CN104016933B - A kind of triazine-based compound containing surface active groups and its preparation method and application - Google Patents
A kind of triazine-based compound containing surface active groups and its preparation method and application Download PDFInfo
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- CN104016933B CN104016933B CN201410281217.4A CN201410281217A CN104016933B CN 104016933 B CN104016933 B CN 104016933B CN 201410281217 A CN201410281217 A CN 201410281217A CN 104016933 B CN104016933 B CN 104016933B
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- triazine
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- surface active
- based compound
- active groups
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 229920000136 polysorbate Polymers 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000003446 ligand Substances 0.000 claims description 50
- 239000013067 intermediate product Substances 0.000 claims description 29
- 239000002736 nonionic surfactant Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- LZKGFGLOQNSMBS-UHFFFAOYSA-N 4,5,6-trichlorotriazine Chemical compound ClC1=NN=NC(Cl)=C1Cl LZKGFGLOQNSMBS-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000004471 Glycine Substances 0.000 claims description 12
- -1 fatty acid ester Chemical class 0.000 claims description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 101710141544 Allatotropin-related peptide Proteins 0.000 claims description 9
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 4
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 3
- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000004899 motility Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 52
- 239000000047 product Substances 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 27
- 239000012071 phase Substances 0.000 description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 20
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 18
- 239000008346 aqueous phase Substances 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 18
- 229920002401 polyacrylamide Polymers 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000009835 boiling Methods 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 13
- 208000035126 Facies Diseases 0.000 description 11
- 150000004699 copper complex Chemical class 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000002051 biphasic effect Effects 0.000 description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 230000004044 response Effects 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000011557 critical solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 229940057995 liquid paraffin Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- CEQFOVLGLXCDCX-UHFFFAOYSA-N 2-[[4-(dimethylamino)phenyl]diazenyl]benzoic acid Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-UHFFFAOYSA-N 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002815 homogeneous catalyst Substances 0.000 description 5
- 238000007037 hydroformylation reaction Methods 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 5
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000001419 dependent effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910002567 K2S2O8 Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical class C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 238000006075 micellar catalysis Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- MEUIIHOXOWVKNP-UHFFFAOYSA-N phosphanylformic acid Chemical compound OC(P)=O MEUIIHOXOWVKNP-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Saccharide Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of triazine-based compound containing surface active groups and its preparation method and application, belong to compou nd synthesis field.A kind of triazine-based compound containing surface active groups, for having following compounds of formula IIn formula, X is Cl, OH, NH2、‑OCH3Or OCH2CH3；R1It is CH2CH2NH2Or CH2COOH；R2It is O (CH2CH2O)nCmH2m+1Or Tween residue, wherein, wherein, n is the integer of 7～16；M is the integer of 12～18.Triazine-based compound containing surface active groups provided by the present invention has reaction raw materials and is easy to get, reacts easily controllable, the motility of operation, the multifarious advantage of product.
Description
Technical field
The present invention relates to a kind of triazine-based compound containing surface active groups and its preparation method and application, belonging to
Compound synthesis field.
Background technology
Homogeneous catalysis technology is widely used in chemical industry, and wherein homogeneous catalyst is due to its active center high degree of dispersion,
Show the higher catalysis activity than heterogeneous catalyst, but homogeneous catalyst mostly is precious metal, expensive, and
Being not readily separated and recycle, easy loss even causes environmental pollution.How by same at heterogenize of homogeneous catalyst
Time keep high activity, and be prone to separate with product, it is possible to efficient recovery, the difficult point that always catalytic field is studied it
One.By the research that the approach of homogeneous catalysis heterogenize is difficult to solve homogeneous catalyst separation, have been subjected to nearly half generation
The course recorded.Add up to, two big classes can be divided into: one is catalyst static state to be fixed on organic polymer or without airborne
Immobilized on body；Another kind of be catalyst dynamically " supporting " is implemented in the liquid phase immiscible with product liquid/
Liquid biphasic catalysis.
1984, by the water of Germany Ruhrchemie AG and France's RhnePoulenc company joint development/organic biphase
The RCH/RP technique of hydroformylation of propene hutanal successfully realizes industrialization, indicates that the biphase research and development of liquid liquid obtain and goes through
History is in progress.It not only advances the further development of water/organic biphasic catalysis, and has expedited the emergence of that non-aqueous liquid liquid is biphase urges
The recent studies on field changed.Water/three sodium sulfonates (TPPTS) of organic biphasic catalysis water-soluble phosphine ligand triphenylphosphine and metal
Complexation forms catalyst.Catalytic reaction is there is in complex catalyst at water oil phase interface.At the end of reaction, by being separated
Reclaim catalyst.Owing to water solublity little Organic substance dissolubility in water is little so that the reaction rate at aqueous phase occurs
In water, spread control by Organic substance and be decreased obviously.
