,6. An inorganic fine particle surface-modified with an aromatic polyamide of any one of 1 to 5,
7. 6의 무기 미립자와 유기 매트릭스 수지를 포함하는 유기·무기 하이브리드 재료,7. An organic-inorganic hybrid material comprising inorganic fine particles and an organic matrix resin,
8. 7의 유기·무기 하이브리드 재료를 사용하여 제작되는 필름8. Film made using organic / inorganic hybrid material of 7
을 제공한다..
본 발명에 의하면, 무기 미립자 표면의 수식제로서 이용 가능한 방향족 폴리아마이드를 제공할 수 있다.According to the present invention, it is possible to provide an aromatic polyamide which can be used as a modifier for the surface of the inorganic fine particles.
이 방향족 폴리아마이드를 사용하여 실리카나 질화붕소 등의 무기 미립자 표면을 수식하고, 폴리이미드 등의 내열성 고분자에 혼합하여 더욱 내열성과 역학 특성을 높인 유기·무기 하이브리드 재료의 개발을 기대할 수 있다.Development of an organic-inorganic hybrid material in which the surface of an inorganic fine particle such as silica or boron nitride is modified by using the aromatic polyamide and mixing with a heat-resistant polymer such as polyimide to further increase heat resistance and mechanical properties can be expected.
이하, 본 발명에 대해서 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 방향족 폴리아마이드는 하기 식(1)으로 표시되는 것이다.The aromatic polyamide according to the present invention is represented by the following formula (1).
식(1)에 있어서, X는 탄소수 1~10의 알킬렌기를 나타내고, R'는 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, R3은 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, n은 2 이상의 정수를 나타내고, k는 1~3의 정수를 나타낸다.In the formula (1), X represents an alkylene group having 1 to 10 carbon atoms, R 'independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 independently represent R 3 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, n represents an integer of 2 or more, and k represents an integer of 1 to 3.
탄소수 1~10의 알킬렌기의 구체예로서는 메틸렌, 에틸렌, 메틸에틸렌, 트라이메틸렌, 프로필렌, 메틸프로필렌, 테트라메틸렌, 펜타메틸렌, 헥사메틸렌, 헵타메틸렌, 옥타메틸렌, 데카메틸렌 등을 들 수 있는데, 그 중에서도 탄소수 1~5의 알킬렌기가 바람직하고, 탄소수 1~3의 알킬렌기가 보다 바람직하며, 트라이메틸렌기가 한층 더 바람직하다.Specific examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, methylethylene, trimethylene, propylene, methylpropylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and decamethylene. An alkylene group having 1 to 5 carbon atoms is preferable, an alkylene group having 1 to 3 carbon atoms is more preferable, and a trimethylene group is still more preferable.
탄소수 1~10의 알킬기의 구체예로서는 메틸, 에틸, n-프로필, 아이소프로필, 사이클로프로필, n-뷰틸, 아이소뷰틸, s-뷰틸, t-뷰틸, n-펜틸, 1-메틸-n-뷰틸, 2-메틸-n-뷰틸, 3-메틸-n-뷰틸, 1,1-다이메틸-n-프로필, 1,2-다이메틸-n-프로필, 2,2-다이메틸-n-프로필, 1-에틸-n-프로필, 사이클로펜틸, n-헥실, 1-메틸-n-펜틸, 2-메틸-n-펜틸, 3-메틸-n-펜틸, 4-메틸-n-펜틸, 1,1-다이메틸-n-뷰틸, 1,2-다이메틸-n-뷰틸, 1,3-다이메틸-n-뷰틸, 2,2-다이메틸-n-뷰틸, 2,3-다이메틸-n-뷰틸, 3,3-다이메틸-n-뷰틸, 1-에틸-n-뷰틸, 2-에틸-n-뷰틸, 1,1,2-트라이메틸-n-프로필, 1,2,2-트라이메틸-n-프로필, 1-에틸-1-메틸-n-프로필, 1-에틸-2-메틸-n-프로필, 사이클로헥실, n-헵틸, n-옥틸, n-노닐, n-데실기 등을 들 수 있다.Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec- Propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-methyl-n-butyl, Propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl- Butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2- Butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl- n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, n-heptyl, n-octyl, .
