CN106588959B - A kind of coupling agent and preparation method thereof containing oligomeric metal alkoxides - Google Patents
A kind of coupling agent and preparation method thereof containing oligomeric metal alkoxides Download PDFInfo
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- CN106588959B CN106588959B CN201610998222.6A CN201610998222A CN106588959B CN 106588959 B CN106588959 B CN 106588959B CN 201610998222 A CN201610998222 A CN 201610998222A CN 106588959 B CN106588959 B CN 106588959B
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- Prior art keywords
- coupling agent
- metal alkoxides
- alcohol
- acid
- ligand molecular
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- 239000007822 coupling agent Substances 0.000 title claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 55
- 239000002184 metal Substances 0.000 title claims abstract description 55
- 150000004703 alkoxides Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 14
- -1 glyoxal alkoxide compounds Chemical class 0.000 claims abstract description 47
- 239000003446 ligand Substances 0.000 claims abstract description 44
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 17
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N alpha-ketodiacetal Natural products O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002848 electrochemical method Methods 0.000 claims abstract description 3
- 229940015043 glyoxal Drugs 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 238000005868 electrolysis reaction Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000012429 reaction media Substances 0.000 claims description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 7
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical class CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000001110 calcium chloride Substances 0.000 claims description 6
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- JOONSONEBWTBLT-UHFFFAOYSA-N 2-tetradecylphenol Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1O JOONSONEBWTBLT-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- 229940055577 oleyl alcohol Drugs 0.000 claims description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 2
- HMWIHOZPGQRZLR-UHFFFAOYSA-N 2-hexadecylphenol Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1O HMWIHOZPGQRZLR-UHFFFAOYSA-N 0.000 claims description 2
- UNYKBGSYYHWZCB-UHFFFAOYSA-N 2-tetradecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UNYKBGSYYHWZCB-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019785 NBF4 Inorganic materials 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 2
- MYOWBHNETUSQPA-UHFFFAOYSA-N tetradecane-1-sulfonic acid Chemical compound CCCCCCCCCCCCCCS(O)(=O)=O MYOWBHNETUSQPA-UHFFFAOYSA-N 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 239000010953 base metal Substances 0.000 claims 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 claims 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims 1
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims 1
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003599 detergent Substances 0.000 claims 1
- 150000008301 phosphite esters Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 125000004429 atom Chemical group 0.000 description 21
- 239000002904 solvent Substances 0.000 description 20
- 238000002156 mixing Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000010792 warming Methods 0.000 description 15
- 230000007062 hydrolysis Effects 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000005060 rubber Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- RAADJDWNEAXLBL-UHFFFAOYSA-N 1,2-di(nonyl)naphthalene Chemical compound C1=CC=CC2=C(CCCCCCCCC)C(CCCCCCCCC)=CC=C21 RAADJDWNEAXLBL-UHFFFAOYSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SFUGSFCZHFPQBZ-UHFFFAOYSA-N 4-(3-phenylpropyl)-2h-triazole Chemical compound C=1C=CC=CC=1CCCC=1C=NNN=1 SFUGSFCZHFPQBZ-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 241000233855 Orchidaceae Species 0.000 description 1
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- ZGUQGPFMMTZGBQ-UHFFFAOYSA-N [Al].[Al].[Zr] Chemical compound [Al].[Al].[Zr] ZGUQGPFMMTZGBQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 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 description 1
- 238000004945 emulsification Methods 0.000 description 1
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- 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
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- ZTFZSHLWORMEHO-UHFFFAOYSA-A pentaaluminum;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ZTFZSHLWORMEHO-UHFFFAOYSA-A 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C08K5/138—Phenolates
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Abstract
The invention discloses a kind of coupling agent and preparation method thereof containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Description
Technical field
The invention belongs to new compound fields, are related to a kind of new compound and its synthetic method, and in particular to a kind of
Coupling agent and preparation method thereof containing oligomeric metal alkoxides.