For solving the application of above-mentioned catalyst by the water miscible restriction of substrate.Occur in that following several method:
1. increase-volume method.Hanson etc. are used in water/organic facies that to add water-miscible methanol, ethanol and acetonitrile etc. organic
Solvent makes reaction rate improve to increase water-insoluble substrate method of dissolubility in aqueous phase, but meanwhile, this method
Also can increase water dissolubility in organic facies, thus cause catalyst more to the problem of organic facies loss.
2. micellar catalysis method.Surfactant forms micelle in water, increases organic substrates dissolubility in water.Cornils
Deng adding cationic surfactant benzyl trimethyl ammonium salt in system, water/organic two that TPPTS/Rh is catalyzed can be made
The conversion ratio of mutually middle 1-hexene hydroformylation brings up to about 50% from about 20%.But, applying surface activating agent can draw
Play its new problem of separating with product and emulsifying may be produced and increase separated difficulty.The problems referred to above are deposited
, Hanson etc. passes through to introduce the linear paraffin of certain length in water-soluble phosphine ligand TPPTS, has synthesized and has had concurrently
The Phosphine ligands of surfactant, it is to avoid the unfavorable factor that applying surface activating agent brings.But due to depositing of surface activity
Still can there is the difficulty that is separated, the problem of catalyst loss.Cyclodextrin is utilized to have lipophile hole and hydrophilic surface
This characteristic, Monflier etc. uses the method adding chemical modification cyclodextrin, makes catalyst shift two alternate realizations.
Based on this principle, the method that the water-soluble phosphine ligand of cyclo-dextrin-modified occurs.Cyclodextrin unites two into one with Phosphine ligands
New part, shows preferable performance in water/organic biphase hydroformylation of C8 alkene.Weak point is, its water
Dissolubility is the biggest, it is difficult to cause part to run off in aqueous phase catalyst " locking " completely.
3.pH regulates method.Phosphine ligands containing amino, hydroxyl and carboxyl is used for the water of 1-octene/organic by Leeuwen etc.
Biphase hydroformylation reaction.The water solublity of these Phosphine ligands depends on the pH value of aqueous solution, and amino phosphine is dissolved in acid Jie
Matter, hydroxyl and carboxyl phosphine then present certain water solublity at alkaline medium.Therefore can be by the pH value of regulation system, will
It is dissolved in the purpose that the catalyst extraction of organic facies reaches to separate with product to aqueous phase.Because of need to through acid and the alternate treatment of alkali,
Can make that system has salt constantly to accumulate, affect reaction rate and catalyst activity.
4. part promotion law.Chaudhari etc. are from the amphipathic property energy angle of regulation water-soluble metal complexes catalyst
Set out, it is proposed that the concept of " promotion part ".By to water-soluble catalyst [HRh (CO) (TPPTS)3Add in]
Enter appropriate oil-soluble promotion ligand triphenylphosphine (TPP), make the hydroformylation reaction speed of 1-octene improve 10～50
Times.
5. temperature control phase transfer method.Gold woods etc. the concept of Cloud Points of Nonionic Surfactants is introduced Phosphine ligands design and
Synthesis, has developed a class and has had the temperature control nonionic water soluble phosphines of converse " temperature-water solublity " characteristic, established
Water/organic biphase " thermoregulated phase transfer catalysis " concept, for being inherently eliminated water/organic biphasic catalysis scope of application the end of by
The problem that thing water solublity limits has started a new way.There is the catalyst of good aqueous solubility, at temperature liter under room temperature
Can separate out to during cloud point from water and be transferred to organic facies.Therefore, catalyst is respectively at substrate before starting the reaction
Biphase, and under the reaction temperature higher than cloud point, catalyst separates out from water, is transferred to organic facies, and substrate coexistence
In organic facies, reaction is carried out in organic facies；Question response terminates, and when being cooled to cloud point temperature below, catalyst is the most extensive
Rehydration dissolubility, returns to aqueous phase from organic facies, so that the catalyst in aqueous phase can be separated by simple and be contained
The organic facies of product separately, reaches the purpose of separation and recovery of catalyst.