탄소수 6~20의 아릴기의 구체예로서는 페닐, α-나프틸, β-나프틸, o-바이페닐릴, m-바이페닐릴, p-바이페닐릴, 1-안트릴, 2-안트릴, 9-안트릴, 1-페난트릴, 2-페난트릴, 3-페난트릴, 4-페난트릴, 9-페난트릴기 등을 들 수 있다.Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl,? -Naphthyl,? -Naphthyl, o-biphenyl, m-biphenylyl, p-biphenylyl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl groups.
이들 중에서도 R', R1, R2로서는 메틸, 에틸기가 바람직하고, 또 R3으로서는 탄소수 1~8의 알킬기가 바람직하고, 탄소수 1~5의 알킬기가 보다 바람직하며, 메틸, 에틸, n-프로필, 아이소프로필, n-뷰틸, n-펜틸, n-옥틸기 등이 적합하다.Of these, R ', R 1 and R 2 are preferably methyl and ethyl, and R 3 is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, , Isopropyl, n-butyl, n-pentyl, n-octyl and the like.
k는 1~3의 정수를 나타내는데, 2 또는 3이 바람직하고, 3이 보다 바람직하다.k represents an integer of 1 to 3, preferably 2 or 3, more preferably 3.
n은 2 이상의 정수이면 특별히 한정되는 것은 아닌데, 2~100의 정수가 바람직하다.n is not particularly limited as long as it is an integer of 2 or more, preferably an integer of 2 to 100.
상기 (1)으로 표시되는 방향족 폴리아마이드로서는 하기 식(2)으로 표시되는 것이 바람직하다.The aromatic polyamide represented by the above-mentioned (1) is preferably represented by the following formula (2).
이상 설명한 방향족 폴리아마이드는 상기 비특허문헌 1의 방법으로 얻어지는 하기 식(3)으로 표시되는 방향족 폴리아마이드를 원료로 하여 얻을 수 있다.The aromatic polyamide described above can be obtained by using the aromatic polyamide represented by the following formula (3) obtained by the method of the above non-patent document 1 as a raw material.
식(3)에 있어서, R은 불포화 결합 함유기를 나타내고, R1, R2, n은 상기와 동일한 의미를 나타낸다.In the formula (3), R represents an unsaturated bond-containing group, and R 1 , R 2 and n have the same meanings as defined above.
불포화 결합 함유기로서는 특별히 한정되는 것은 아닌데, 나중의 티올과의 래디컬 부가 반응 효율을 고려하면, 바이닐, 알릴, 호모알릴기 등의 말단 이중 결합을 가지는 기가 바람직하고, 이 경우 R에 따라 각종의 스페이서를 가지는 방향족 폴리아마이드가 얻어지는데, 상기 식(1)으로 표시되는 방향족 폴리아마이드를 얻기 위해서는 하기 식(4)으로 표시되는 R이 알릴기인 방향족 폴리아마이드를 사용할 필요가 있다.The unsaturated bond-containing group is not particularly limited, but a group having a terminal double bond such as a vinyl, allyl, or homoallyl group is preferable in view of the radical reaction efficiency with the subsequent thiol. In this case, . In order to obtain the aromatic polyamide represented by the formula (1), it is necessary to use an aromatic polyamide represented by the following formula (4) wherein R is an allyl group.
(식 중, R1, R2 및 n은 상기와 동일하다.)(Wherein R 1 , R 2 and n are the same as above)
상기 식(4)으로 표시되는 알릴기를 가지는 방향족 폴리아마이드와, 알콕시실릴기 함유 티올 화합물을 래디컬 부가 반응시켜 식(1)으로 표시되는 방향족 폴리아마이드가 얻어진다.The aromatic polyamide having an allyl group represented by the formula (4) and the alkoxysilyl group-containing thiol compound are subjected to radical addition reaction to obtain an aromatic polyamide represented by the formula (1).