Background technique
Coupling agent is also referred to as surface treating agent, it is led between inorganic material and organic material or different organic materials
Physics chemical action is crossed, a kind of organic compound for improving the two compatibility.The maximum feature of coupling agent molecule structure
Be in molecule containing two kinds of groups that chemical property is different: a kind of group can be reacted with the chemical group of mineral surfaces, be formed
Strong chemical bonding；Another group then has organophilic property, can with reactive organic molecule or physical entanglement, thus
Two kinds of different materials of property are combined.And then greatly improve the physical property, thermodynamic property, photoelectricity of composite material
Performance etc..
In recent years, coupling agent has been widely used for coating, bonding agent, plastics, rubber, glass reinforced plastic, ink, laminated product
And in the surface modification of a variety of materials.It can be effectively improved processing performance, product quality is improved, reduce cost of material, for exploitation
New product, expansion new application are laid a good foundation, and are an indispensable analog assistants in production and living.Last century the fifties U.S.
E.I.Du Pont Company takes the lead in having invented " fertile orchid " serial chromium system coupling agent, and is widely used in the surface treatment of glass fibre, still
Since the toxicity of chromium ion will cause environmental pollution, which is not promoted more；At the same time, American Association
The silicon system coupling agent of amino silane series has been invented by Carbide, and this coupling agent is widely used in plastics industry and rubber adds
In work, and significant effect；Kenrich Petrochemicals, Inc., the seventies U.S. is proposed titanium system coupling agent, for plastics,
Coating, bonding agent etc..
At present for the research of coupling agent, production and application still based on silicon, aluminium, titanium system, the coupling of these systems
Agent is mostly using respective anhydrous chloride to disclose a kind of aluminium chloride and alkali in raw material, such as CN100386332C
The novel aluminum-zirconium coupling agent of formula zirconium chloride preparation, increases the hydrolytic stability of coupling agent, reduces the viscosity of coating.But by
In containing chlorine element, certain corrosion can be will also result in production equipment, while also having injury to production operation personnel, these because
Element integrates, it will raises the final price of product, limits their further popularization and application.It is public in CN85102942A
A kind of method with aluminum alkoxide production coupling agent is opened, which synthesizes aluminum alkoxide using chemical preparation method, not
The applicability of other central atoms is studied.
In addition, with the continuous development of composite material, and the raising of the performance requirement to modification of synthetic materials, people by
Gradually recognize that traditional coupling agent has been difficult to meet the growing requirement of polymer rigid, toughness.Research emphasis from now on will
It is placed on applied widely, one multipotency, the novel coupling agent that modified effect is more preferable, cost is less expensive and corresponding coupling technology
On, this is to the development of China's chemical industry and improves product quality, reduces cost, improves benefit, significant.
Summary of the invention
The technical issues of solution: it in order to overcome the drawbacks of the prior art, obtains a kind of with multiple central atoms, crosslinking knot
Stable, applied widely, modified effect is good, product purity the is high coupling agent of structure, the present invention provides one kind to contain oligomeric alkoxy
Coupling agent of metal and preparation method thereof.
Technical solution: a kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is the central atom of coupling agent；OR is alkoxy；R ' is long chain alkane；L is ligand molecular, and p, q are to match
Body molecular number；A, b is the degree of polymerization and a+b < 5.
Preferably, the central atom is magnesium, aluminium, germanium, gallium, titanium, zirconium, tantalum, niobium, scandium or yttrium.
Preferably, the long chain alkane is alcohols, phenols, carboxylic acids, phosphoric acid ester or sulphonic acids.
Further, the long chain alkane is octanol, decyl alcohol, oleyl alcohol, sub- oleyl alcohol, soft lipidol, stearyl alcohol, laruyl alcohol, beans
Cool alcohol, dodecyl phenol, myristyl phenol, cetyl phenol, australol, octanoic acid, capric acid, oleic acid, sub- oil
Acid, ricinoleic acid, linolenic acid, palmitic acid, stearic acid, lauric acid, myristic acid, diisooctyl phosphoric acid ester, diisooctyl phosphorous
Acid esters, diisooctyl pyrophosphate, diisooctyl pyrophosphite, such as dodecyl sodium sulfonate, dodecyl benzene sulfonic acid, two (ten
Dialkyl group) benzene sulfonic acid, three (dodecyl) benzene sulfonic acids, myristyl sulfonic acid or myristyl benzene sulfonic acid.