Temperature control non-aqueous liquid liquid biphasic catalysis is to there is critical solution temperature based on some bi-component or multicomponent dicyandiamide solution
(CST) two kinds of solvents immiscible under characteristic, i.e. room temperature are when rising to CST, in state of dissolving each other completely, thus
Regulating and controlling temperature can be passed through, reach the purpose of " homogeneous reaction, two-phase laminated flow ".Continue water/organic in liquid liquid biphasic catalysis field
Another hot fields after biphasic catalysis.It not only compensate for water/organic biphasic catalysis range of application and is limited by substrate water solublity
Problem, and may be used for the composition catalyst to water sensitive and to the substrate of water sensitive or product, widened and joined
The range of choice of body, catalyst and substrate.1. FBS strategy, early 1990s, Horvath etc. is based on entirely
The characteristic that fluorous solvent is limited with most organic solvent intermiscibilities at low temperatures and dissolves each other under high temperature, it is proposed that " fluorine two-phase mixture
System (fluorous biphasicsystem, FBS) ", and it is successfully used to homogeneous complex catalysis reaction, start a letter
The new way that single, effective homogeneous catalyst separation reclaims.The most organic liquid liquid biphasic catalysis, low-carbon alcohols/alkane two-phase mixture
System, alkane two-phase system, ethylene (third) alkene ester/alkane two-phase system, Polyethylene Glycol (PEG) two-phase system, temperature control
The principle that the systems such as non-aqueous ionic liquid system exist critical solution temperature all in accordance with bi-component or multicomponent dicyandiamide solution is real
The recovery of existing catalyst.3. Thermoregulated phase separation catalysis, gold woods, Wang Yanhua etc. are based on being referred to as temperature control phase transfer part
Nonionic surfactant Phosphine ligands and organic solvent there may be the imagination of critical solution temperature (CST).Temperature control divides mutually
Feature from catalytic process is that the sticky shape liquid catalyst formed by thermoregulated ligand and Rh, Ru is less than Critical Solution
Certainly becoming a phase insoluble in organic solvent during temperature, when reaction temperature rises to more than critical solution temperature, catalyst is molten
In organic facies in homogeneous system；When reacting end and being cooled to less than critical solution temperature, catalyst is again from product phase
Separating out, system recovers biphase, can pass through decant, is separated with catalyst by product easily.But, such is joined
Transition metal needed for body complexation is limited, and is all noble metal, such as rhodium, platinum, ruthenium etc., expensive.
Summary of the invention
It is an object of the invention to provide a kind of triazine-based compound containing surface active groups.
A kind of triazine-based compound containing surface active groups, for having following compounds of formula I
In formula, X is-Cl ,-OH ,-NH2、-OCH3Or-OCH2CH3；
R1It is-CH2CH2NH2Or-CH2COOH；
R2It is-O (CH2CH2O)nCmH2m+1Or Tween residue, wherein, wherein, n is the integer of 7～16；m
It it is the integer of 12～18.
The preferred described n of triazine-based compound containing surface active groups of the present invention is the integer of 7～9.
The preferred described m of triazine-based compound containing surface active groups of the present invention is the integer of 12～14.
The preferred described Tween residue of triazine-based compound containing surface active groups of the present invention is for having formula
The group of Ia, Ib or Ic:
Wherein, x+y+z+w=4 or 20, R are-CpH2p+1Or-CpH2p-1, p is the integer of 12～18.
It is a further object of the present invention to provide the preparation method of the above-mentioned triazine-based compound containing surface active groups.
A kind of preparation method of the triazine-based compound containing surface active groups, at 5～35 DEG C, by trichloro-triazine with
Nonionic surfactant react, separated after intermediate product；At 60～70 DEG C, by gained intermediate product and ethylenediamine
Or glycine reaction.
In technique scheme it is significant to note that, described utilize trichloro-triazine anti-with nonionic surfactant
The step answered occurred under conditions of solvent-free (including water).
In technique scheme, the described step utilizing trichloro-triazine and nonionic surfactant to react is in course of reaction
It is preferably pressed into dry air.The HCl utilizing dry air reaction to be generated discharges reaction system, and the HCl of discharge can use
Method known in the art absorbs, and NaOH solution is preferably used and absorbs.For determining reaction end, preferably make
The HCl of discharge system is absorbed, when NaOH solution is become powder from yellow by the NaOH solution containing methyl red indicator
Time red, i.e. reach reaction end, obtain intermediate product.
In technique scheme, described nonionic surfactant is 1:1～1.3 with the mol ratio of trichloro-triazine；Preferably
Described nonionic surfactant is 1:1～1.6 with the mol ratio of ethylenediamine (or glycine)；In particular it is preferred to institute
Stating nonionic surfactant with trichloro-triazine, the mol ratio of ethylenediamine (or glycine) is 1:1～1.3:1～1.6.
Nonionic surfactant of the present invention is the nonionic surfactant chemical combination containing polyoxyethylene groups
Thing, preferably fatty alcohol-polyoxyethylene ether (AEO) or anhydrous sorbitol mono fatty acid ester polyoxyethylene ether (TWEEN).
Anhydrous sorbitol mono fatty acid ester polyoxyethylene ether of the present invention is the compound with following structural formula:
Wherein, x+y+z+w=4 or 20, R are-CpH2p+1Or-CpH2p-1, p is the integer of 12～18.
Further, described fatty alcohol-polyoxyethylene ether is preferably H2m+1CmO(CH2CH2O)nH, wherein, n is
The integer of 7～16, m is the integer of 12～18；Further preferably n is the integer of 7～9, and m is the integer of 12～14；
Especially, described fatty alcohol-polyoxyethylene ether is most preferably AEO-7 or AEO-9.
Further, described anhydrous sorbitol mono fatty acid ester polyoxyethylene ether (TWEEN) is preferably TWEEN20
Or TWEEN80.
In the step of " gained intermediate product reacts with ethylenediamine or glycine " of the present invention, preferably its reaction is molten
Agent is the mixed liquor of aqueous sodium carbonate and oxolane 1～1.5:2 composition by volume, and its pH value is 7～8.Wherein,
The preferably concentration of aqueous sodium carbonate is 5mol/L.