이 경우, 식(4)의 방향족 폴리아마이드, 알콕시실릴기 함유 티올 화합물의 반응 비율은 특별히 한정되는 것은 아닌데, 반응 효율 등을 고려하면, 식(4)의 방향족 폴리아마이드 1mol에 대하여 티올 화합물 1~100mol 정도로 할 수 있는데, 5~50mol이 바람직하고, 10~30mol이 보다 바람직하다.In this case, the reaction ratio of the aromatic polyamide and the alkoxysilyl group-containing thiol compound represented by the formula (4) is not particularly limited. In view of the reaction efficiency and the like, the amount of the thiol compound It is preferably 5 to 50 mol, and more preferably 10 to 30 mol.
알콕시실릴기 함유 티올 화합물의 구체예로서는 3-(트라이메톡시실릴)프로페인티올, 3-(트라이에톡시실릴)프로페인티올 등을 들 수 있다.Specific examples of the alkoxysilyl group-containing thiol compound include 3- (trimethoxysilyl) propanethiol and 3- (triethoxysilyl) propanethiol.
중합 개시제로서는 열 또는 환원성 물질 등에 의해 분해하여 래디컬종을 발생시키는 것이면 특별히 한정은 없고, 예를 들면 2,2'-아조비스아이소뷰티로나이트릴 등의 아조 화합물, 벤조일퍼옥사이드, t-뷰틸퍼벤조에이트, t-뷰틸하이드로퍼옥사이드, 다이-t-뷰틸퍼옥사이드, 쿠멘하이드로퍼옥사이드 등의 과산화물 등을 들 수 있고, 이들은 단독으로 사용해도 되고, 2종 이상을 조합하여 사용해도 된다.The polymerization initiator is not particularly limited as long as it is decomposed by heat or a reducing substance to generate radical species. Examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile, benzoyl peroxide, Peroxide such as benzoate, t-butyl hydroperoxide, di-tert-butylperoxide, cumene hydroperoxide and the like, and these may be used alone or in combination of two or more.
상기 반응은 유기 용매 중에서 행할 수도 있다.The reaction may be carried out in an organic solvent.
이 반응에 사용되는 용매로서는 방향족 폴리아마이드가 용해하고, 중합 반응을 방해하지 않는 것이면 임의이며, 예를 들면 펜테인, 헥세인, 헵테인, 옥테인, 사이클로헥세인 등의 지방족 탄화수소류; 다이에틸에터, 다이아이소프로필에터, 다이뷰틸에터, 사이클로펜틸메틸에터, 테트라하이드로퓨란, 1,4-다이옥세인 등의 에터류; 벤젠, 톨루엔, 자일렌, 메시틸렌, 아니솔 등의 방향족 탄화수소류; 클로로폼, 다이클로로메테인, 다이클로로에테인, 사염화탄소 등의 할로겐화 탄화수소류, 아세토나이트릴, 프로피오나이트릴 등의 나이트릴류 등을 들 수 있는데, 나이트릴류가 바람직하고, 특히 아세토나이트릴이 적합하다.The solvent used in this reaction is not particularly limited as long as the aromatic polyamide dissolves and does not interfere with the polymerization reaction. Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and anisole; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and carbon tetrachloride, and nitrites such as acetonitrile and propionitrile. Of these, nitrites are preferable, and acetonitrile is particularly suitable.
반응 온도는 50~150℃ 정도가 바람직하고, 60~100℃ 정도가 보다 바람직하다.The reaction temperature is preferably about 50 to 150 占 폚, more preferably about 60 to 100 占 폚.
반응 시간은 통상 1~120시간 정도이다.The reaction time is usually about 1 to 120 hours.
반응 종료 후는 정법에 따라 후처리를 하고, 필요에 따라 재침전 등의 정제를 시행하여 목적물을 얻을 수 있다.After the completion of the reaction, post treatment is carried out according to a regular method, and purification, such as re-precipitation, may be carried out, if necessary, to obtain the desired product.
얻어진 식(1)으로 표시되는 방향족 폴리아마이드는 그 말단에 알콕시실릴기를 가지고 있기 때문에, 이 알콕시실릴기를 이용하여 무기 미립자의 표면이나 무기 기판의 표면 등을 수식할 수 있다.Since the obtained aromatic polyamide represented by the formula (1) has an alkoxysilyl group at the terminal thereof, the alkoxysilyl group can be used to modify the surface of the inorganic fine particles or the surface of the inorganic substrate.