Preferably, the ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
Step 1, using electrochemical method by central atom electrosynthesis glyoxal alkoxide compound, catalyzing and condensing obtains oligomeric state
Metal alkoxides；
Step 2 mixes oligomeric state metal alkoxides, long chain alkane and ligand molecular, wherein the oligomeric state of every 1 part of quality
The ligand molecular of metal alkoxides, the long chain alkane and 1.5~3 parts of quality that need 2~3 parts of quality is reacted；By mixture
It is placed in Soxhlet extractor and carries out heating reflux reaction, heating temperature is 90~160 DEG C, and back flow reaction carries out 4~6h, is contained
The coupling agent of oligomeric metal alkoxides.
Preferably, the reaction process of step 1 are as follows:
Wherein, R " OH is Alcohol Electrolysis；Reaction medium is n,N dimethylformamide, and electrolytic cell pressure is 10~50V, when electrolysis
Between be 30~70h；Using Pt as cathode, using the block stock of central atom as anode；Water-bath is carried out to product after electrolysis to add
2~4h of heat, temperature are 70~100 DEG C.
Preferably, the Alcohol Electrolysis is the lower alcohol containing 1~6 carbon atom, specially methanol, ethyl alcohol, normal propyl alcohol, isopropyl
At least one of alcohol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol.
Preferably, the supporting electrolyte is Me4NCl、R4NBr、R4NBF4、LiClO4、Bu4NCl、NaCl、CaCl2、
NH4Cl、AlCl3, at least one of NaBr, LiCl, KI.
Preferably, the reaction process of step 2 are as follows:
Wherein, n is the degree of polymerization, n < 5；X and m is reactant parameter, x > b, m > p+q；By oligomeric state metal alkoxides, long-chain
Paraffinic feedstock, ligand molecular are mixed, and the dimethylbenzene with quality such as mixtures is added as reaction medium.
Further, by taking metallic aluminium as an example, the reaction principle of the preparation method of the oligomeric metal alkoxides are as follows:
The N of its quality 10~20%, N dimethyl formyl is added in the alkoxide compound of metallic atom in first stage
Amine (DMF) is used as solvent, and the distilled water of mixture quality 2~5% is added dropwise after being warming up to 100 DEG C, and heat preservation 2~3h of reflux promotes
There is partial hydrolysis in alkoxide compound；
4~8% sodium hydroxide, the alkoxide compound of catalysed partial hydrolysis is added dropwise in second stage in mixed system
Carry out dehydrating condensation；
It is third and fourth stage, identical as the principle in the first and second stage；Reaction continues to that system does not have water vapour at 100 DEG C
Until spilling, being warming up to 160 DEG C at this time evaporates solvent, is warming up to 220~260 DEG C after system stops boiling, will evaporate
The liquid come is condensed, is collected.
The utility model has the advantages that (1) synthesizes alkoxide compound using different central atom, and with long chain alkane, ligand molecular
React the coupling agent for preparing, it is applied widely, modified effect is good, low in cost；(2) the method for the invention is coupled
The yield of agent is high, and reachable 80% or more, purity is high, and the generation without harmful element chlorine；(3) coupling agent that the present invention obtains has
Multiple central atoms have bigger Space adjustment water-disintegrable and associativity, and HLB value is wide in range, cross-linked structure is big and stablizes；(4)
Coupling agent of the present invention improves the additional amount of inorganic filler in rubber industry, extends the service life of rubber；(5) this hair
The bright coupling agent can be improved the mechanical strength, dispersibility and stability of water paint.