" separation " of the present invention preferably employs pillar layer separation.Further, described pillar layer separation preferable separate
Filler is the silica gel of 150～200 mesh, and eluant is the mixture being made up of with acetone 5:2 by volume oxolane.
It is a further object of the present invention to provide the copper complex of a kind of thermoregulated ligand.
The copper complex of a kind of thermoregulated ligand, uses the above-mentioned triazine-based compound containing surface active groups and copper ion
Complexation gained, wherein, mol ratio n (CuCl2·2H2O): n (the triazine radical chemical combination containing surface active groups
Thing)=1:1～2.5, concrete preparation process is as follows: the triazine-based compound containing surface active groups presses 0.01mol:
20～45mL are dissolved in deionized water, by CuCl2·2H2O is dissolved in deionized water by 0.005mol:10mL,
Dropping under stirring containing in the aqueous solution of the triazine-based compound of surface active groups, stirring will after reacting 1h
Solution adjusts pH value to 7.
It is yet another object of the invention to provide the application in ATRP polymerization is reacted of the above-mentioned thermoregulated ligand.
The copper complex of above-mentioned thermoregulated ligand is used for ATRP polymerization reaction, and an exemplary technical scheme is as follows:
The copper complex formazan concentration of thermoregulated ligand is 5.28 × 10-3(this concentration is that thermoregulated ligand copper complex is in aqueous phase to mol/L
Concentration with oil-phase solution summation)；Aqueous phase is by deionized water, acrylamide and K2S2O8Composition, wherein, acryloyl
Amine concentration is mol ratio n (K in 1.7mol/L, and aqueous phase2S2O8): n (acrylamide)=0.11:400；Oil phase is by liquid
Paraffin and emulsifying agent composition, wherein emulsifying agent span20 consumption is 2% (relative to oil phase liquid paraffin body usage percentage)；
V (oil phase): V (aqueous phase)=1:1, the response time is 6h, and reaction temperature is 30 DEG C.
The invention has the beneficial effects as follows: the triazine-based compound containing surface active groups provided by the present invention, possess
Advantages below: one, reaction raw materials is easy to get: the nonionic surfactant utilizing large-scale production is raw material.Two,
React easily controllable: according to the difference of activity when three chloride ion are replaced on Cyanuric Chloride molecule, reacted by control
Temperature can effectively control the degree that substitution reaction is carried out.Three, the motility of operation, product various
Property: select different nonionic surfactants can obtain the part of different cloud point；Meanwhile, different cooperations is changed
Thing, it is also possible to prepare different parts.It addition, the reaction related in this experiment, the thermoregulated ligand of synthesis, linker
In Cyanuric Chloride, the Cyanuric Chloride of a part has two chlorine atoms to be replaced, and also a chlorine atom is unsubstituted.According to temperature
Control part participates in the temperature range that the system of reaction requires, can also make thermoregulated ligand by replacing the 3rd chlorine atom
Final cloud point meet the requirements.If the temperature range that i.e., the cloud point of thermoregulated ligand requires higher than reaction system, then the
Three chloride ion can be substituted off with the group of hydrophobic group, to reduce its cloud point.Otherwise, then take with the group of hydrophilic group
In generation, to improve cloud point.According to the difference of reaction system, the difference of temperature required scope, can select different non-from
Sub-surface activating agent, and the different coordination compounds with coordination atom, prepare suitable thermoregulated ligand, thus more preferably
Form complex with transition metal, get up and effectively control the effect of reaction.The thermoregulated ligand of the type, maximum advantage
It is that it can synthesize the thermoregulated ligand of multiple different cloud point, the thermoregulated ligand of multiple different coordination atoms.To sum up, should
The thermoregulated ligand of type will have good application prospect.
Accompanying drawing explanation
Fig. 1 be during in application examples 1, inverse emulsion system prepares polyacrylamide course of reaction the response time to acrylamide
The impact of conversion ratio；
Fig. 2 is the reaction first order kinetics curve chart that application examples 1 inverse emulsion system prepares polyacrylamide；
Fig. 3 be during in application examples 2, inverse emulsion system prepares polyacrylamide course of reaction the response time to acrylamide
The impact of conversion ratio；
Fig. 4 is the reaction first order kinetics curve chart that application examples 2 inverse emulsion system prepares polyacrylamide；
Fig. 5 is polyacrylamide (using the thermoregulated ligand complex prepared using AEO9 for initiation material as controlling agent)
Infrared spectrogram；
Fig. 6 is polyacrylamide gel chromatogram (Cu2+The complex formed with thermoregulated ligand reacts as ATRP
Controlling agent).