방향족 폴리아마이드는 내열성이 우수하기 때문에, 본 발명의 방향족 폴리아마이드를 무기 재료의 표면 처리제로서 사용함과 아울러, 유기 매트릭스로서도 폴리이미드나 폴리아마이드 등의 내열성이 우수한 수지를 사용함으로써, 내열성 및 역학 특성이 우수한 유기·무기 하이브리드 재료의 개발을 기대할 수 있다.Since the aromatic polyamide has excellent heat resistance, the aromatic polyamide of the present invention is used as a surface treatment agent for an inorganic material, and a resin having excellent heat resistance such as polyimide or polyamide is used as an organic matrix, It can be expected to develop excellent organic-inorganic hybrid materials.
(실시예)(Example)
이하, 실시예를 들어 본 발명을 보다 구체적으로 설명하는데, 본 발명은 하기의 실시예에 한정되는 것은 아니다. 실시예에서 사용한 각 측정 장치는 이하와 같다.Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples. Each measuring device used in the embodiment is as follows.
[GPC][GPC]
(1) Poly1, Poly2(1) Poly1, Poly2
장치 : Shodex GPC-101(쇼와덴코(주)제)Apparatus: Shodex GPC-101 (manufactured by Showa Denko K.K.)
칼럼 : Shodex KF-804L 2개(쇼와덴코(주)제)Column: Two Shodex KF-804L (manufactured by Showa Denko K.K.)
칼럼 온도 : 40℃Column temperature: 40 DEG C
용매 : 테트라하이드로퓨란 1mL/분Solvent: tetrahydrofuran 1 mL / min
검출기 : UV(254nm), RIDetector: UV (254 nm), RI
검량선 : 표준 폴리스타이렌Calibration curve: standard polystyrene
(2) 폴리아믹산 S1(2) Polyamic acid S1
장치 : Shodex GPC-101(쇼와덴코(주)제)Apparatus: Shodex GPC-101 (manufactured by Showa Denko K.K.)
칼럼 : Shodex KD801 및 KD805(쇼와덴코(주)제)Column: Shodex KD801 and KD805 (manufactured by Showa Denko K.K.)
칼럼 온도 : 40℃Column temperature: 40 DEG C
용매 : 다이메틸폼아마이드/LiBr·H2O(29.6mM)/H3PO4(29.6mM)/Solvent: dimethylformamide / LiBr.H 2 O (29.6 mM) / H 3 PO 4 (29.6 mM) /
검출기 : UV(254nm), RIDetector: UV (254 nm), RI
검량선 : 표준 폴리에틸렌옥사이드Calibration curve: Standard polyethylene oxide
[1H-NMR][ 1 H-NMR]
장치 : JEOL ECA-500 and ECA-600Devices: JEOL ECA-500 and ECA-600
[TG-DTA][TG-DTA]
장치 : Seiko Instruments Inc. TG/DTA 6200Device: Seiko Instruments Inc. TG / DTA 6200
[실시예 1] Poly1의 제조 [Example 1] Production of Poly1
100mL 가지 플라스크를 감압하 히트 건을 사용하여 가열 후, 아르곤 치환하여 실온까지 냉각했다. 또한 -10℃까지 냉각하고, 질소 기류하에서 1M LiHMDS의 THF 용액 11mL(11.0mmol)를 가하고, 질소 기류하에서 건조 THF 5.2mL에 용해시킨 4-알릴옥시벤조산메틸(1) 0.21g(1.11mmol)을 가했다. 그 후, 곧 건조 THF 13.0mL에 용해시킨 3-(에틸아미노)벤조산에틸(2) 2.04g(10.54mmol)을 40분간에 걸쳐 적하하고, 그 후 -10℃에서 교반했다. 6분 후에 샘플링하여 반응 경과를 관찰하고, 2시간 후에 포화 염화암모늄 수용액으로 중합을 정지시켰다. 염화메틸렌으로 추출, 물로 3회 세정 후에 무수 황산마그네슘으로 건조시켰다. 감압하에서 용매를 증류제거하고, 얻어진 조생성물을 양용매로서 클로로폼, 빈용매로서 에터를 사용하여 침전 정제를 행하여, 황색 고체를 수량 1.30g(수율 70%)으로 얻었다(Mn=2500, Mw/Mn=1.23, 평균 중합도=20.2).The 100 mL eggplant flask was heated under reduced pressure using a heat gun, and then argon was replaced and cooled to room temperature. Further, 11 mL (11.0 mmol) of a 1 M LiHMDS THF solution was added under nitrogen flow, 0.21 g (1.11 mmol) of methyl 4-allyloxybenzoate (1) dissolved in 5.2 mL of dry THF under a nitrogen stream was added He said. Then, 2.04 g (10.54 mmol) of ethyl 3- (ethylamino) benzoate (2) dissolved in 13.0 mL of dry THF was added dropwise over 40 minutes, and then the mixture was stirred at -10 ° C. After 6 minutes, the reaction was observed by observing the progress of the reaction. After 2 hours, the polymerization was stopped with a saturated aqueous solution of ammonium chloride. Extracted with methylene chloride, washed three times with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was subjected to precipitation purification using chloroform as a good solvent and ether as a poor solvent to obtain 1.30 g (yield: 70%) of a yellow solid (M n = 2500, M w / M n = 1.23, average degree of polymerization = 20.2).