Specific embodiment
Following embodiment further illustrates the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where spirit of that invention and essence, to modification made by the method for the present invention, step or condition and replaces, belong to the present invention
Range.Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Embodiment 1
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is magnesium；OR is alkoxy；R ' is octanol；L is ligand molecular, and p, q are ligand molecular numbers；A, b is polymerization
Degree and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
10V, electrolysis time 70h, to obtain alkoxide compound.Heating water bath 2h is carried out to product after electrolysis, temperature is
80 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 10%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature reflux 3h, alkoxide compound is promoted partial hydrolysis occur to the distilled water of dropwise addition mixture quality 2% after 100 DEG C；
Then 6% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；Reaction
Until continueing to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system stops boiling
It is warming up to 220 DEG C after rising, the liquid being evaporated is condensed, oligomeric state metal alkoxides can be obtained.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 90
DEG C, back flow reaction carries out 6h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is ethyl alcohol and normal propyl alcohol with volume ratio 2:1 mixing.
The supporting electrolyte is AlCl3And CaCl2The mixing of 1:2 in mass ratio.
The oligomeric state alkoxyl magnesium, octanol and ligand molecular are with mass ratio 1:3:2 mixing.
Embodiment 2
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is magnesium；OR is alkoxy；R ' is diisooctyl pyrophosphate；L is ligand molecular, and p, q are ligand moleculars
Number；A, b is the degree of polymerization and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
50V, electrolysis time 30h, to obtain alkoxide compound.Heating water bath 4h is carried out to product after electrolysis, temperature is
70 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 15%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature reflux 2h, alkoxide compound is promoted partial hydrolysis occur to the distilled water of dropwise addition mixture quality 4% after 100 DEG C；
Then 8% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；Reaction
Until continueing to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system stops boiling
It is warming up to 260 DEG C after rising, the liquid being evaporated is condensed, oligomeric state metal alkoxides can be obtained.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 160
DEG C, back flow reaction carries out 4h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is methanol and ethyl alcohol with volume ratio 2:3 mixing.
The supporting electrolyte is NaCl and CaCl2The mixing of 2:1 in mass ratio.
Oligomeric state alkoxyl magnesium, diisooctyl pyrophosphate and ligand molecular are with mass ratio 1:3:1.5 mixing.
Embodiment 3
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is zirconium；OR is alkoxy；R ' is dodecyl benzene sulfonic acid；L is ligand molecular, and p, q are ligand molecular numbers；
A, b is the degree of polymerization and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
30V, electrolysis time 60h, to obtain alkoxide compound.Heating water bath 3h is carried out to product after electrolysis, temperature is
100 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 20%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature reflux 3h, alkoxide compound is promoted partial hydrolysis occur to the distilled water of dropwise addition mixture quality 5% after 100 DEG C；
Then 4% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；Reaction
Until continueing to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system stops boiling
It is warming up to 240 DEG C after rising, the liquid being evaporated is condensed, oligomeric state metal alkoxides can be obtained.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 100
DEG C, back flow reaction carries out 5h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is normal propyl alcohol and n-butanol with volume ratio 1:1 mixing.
The supporting electrolyte is NaCl, CaCl2And NH4Cl 1:1:1 in mass ratio mixing.
The oligomeric state zirconium alkoxide, dodecyl benzene sulfonic acid and ligand molecular are with mass ratio 1:2:2 mixing.
Embodiment 4
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is germanium；OR is alkoxy；R ' is myristyl phenol；L is ligand molecular, and p, q are ligand molecular numbers；a,
B is the degree of polymerization and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
40V, electrolysis time 60h, to obtain alkoxide compound.Heating water bath 2.5h, temperature are carried out to product after electrolysis
It is 80 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 10%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature 2~3h of reflux, alkoxide compound is promoted part water occur to the distilled water of dropwise addition mixture quality 3% after 100 DEG C
Solution；Then 7% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；
Until reaction continues to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system is stopped
Defervescence is warming up to 250 DEG C after rising, the liquid being evaporated is condensed, and can obtain oligomeric state metal alkoxides.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 140
DEG C, back flow reaction carries out 4h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is methanol and normal propyl alcohol with volume ratio 3:2 mixing.