Detailed description of the invention
One exemplary aspect of the invention is:
A kind of preparation method of the triazine-based compound containing surface active groups, at 5～35 DEG C, by trichloro-triazine with
Nonionic surfactant react, separated after intermediate product；At 60～70 DEG C, by gained intermediate product and ethylenediamine
Reaction 24h,
Wherein, n (nonionic surfactant): n (trichloro-triazine): n (ethylenediamine)=1:1～1.3:1～1.6；Middle product
Thing is aqueous sodium carbonate (concentration is 5mol/L) and oxolane 1.5:2 by volume with the reaction dissolvent of reacting ethylenediamine
The mixed liquor of composition, its pH value is 7～8.
In the embodiment above, including the step carrying out with reacting ethylenediamine products obtained therefrom separating by intermediate product, described
Separation preferably employs pillar layer separation；Further, described pillar layer separation preferable separate filler is 150～200 purposes
Silica gel, eluant is the mixture being made up of with methanol 3:5 by volume oxolane.
In the embodiment above, as n (nonionic surfactant): n (trichloro-triazine): n (ethylenediamine)=1:1～1.3:
When 1～1.6, its chemical equation is following (being as a example by fatty alcohol-polyoxyethylene ether by nonionic surfactant):
Another exemplary embodiment of the present invention is:
A kind of preparation method of the triazine-based compound containing surface active groups, at 5～35 DEG C, by trichloro-triazine with
Nonionic surfactant react, separated after intermediate product；At 60～70 DEG C, by gained intermediate product and amino
Acetic acidreaction 24h,
Wherein, n (nonionic surfactant): n (trichloro-triazine): n (glycine)=1:1～1.3:1～1.6；Middle
The reaction dissolvent that product and glycine react is aqueous sodium carbonate (concentration is 5mol/L) with oxolane by volume
The mixed liquor of 1:2 composition, its pH value is 7～8.
In the embodiment above, including intermediate product to be reacted the step that products obtained therefrom carries out separating, institute with glycine
State separation and preferably employ pillar layer separation.Further, described pillar layer separation preferable separate filler is 150～200 mesh
Silica gel, eluant is the mixture being made up of with methanol 2:1 by volume oxolane.
In the embodiment above, reaction process is following (being as a example by fatty alcohol-polyoxyethylene ether by nonionic surfactant):
Following non-limiting example can make those of ordinary skill in the art that the present invention be more fully understood, but not with
Any mode limits the present invention.
Test method described in following embodiment, if no special instructions, is conventional method；Described reagent and material,
If no special instructions, the most commercially obtain.
Embodiment 1
The synthesis of AEO9-trichloro-triazine-ethylenediamine thermoregulated ligand
AEO-9 9.700g (0.0167mol), trichloro-triazine 3.690g (0.02mol) are placed in four-hole boiling flask, water-bath
Heating, stirring, solvent-free at 35 DEG C directly react.Course of reaction is passed through in four-hole boiling flask dry air
In order to the HCl gas produced in discharge system, thus improve the conversion ratio of reaction.The HCl 0.5mol/L discharged
NaOH solution (NaOH be 0.800g preparation) absorb.Give instruction agent with C.I. 13020., the terminal of inspection reaction.
When NaOH solution is become pink from yellow, i.e. reach reaction end, obtain intermediate product.
Natrium carbonicum calcinatum 0.529g (0.05mol) is dissolved in 10ml deionized water；1.200g (0.02mol) anhydrous ethylenediamine
It is dissolved in 10ml oxolane, inserts separatory funnel after being mixed by above two solution and be added drop-wise to above-mentioned containing intermediate product
Four-hole boiling flask in, heating in water bath to 60 DEG C, stirring reaction 24h.React product at reduced pressure sucking filtration after terminating, then
Wash filter cake with deionized water and oxolane, obtain thick product.Thick product utilization chromatographic column being separated, recrystallization obtains
AEO9-trichloro-triazine-ethylenediamine thermoregulated ligand, the cloud point of gained part is 20 DEG C (pH=8,1% aqueous solutions).
After tested, the cloud point of gained intermediate product is 46 DEG C (pH=7,1% aqueous solutions), and method of testing is as follows: by gained
Intermediate product absolute ether washs, and filters, and is dried and to obtain white powdery solids, measure its cloud point be 46 DEG C (pH=7,
1% aqueous solution).
Embodiment 2
The synthesis of AEO7-trichloro-triazine-ethylenediamine thermoregulated ligand
AEO-7 8.250g (0.0167mol), trichloro-triazine 3.690g (0.02mol) are placed in four-hole boiling flask.Water-bath
Heating, stirring, solvent-free at 35 DEG C directly react.In course of reaction in four-hole boiling flask logical dry air with
The HCl gas produced in reaction system is discharged, improves the conversion ratio of reaction.The HCl 0.5mol/L's discharged
NaOH solution (NaOH is 0.800g preparation) absorbs.Give instruction agent with C.I. 13020., the terminal of inspection reaction.When
NaOH solution from yellow become pink time, i.e. reach reaction end, obtain intermediate product.