[실시예 2] Poly2의 제조 [Example 2] Production of Poly2
20mL 내압 반응관에 건조 아세토나이트릴 14.70mL, Poly1 0.70g(0.22mmol), 3-(트라이메톡시실릴)프로페인티올 2.99mL(15.40mmol), 및 2,2'-아조비스아이소뷰티로나이트릴 18.50mg(0.11mmol)을 가했다. 액체 질소로 냉동한 후, 반응 용기 내부를 감압하고 밀폐한 후에 실온으로 되돌리고, 용매 중의 용존 가스를 발포시켰다. 이 일련의 조작(동결 탈기)을 5회 행한 후, 80℃에서 12시간 교반했다. 용매를 증류제거하고, 얻어진 생성물을 양용매로서 클로로폼, 빈용매로서 헥세인:다이옥세인=10:1(v/v)의 혼합 용액을 사용하여 침전 정제를 행하여, 황백색 고체를 수량 0.52g(수율 70%)으로 얻었다.To a 20 mL pressure-resistant reaction tube were added 14.70 mL of dry acetonitrile, 0.70 g (0.22 mmol) of Poly1, 2.99 mL (15.40 mmol) of 3- (trimethoxysilyl) propanethiol, and 2,2'-azobisisobutyronitrile Reil 18.50 mg (0.11 mmol) was added. After freezing with liquid nitrogen, the inside of the reaction vessel was decompressed and sealed, then returned to room temperature, and the dissolved gas in the solvent was foamed. This series of operations (freeze-thawing) was conducted five times, followed by stirring at 80 DEG C for 12 hours. The solvent was distilled off and the obtained product was subjected to precipitation purification using chloroform as a good solvent and a mixed solution of hexane: dioxane = 10: 1 (v / v) as a poor solvent to obtain a yellowish white solid in an amount of 0.52 g Yield: 70%).
[실시예 3] 실리카 졸의 합성 [Example 3] Synthesis of silica sol
내압 반응관에 실시예 2에서 얻어진 Poly2(Mn=2100, Mw/Mn=1.18, 평균 중합도=15) 0.0878g(0.03mmol), DMAc 1.0g을 가하고, 실온에서 교반한 후, DMAc-실리카 졸 용액 0.64g(실리카 함유량 : 0.128g)을 가하고, 50℃에서 교반하여, 12시간 후에 반응을 멈췄다. 반응 후의 용액을 감압하에서 증류제거하고, 얻어진 생성물에 클로로폼을 가하고, 디캔테이션을 행하여, 가용부(30%)와 불용부(70%)로 나누었다. 가용부를 농축하고, 각각 얻어진 생성물을 감압 건조시켰다.0.0878 g (0.03 mmol) of Poly 2 (Mn = 2100, Mw / Mn = 1.18, average degree of polymerization = 15) obtained in Example 2 and 1.0 g of DMAc obtained in Example 2 were added to the reaction tube and stirred at room temperature. 0.64 g (silica content: 0.128 g) was added, stirred at 50 캜, and the reaction was stopped after 12 hours. The solution after the reaction was distilled off under reduced pressure, chloroform was added to the obtained product, and the mixture was divided into soluble (30%) and insoluble (70%) by decantation. The soluble fraction was concentrated, and the obtained product was dried under reduced pressure.