The supporting electrolyte is LiCl and AlCl3The mixing of 1:2 in mass ratio.
The oligomeric state alkoxy germanium, myristyl phenol and ligand molecular are with mass ratio 1:4:2 mixing.
Embodiment 5
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is aluminium；OR is alkoxy；R ' is lauric acid；L is ligand molecular, and p, q are ligand molecular numbers；A, b is poly-
Right and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
35V, electrolysis time 45h, to obtain alkoxide compound.Heating water bath 3.5h, temperature are carried out to product after electrolysis
It is 85 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 15%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature reflux 2h, alkoxide compound is promoted partial hydrolysis occur to the distilled water of dropwise addition mixture quality 4% after 100 DEG C；
Then 6% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；Reaction
Until continueing to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system stops boiling
It is warming up to 230 DEG C after rising, the liquid being evaporated is condensed, oligomeric state metal alkoxides can be obtained.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 120
DEG C, back flow reaction carries out 4h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is methanol and ethyl alcohol with volume ratio 1:2 mixing.
The supporting electrolyte is NaCl and NH4Cl 1:1 in mass ratio mixing.
The oligomeric state aluminum alkoxide, lauric acid and ligand molecular are with mass ratio 1:4:3 mixing.
Embodiment 6
A kind of coupling agent containing oligomeric metal alkoxides, the general formula of the coupling agent are as follows:
Wherein, M is aluminium；OR is alkoxy；R ' is diisooctyl pyrophosphate；L is ligand molecular, and p, q are ligand moleculars
Number；A, b is the degree of polymerization and a+b < 5.
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1.
The preparation method of the coupling agent containing oligomeric metal alkoxides comprising the steps of:
The block stock of central atom is prepared into electrode by step 1, is inserted by Alcohol Electrolysis, n,N dimethylformamide, branch
In the cell liquid for holding electrolyte composition, using Pt as cathode, using the block stock of central atom as anode.Electrolytic cell is voltage-controlled to be made as
45V, electrolysis time 55h, to obtain alkoxide compound.Heating water bath 3h is carried out to product after electrolysis, temperature is
90 DEG C, promotes the alcohol for wherein having neither part nor lot in reaction and solvent to volatilize, obtain the alkoxide compound of purification.
Step 2, in the alkoxide compound of purification, be added 20%N, N-dimethylformamide (DMF) be used as solvent, rise
Temperature keeps the temperature reflux 2h, alkoxide compound is promoted partial hydrolysis occur to the distilled water of dropwise addition mixture quality 5% after 100 DEG C；
Then 5% sodium hydroxide is added dropwise in mixed system, the alkoxide compound of catalysed partial hydrolysis carries out dehydrating condensation；Reaction
Until continueing to that system does not have water vapour spilling at 100 DEG C, being warming up to 160 DEG C at this time evaporates solvent, when system stops boiling
It is warming up to 240 DEG C after rising, the liquid being evaporated is condensed, oligomeric state metal alkoxides can be obtained.
Oligomeric state metal alkoxides, long chain alkane raw material, ligand molecular are mixed, are added and the matter such as mixture
The dimethylbenzene of amount is as reaction medium, and reaction system, which is placed in Soxhlet extractor, carries out heating reflux reaction, heating temperature 150
DEG C,
Back flow reaction carries out 5h, can be obtained the coupling agent containing oligomeric state metal alkoxides.
The Alcohol Electrolysis is ethyl alcohol and normal propyl alcohol with volume ratio 2:1 mixing.
The supporting electrolyte is NaCl and CaCl2The mixing of 1:1 in mass ratio.
The oligomeric state aluminum alkoxide, diisooctyl pyrophosphate and ligand molecular are with mass ratio 1:3:3 mixing.