Take 0.529g (0.05mol) natrium carbonicum calcinatum and be dissolved in 10ml deionized water；By 1.200g (0.02mol) anhydrous second
Diamidogen is dissolved in 10ml oxolane, drops to above-mentioned containing intermediate product after being mixed by above two solution with separatory funnel
Flask in, heating in water bath to 60 DEG C, stirring reaction 24h.Decompression sucking filtration, washs with deionized water and oxolane
Filter cake, obtains thick product.Thick product utilization chromatographic column being separated, recrystallization obtains AEO7-trichloro-triazine-ethylenediamine temperature control
Part, the cloud point of this part is 3 DEG C (pH=8,1% aqueous solutions)
After tested, the cloud point of gained intermediate product is 39 DEG C (pH=7,1% aqueous solutions).
Embodiment 3
The synthesis of AEO9-trichloro-triazine-glycine thermoregulated ligand
AEO-9 9.700g (0.0167mol), trichloro-triazine 3.690g (0.02mol) are placed in four-hole boiling flask.Water-bath
It is heated at 35 DEG C stirring reaction.Course of reaction is led in four-hole boiling flask dry air with by generation in reaction system
HCl gas is discharged, and improves the conversion ratio of reaction.(NaOH is the NaOH solution of the HCl 0.5mol/L discharged
0.800g prepares) absorb.Give instruction agent with C.I. 13020., the terminal of inspection reaction.When NaOH solution is become from yellow
During pink, i.e. reach reaction end, obtain intermediate product.
Natrium carbonicum calcinatum 0.529g (0.05mol) is dissolved in 10mL deionized water；By 1.501g (0.02mol) amino second
Acid mixes with sodium carbonate liquor after being dissolved in 10ml deionized water, then adds the oxolane of 40ml in above-mentioned solution,
Then being added drop-wise in the above-mentioned four-hole boiling flask containing intermediate product by above-mentioned gained mixed solution with separatory funnel, water-bath adds
Heat 70 DEG C, under agitation reacts 22h.After reaction, reduce pressure sucking filtration, then with deionized water and oxolane washing filter
Cake, obtains thick product.Thick product utilization chromatographic column being separated, recrystallization obtains AEO9-trichloro-triazine-glycine temperature control
Part, the cloud point of this part is 77 DEG C (pH=5,1% aqueous solutions).
After tested, the cloud point of gained intermediate product is 46 DEG C (pH=7,1% aqueous solutions).
Embodiment 4
The synthesis of AEO7-trichloro-triazine-glycine thermoregulated ligand
AEO-7 8.250g (0.0167mol), trichloro-triazine 3.690g (0.02mol) are placed in four-hole boiling flask, at 35 DEG C
Under solvent-free directly react.Course of reaction is led in four-hole boiling flask dry air with by generation in reaction system
HCl gas is discharged, and improves the conversion ratio of reaction.It is water-soluble that HCl 0.800g (0.02mol) NaOH discharged prepares
Liquid absorbs.C.I. 13020. is utilized to give instruction agent, the terminal of inspection reaction.When NaOH solution is become pink from yellow,
I.e. reach reaction end, obtain intermediate product.
Natrium carbonicum calcinatum 0.529g (0.05mol) is dissolved in 10ml deionized water；By 1.501g (0.02mol) amino second
Acid mixes with sodium carbonate liquor after being dissolved in 10ml deionized water, then adds the oxolane of 40ml in above-mentioned solution,
Then being added drop-wise in the above-mentioned four-hole boiling flask containing intermediate product by above-mentioned gained mixed solution with separatory funnel, water-bath adds
Heat 70 DEG C, under agitation reacts 22h.After reaction, reduce pressure sucking filtration, then with deionized water and oxolane washing filter
Cake, obtains thick product.Thick product utilization chromatographic column being separated, recrystallization obtains AEO7-trichloro-triazine-glycine temperature control
Part.The cloud point of this part is 75 DEG C (pH=5,1% aqueous solutions).
After tested, the cloud point of gained intermediate product is 39 DEG C (pH=7,1% aqueous solutions).
Embodiment 5
The synthesis of TWEEN20-trichloro-triazine-ethylenediamine thermoregulated ligand
By polyoxyethylene 20 sorbitan monolaurate (TWEEN20) 14.730g (0.012mol), trichloro-triazine
1.850g (0.01mol) is placed in four-hole boiling flask, and reaction temperature is 30 DEG C.Course of reaction is led in four-hole boiling flask and is dried
Air is discharged with the HCl gas that will produce in reaction system, improves the conversion ratio of reaction.The HCl discharged uses
The aqueous solution of 0.400g (0.01mol) NaOH preparation absorbs.C.I. 13020. is utilized to give instruction agent, the terminal of inspection reaction.
When NaOH solution is become pink from yellow, i.e. reaching reaction end, the response time is 5h, obtains intermediate product.