가용부의 일부를 질량 측정하면서 샘플링을 행하고, 내부 표준 물질로서 테레프탈알데하이드를 가하여, 1H-NMR 스펙트럼으로부터 트라이메톡시실릴기의 전화율을 산출했더니 전화율은 99%였다. 또 가용부와 불용부의 TG-DTA를 측정하고, 중량 감소율로부터 실리카 중의 폴리아마이드의 비율을 산출했다. 가용부는 84%, 불용부는 22%였다. 또 가용부를 DMAc에 고형분 10%가 되도록 재용해시켰다.A portion of the soluble portion was subjected to sampling while mass measurement, terephthalaldehyde was added as an internal standard substance, and the conversion rate of the trimethoxysilyl group was calculated from the 1 H-NMR spectrum. The conversion rate was 99%. The TG-DTA of the soluble portion and the insoluble portion was measured, and the ratio of the polyamide in the silica was calculated from the weight reduction ratio. 84% available and 22% insoluble. The soluble portion was redissolved in DMAc to a solid content of 10%.
[실시예 4] 하이브리드 필름의 제작[Example 4] Production of hybrid film
(1) 폴리아믹산(S1)의 합성(1) Synthesis of polyamic acid (S1)
p-페닐렌다이아민 3.218g(30mmol)을 DMAc 88.2g에 용해시켰다. 얻어진 용액에 3,3',4,4'-바이페닐테트라카복실산 이무수물 8.581g(29mmol)을 가하고, 질소 분위기하 23℃에서 24시간 반응시켰다. 얻어진 폴리아믹산의 Mw는 107,300, 분자량 분포 4.6이었다.3.218 g (30 mmol) of p-phenylenediamine were dissolved in 88.2 g of DMAc. To the obtained solution, 8.581 g (29 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride was added, and the reaction was allowed to proceed at 23 deg. C in a nitrogen atmosphere for 24 hours. The Mw of the obtained polyamic acid was 107,300 and the molecular weight distribution was 4.6.
(2) 하이브리드 필름의 제작(2) Production of hybrid films
상기에서 얻어진 폴리아믹산 6.0g에 실시예 3에서 제작한 실리카 졸 용액(가용부) 0.90g을 첨가하고, 23℃에서 3시간 교반하여 바니시를 조제했다. 그 후, 유리 기판 상에 이 바니시를 바 코터로 도포하여 막두께 250μm의 도포막을 제작하고, 80℃에서 1시간, 300℃에서 1시간 소성했다.0.90 g of the silica sol solution (soluble portion) prepared in Example 3 was added to 6.0 g of the polyamic acid obtained above, and the mixture was stirred at 23 占 폚 for 3 hours to prepare a varnish. Thereafter, this varnish was coated on a glass substrate with a bar coater to prepare a coating film having a film thickness of 250 mu m, followed by baking at 80 DEG C for 1 hour and at 300 DEG C for 1 hour.
얻어진 필름에 백탁은 없고, 황색의 깨끗한 필름이었다. 또 이 필름을 커터로 유리 기판으로부터 박리했더니 용이하게 박리되었다. 박리된 필름은 강한 자기 지지성이 보였다.The obtained film had no white turbidity and was a yellow, clear film. This film was peeled off from the glass substrate with a cutter, and was easily peeled off. The peeled film showed strong self-supporting properties.
[실시예 5] 하이브리드 필름의 제작[Example 5] Production of hybrid film
상기에서 얻어진 폴리아믹산 1.0g에 실시예 3에서 제작한 실리카 졸 용액(가용부) 1.50g 용액을 첨가하고, 23℃에서 3시간 교반하여 바니시를 조제했다. 그 후, 유리 기판 상에 이 바니시를 바 코터로 도포하여 막두께 250μm의 도포막을 제작하고, 80℃에서 1시간, 300℃에서 1시간 소성했다.A solution of 1.50 g of the silica sol solution (soluble portion) prepared in Example 3 was added to 1.0 g of the polyamic acid obtained above, and the mixture was stirred at 23 캜 for 3 hours to prepare a varnish. Thereafter, this varnish was coated on a glass substrate with a bar coater to prepare a coating film having a film thickness of 250 mu m, followed by baking at 80 DEG C for 1 hour and at 300 DEG C for 1 hour.