The coupling agent containing oligomeric state metal alkoxides that Examples 1 to 6 is prepared is used for the aqueous of following component
In coating: aqueous epoxy resins (aqueous E-44) 55%, curing agent (emulsification polyamine curing agent) 5%, coalescing agent (ethyl alcohol:
Butanol: butyl glycol ether=10:5:1) 3%, filler (trbasic zinc phosphate: zinc molybdate: aluminium triphosphate: titanium dioxide: talcum powder=3:3:
2:1:1) 28%, corrosion inhibiter (dinonyl naphthalene sulfonate barium: dodecenylsuccinic acid: phenylpropyl triazole=3:1:1) 2%, the present invention
Coupling agent 7%.
Above-mentioned coating is tested after forming coating, as a result as shown in the table:
Claims (5)
1. a kind of coupling agent containing oligomeric metal alkoxides, which is characterized in that the general formula of the coupling agent is as follows:
Wherein, M is the central atom of coupling agent；OR is alkoxy；R ' is octanol, decyl alcohol, oleyl alcohol, sub- oleyl alcohol, soft lipidol, tristearin
Alcohol, laruyl alcohol, cardanol, dodecyl phenol, myristyl phenol, cetyl phenol, australol, octanoic acid, the last of the ten Heavenly stems
Acid, oleic acid, linoleic acid, ricinoleic acid, linolenic acid, palmitic acid, stearic acid, lauric acid, myristic acid, diisooctyl phosphoric acid ester,
Diisooctyl phosphite ester, diisooctyl pyrophosphate, diisooctyl pyrophosphite, dodecyl sodium sulfonate, detergent alkylate
Sulfonic acid, two (dodecyl) benzene sulfonic acids, three (dodecyl) benzene sulfonic acids, myristyl sulfonic acid or myristyl benzene sulfonic acid；L be with
Body molecule, p, q are ligand molecular numbers；A, b is the degree of polymerization and a+b < 5；
The central atom is magnesium, aluminium, germanium, gallium, titanium, zirconium, tantalum, niobium, scandium or yttrium；
The ligand molecular is ethamine and ethylenediamine with the mixture of molar ratio 1:1；
The coupling agent containing oligomeric metal alkoxides is made by following methods:
Step 1, using electrochemical method by central atom electrosynthesis glyoxal alkoxide compound, catalyzing and condensing obtains oligomeric state alcoxyl
Base Metal；
Step 2 mixes oligomeric state metal alkoxides, long chain alkane and ligand molecular, wherein the oligomeric state alcoxyl of every 1 part of quality
The ligand molecular of Base Metal, the long chain alkane and 1.5~3 parts of quality that need 2~3 parts of quality is reacted；Mixture is placed in
Heating reflux reaction is carried out in Soxhlet extractor, heating temperature is 90~160 DEG C, and back flow reaction carries out 4~6h, obtains containing oligomeric
The coupling agent of metal alkoxides.
2. the coupling agent according to claim 1 containing oligomeric metal alkoxides, which is characterized in that the reaction process of step 1
Are as follows:
Wherein, R " OH is Alcohol Electrolysis；Reaction medium is n,N dimethylformamide, and electrolytic cell pressure is 10~50V, and electrolysis time is
30~70h；Using Pt as cathode, using the block stock of central atom as anode；After electrolysis to product carry out heating water bath 2~
4h, temperature are 70~100 DEG C.
3. the coupling agent according to claim 1 containing oligomeric metal alkoxides, which is characterized in that the Alcohol Electrolysis is first
At least one of alcohol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, amylalcohol, hexanol.
4. the coupling agent according to claim 1 containing oligomeric metal alkoxides, which is characterized in that the supporting electrolyte is
Me4NCl、R4NBr、R4NBF4、LiClO4、Bu4NCl、NaCl、CaCl2、NH4Cl、AlCl3, in NaBr, LiCl, KI at least one
Kind.
5. the coupling agent according to claim 1 containing oligomeric metal alkoxides, which is characterized in that the reaction process of step 2
Are as follows:
Wherein, n is the degree of polymerization, n < 5；X and m is reactant parameter, x > b, m > p+q；By oligomeric state metal alkoxides, long chain alkane
Raw material, ligand molecular are mixed, and the dimethylbenzene with quality such as mixtures is added as reaction medium.
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