Natrium carbonicum calcinatum 0.529g (0.05mol) is dissolved in 10ml deionized water；By 0.72g (0.012mol) ethylenediamine
Mix with sodium carbonate liquor after being dissolved in 10ml oxolane, then with separatory funnel, above-mentioned gained mixed solution is added drop-wise to
In the above-mentioned four-hole boiling flask containing intermediate product, heating in water bath 55 DEG C, under agitation reacts 5h.After reaction, decompression is taken out
Filter, then with deionized water and oxolane washing filter cake, obtains thick product.Thick product utilization chromatographic column is separated, weight
Crystallize to obtain TWEEN20-trichloro-triazine-ethylenediamine thermoregulated ligand.The cloud point of this part is 61 DEG C of (pH=8,1% water
Solution).
After tested, the cloud point of gained intermediate product is 42 DEG C (pH=7,1% aqueous solutions).
Application examples 1
The application in acrylamide (AM) controllable polymerization (ATRP polymerization) of the gained thermoregulated ligand:
Polyacrylamide is a widely used water-soluble polymer of class, be mainly used in oil field intensified oil reduction, sewage disposal,
The fields such as paper making additive.ATRP polymerization method is used to can get the polyacrylamide that molecular weight distribution is narrower, and energy
The enough control by transition metal complex to reaction, solve polymerization system due to monomer-polymer excessive and cause
The problems such as product thermal degradation, crosslinking.But conventional transition metal complex cannot be by the side being separated in system
Method efficiently separates with product, and the purity that may result in product declines, controlling agent cannot the difficult problem such as secondary recovery utilization, and adopt
The controlling agent that the complex prepared with thermoregulated ligand and transition metal reacts as ATRP, reaction end is warming up to part
The cloud point temperature of complex, complex from product mutually separate, it is easy to removing, product purity is high, and to reaction controlling
Property is good.
The product AEO9-trichloro-triazine-ethylenediamine thermoregulated ligand of gained in embodiment 1 is used to generate network with copper ion
Compound, wherein, mol ratio n (CuCl2·2H2O): n (AEO9-trichloro-triazine-ethylenediamine)=1:2, gained complex
Cloud point be 60 DEG C (pH=7,1% aqueous solutions), this complex can as acrylamide ATRP react control
Agent.
Concrete preparation process is as follows: by 7.535g (0.01mol) embodiment 1 gained AEO9-trichloro-triazine-second two
Amine thermoregulated ligand is dissolved in 45mL deionized water, by 0.85g (0.005mol) CuCl2·2H2O is dissolved in 10mL and goes
In ionized water, drop in the aqueous solution of AEO9-trichloro-triazine-ethylenediamine thermoregulated ligand under stirring, stirring
Reaction 1h, obtains the copper complex formazan aqueous solution of thermoregulated ligand, adjusts pH value extremely with the sodium hydrate aqueous solution of 0.5mol/L
7。
The copper complex formazan concentration of thermoregulated ligand is 5.28 × 10-3(this concentration is that thermoregulated ligand copper complex is in aqueous phase to mol/L
Concentration with oil-phase solution summation)；Aqueous phase is by deionized water, acrylamide and K2S2O8Composition, wherein, acryloyl
Amine concentration is mol ratio n (K in 1.7mol/L, and aqueous phase2S2O8): n (acrylamide)=0.11:400；Oil phase is by liquid
Paraffin and emulsifying agent composition, wherein emulsifying agent span20 consumption is 2% (relative to oil phase liquid paraffin body usage percentage)；
V (oil phase): V (aqueous phase)=1:1, the response time is 6h, and reaction temperature is 30 DEG C.With this understanding, acrylamide monomer
Conversion ratio is 96.1%, and the most linear growth of monomer conversion, and linearly dependent coefficient is 0.98, reaction
There is good controllability.Reaction temperature is increased to part cloud point temperature 60 DEG C by the later stage, and whole reaction is little in experience 8
Shi Hou, the final conversion ratio of its acrylamide reaches 97%.Result is as shown in Figure 1 and Figure 2.
The product AEO7-trichloro-triazine-ethylenediamine thermoregulated ligand of gained in embodiment 2 is used to generate network with copper ion
Compound, wherein, mol ratio n (CuCl2·2H2O): n (AEO7-trichloro-triazine-ethylenediamine)=1:2, gained complex
Cloud point is 58 DEG C (pH=7,1% aqueous solutions), the controlling agent that this complex can react as the ATRP of acrylamide.