얻어진 필름에 백탁은 없고, 황색의 깨끗한 필름이었다. 이 필름을 커터로 박리했더니 용이하게 박리되었다. 박리된 필름은 강한 자기 지지성이 보였다.The obtained film had no white turbidity and was a yellow, clear film. The film was peeled off with a cutter and easily peeled off. The peeled film showed strong self-supporting properties.
Claims (8)
(식 중, X는 탄소수 1~10의 알킬렌기를 나타내고, R'는 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, R3은 서로 독립적으로 탄소수 1~10의 알킬기 또는 탄소수 6~20의 아릴기를 나타내고, n은 2 이상의 정수를 나타내고, k는 1~3의 정수를 나타낸다.)An aromatic polyamide characterized by the formula (1).
(Wherein X represents an alkylene group having 1 to 10 carbon atoms, R 'independently represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 1 and R 2 independently represent an alkyl group having 1 to 10 carbon atoms, 10 shows an alkyl group, R 3 independently represent an aryl group having 1 to 10 carbon atoms or an alkyl group having from 6 to 20 carbon atoms, n is an integer of 2 or, k represents an integer of 1 to 3.)
(식 중, R', R1, R2 및 n은 상기와 동일하다.)The aromatic polyamide according to claim 1, which is represented by the formula (2).
(Wherein R ', R 1 , R 2 and n are as defined above)
(식 중, R은 불포화 결합 함유기를 나타내고, R1 및 R2는 서로 독립적으로 탄소수 1~10의 알킬기를 나타내고, n은 2 이상의 정수를 나타낸다.)An aromatic polyamide represented by the formula (3).
(Wherein R represents an unsaturated bond-containing group, R 1 and R 2 independently represent an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 2 or more).
(식 중, R1, R2 및 n은 상기와 동일하다.)4. The aromatic polyamide according to claim 3, which is represented by the formula (4).
(Wherein R 1 , R 2 and n are the same as above)
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| PCT/JP2017/002135 WO2017130905A1 (en) | 2016-01-26 | 2017-01-23 | Aromatic polyamide surface modifier of silica sol |
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| KR20200071380A (en) | 2018-12-11 | 2020-06-19 | 주식회사 제넨셀 | Composition for improving premenstrual syndrome symptom comprising extract of Aucklandiae radix |
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| EP0046954A3 (en) * | 1980-08-25 | 1982-03-24 | Teijin Limited | Shaped article of aromatic polyamide |
| JPS5740556A (en) * | 1980-08-25 | 1982-03-06 | Teijin Ltd | Molded aromatic polyamide article |
| JPH0687807B2 (en) * | 1987-07-14 | 1994-11-09 | 宇部興産株式会社 | Tape rubber for shoes |
| JPH04130115A (en) * | 1990-09-21 | 1992-05-01 | Showa Highpolymer Co Ltd | Unsaturated aromatic polyamide oligomer and its production |
| JPH06322072A (en) * | 1993-05-17 | 1994-11-22 | Showa Highpolymer Co Ltd | Thermosetting resin composition |
| DE69311290T2 (en) * | 1992-08-03 | 1997-10-30 | Showa Highpolymer | HEAT-CURABLE RESIN COMPOSITION AND THE PRODUCTION THEREOF FROM COPPER-COATED LAMINATE PANELS |
| JPH07168356A (en) * | 1993-12-16 | 1995-07-04 | Res Dev Corp Of Japan | Method for fixing nitrogen-containing high molecular compound |
| FR2721035B1 (en) * | 1994-06-08 | 1997-05-23 | Atochem Elf Sa | Polyamides with improved thermomechanical performances, their preparation process and their use after crosslinking. |
| SG105450A1 (en) * | 1998-07-02 | 2004-08-27 | Nat Starch Chem Invest | Allylated amide compounds and die attach adhesives prepared therefrom |
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