Concrete preparation process is as follows: by 6.655g (0.01mol) embodiment 2 gained AEO7-trichloro-triazine-second two
Amine thermoregulated ligand is dissolved in 45mL deionized water, by 0.85g (0.005mol) CuCl2·2H2O is dissolved in 10mL and goes
In ionized water, drop in the aqueous solution of AEO7-trichloro-triazine-ethylenediamine thermoregulated ligand under stirring, stirring
Reaction 1h, obtains the copper complex formazan aqueous solution of thermoregulated ligand, adjusts pH value extremely with the sodium hydrate aqueous solution of 0.5mol/L
7。
The copper complex formazan concentration of thermoregulated ligand is 4.28 × 10-3(this concentration is that thermoregulated ligand copper complex is in aqueous phase to mol/L
Concentration with oil-phase solution summation)；Aqueous phase is by deionized water, acrylamide and K2S2O8Composition, wherein, acryloyl
Amine concentration is mol ratio n (K in 1.7mol/L, and aqueous phase2S2O8): n (AM)=0.11:400；Oil phase is molten by liquid paraffin
Forming with emulsifying agent, wherein emulsifying agent span20 consumption is 1% (relative to oil phase liquid paraffin body usage percentage)；V (oil
Phase): V (aqueous phase)=1:1, the response time is 6h, and reaction temperature is 30 DEG C.With this understanding, acrylamide monomer converts
Rate is 85%, and the most linear growth of monomer conversion, and linearly dependent coefficient is 0.99, and reaction has good
Good controllability.Reaction temperature is increased to part cloud point 58 DEG C by the later stage, and whole reaction is after experience 8 hours, and it is third years old
The final conversion ratio of acrylamide reaches 94%.Result is as shown in Figure 3, Figure 4.
Fig. 1 be during in application examples 1, inverse emulsion system prepares polyacrylamide course of reaction the response time to acrylamide
The impact of conversion ratio.As it is shown in figure 1, in optimal complex concentration C(AEO-9 temperature control complex)=5.28 × 10-3During mol/L,
Acrylamide conversion ratio is up to 97%.
Fig. 2 is the reaction first order kinetics curve chart that application examples 1 inverse emulsion system prepares polyacrylamide, such as figure institute
Showing, its linearly dependent coefficient is 0.98, presents good linear relationship.
Fig. 3 be during in application examples 2, inverse emulsion system prepares polyacrylamide course of reaction the response time to acrylamide
The impact of conversion ratio.As in figure 2 it is shown, in optimal complex concentration C(AEO-7 temperature control complex)=4.28 × 10-3During mol/L,
Acrylamide conversion ratio is up to 94%.
Fig. 4 is the reaction first order kinetics curve chart that application examples 2 inverse emulsion system prepares polyacrylamide, such as figure institute
Showing, its linearly dependent coefficient is 0.99, presents good linear relationship.
The infrared spectrogram of gained polyreaction product (polyacrylamide) is shown in Fig. 5, consults polyacrylamide standard IR
Spectrogram, it is known that 3343.58cm-1It is-NH2Stretching vibration absworption peak, 2888.65cm-1For-CH2-stretching vibration
Absworption peak, 1720.82cm-1It is the stretching vibration absworption peak of carbonyl in amide group, 1467.58cm-1It it is C-N key
Stretching vibration absworption peak.So may determine that product is polyacrylamide.
Fig. 6 is the gel chromatography figure of the polyacrylamide that application examples 1 prepares.As it can be seen, product peak is the narrowest in figure,
May certify that the polyacrylamide of gained has the feature of molecular weight narrow ditribution.
Claims (6)
1. the triazine-based compound containing surface active groups, for having following compounds of formula I
In formula, X is-Cl；
R1It is-CH2CH2NH2Or-CH2COOH；
R2It is-O (CH2CH2O)nCmH2m+1, wherein, n is the integer of 7～9；M is the integer of 12～14；R2
Or TWEEN residue, it is the group with formula Ia, Ib or Ic:
Wherein, x+y+z+w=20, described Tween are TWEEN20 or TWEEN80.
2. containing the preparation method of the triazine-based compound of surface active groups as claimed in claim 1, its feature exists
In: at 5～35 DEG C, trichloro-triazine is reacted with nonionic surfactant, after separation, obtain intermediate product；60～70 DEG C
Under, gained intermediate product is reacted with ethylenediamine or glycine；
Described nonionic surfactant is fatty alcohol-polyoxyethylene ether or anhydrous sorbitol mono fatty acid ester polyoxyethylene
Ether；
Described fatty alcohol-polyoxyethylene ether is TWEEN20 or TWEEN80.
Method the most according to claim 2, it is characterised in that: described nonionic surfactant is equal with trichlorine
The mol ratio of triazine is 1:1～1.3；Described nonionic surfactant with the mol ratio of ethylenediamine or glycine is
1:1～1.6.
Method the most according to claim 3, it is characterised in that: gained intermediate product and ethylenediamine or amino second
In the step of acid reaction, its reaction dissolvent be concentration be aqueous sodium carbonate and the oxolane of 5mol/L by volume
The mixed liquor of 1～1.5:2 composition.
5. the complex of a thermoregulated ligand, it is characterised in that: use compound described in claim 1 and copper ion network
Close gained, wherein, mol ratio CuCl2·2H2O: containing the triazine-based compound=1:1～2.5 of surface active groups, tool
Production procedure is as follows: be dissolved in by 0.01mol:20～45mL by the triazine-based compound containing surface active groups
In ionized water, by CuCl2·2H2O is dissolved in deionized water by 0.005mol:10mL, drips under stirring
To containing in the aqueous solution of the triazine-based compound of surface active groups, after stirring reaction 1h, adjust pH value to 7 solution.
6. the complex of thermoregulated ligand described in claim 5 application in ATRP polymerization is reacted.
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