CN109942501A - Poly- benzotriazole-ionic liquid copolymer containing anchoring group and its preparation method and application - Google Patents
Poly- benzotriazole-ionic liquid copolymer containing anchoring group and its preparation method and application Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 96
- 229920001577 copolymer Polymers 0.000 title claims abstract description 62
- 238000004873 anchoring Methods 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 38
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical group NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 229960003638 dopamine Drugs 0.000 claims abstract description 11
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011984 grubbs catalyst Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000011259 mixed solution Substances 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000012964 benzotriazole Substances 0.000 claims description 30
- -1 benzotriazole compound Chemical class 0.000 claims description 25
- QXPWKLBWUZALNM-UHFFFAOYSA-N 2h-benzotriazole;1h-imidazole Chemical class C1=CNC=N1.C1=CC=CC2=NNN=C21 QXPWKLBWUZALNM-UHFFFAOYSA-N 0.000 claims description 22
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 20
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 20
- CKUIXMZIYINDMQ-UHFFFAOYSA-N 4-(bromomethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CBr)C2 CKUIXMZIYINDMQ-UHFFFAOYSA-N 0.000 claims description 19
- 230000003373 anti-fouling effect Effects 0.000 claims description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- 238000005292 vacuum distillation Methods 0.000 claims description 15
- 229910001914 chlorine tetroxide Inorganic materials 0.000 claims description 14
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000002152 alkylating effect Effects 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000005349 anion exchange Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- VSEROABGEVRIRY-UHFFFAOYSA-N 1-(chloromethyl)benzotriazole Chemical compound C1=CC=C2N(CCl)N=NC2=C1 VSEROABGEVRIRY-UHFFFAOYSA-N 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 229910002056 binary alloy Inorganic materials 0.000 abstract 1
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000007853 buffer solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 241000195649 Chlorella <Chlorellales> Species 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- KCMZYCFSSYXEQR-UHFFFAOYSA-N CCCC[K] Chemical compound CCCC[K] KCMZYCFSSYXEQR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention belongs to material chemistry technical fields, disclose a kind of poly- benzotriazole-ionic liquid copolymer and its preparation method and application containing anchoring group.The preparation method comprises the following steps: first by designing and preparing the monomer containing poly- benzotriazole-ionic liquid, then under Grubbs catalyst, method by ring-opening metathesis polymerization and the Anchor Agent combined polymerization for having dopamine structure, can obtain the marine anti-pollution material of poly- benzotriazole-ionic liquid binary system.This preparation method cost of material is low, easy to operate, and the copolymer assembling property of acquisition is strong, has the effect of good marine anti-pollution.
Description
Technical field
The invention belongs to material chemistry technical fields, be related to marine anti-pollution material, and in particular to a kind of containing anchoring group
Poly- benzotriazole-ionic liquid copolymer and its preparation method and application.
Background technique
Marine fouling organism be to being grown in the animal on ocean underwater facility surface, the general name of plant and microorganism, it is attached
Seriously restrict the exploitation and utilization of marine resources, caused to sea transport and the exploration of marine resources, exploitation huge
Harm: increasing the resistance on naval vessel, increases amount of fuel, ship's speed reduces；Cause oceanographic instrumentation distorted signals, reduced performance even instrument
Device failure；Block the seawater pipeline on instrument facility；The Anaerobic Corrosion of metal is caused, Ship Life is shortened；Influence ship
Safety of oceangoing ship etc..Furthermore marine fouling organism can also move into other sea areas with ship, balance to local marine ecology
It impacts.Therefore the biological attachment for effectively solving underwater sailing body will safeguard that maritime rights and interests, Development of Marine have weight to China
Profound significance greatly.
It includes the spies such as biocompatibility, anticorrosion and antifouling, molecular recognition that polymer, which can assign the various properties of material,
Property, so substrate surface grafting antifouling polymers are to prepare one of effective means of anti-fouling material.Antifouling polymerization common at present
Object includes: polyethylene glycol and its derivative, amphoteric ion polymer, containing functional groups' cationic polymers such as pyridine, quaternary ammonium salts.Benzene
And triazole is an important aromatic aza cycle compound, can be used as the isostere of benzimidazole, imidazoles, triazole etc., can be led to
It crosses to form the lipid that hydrogen bond, ionic bond, intermolecular pi-pi accumulation, electrostatic interaction etc. effectively adjust drug molecule, change
The physicochemical property of drug molecule improves the pharmacokinetic property of drug, and then improves bioactivity；It is also frequently as a kind of normal
Metal antirusting agent and corrosion inhibiter can form covalent bond and coordinate bond with copper atom and keep away in copper surface composition multilayer resist
It is from being corroded, while also having certain rust-proof effect to metals such as steel, aluminium.Furthermore studies have shown that the ionic liquid containing glyoxaline structure
Body has excellent anti-protein adsorption performance, high-efficiency antimicrobial activity and the good characteristic for inhibiting marine organisms attachment.Due to
The compound of one-component has the defects of anti-halobios adhersion type is single-minded, antifouling life is short, therefore one of thinking solved is just
It is to construct multiple elements design structure, it is antifouling carries out multicomponent collaboration.
Summary of the invention
It is an object of the present invention to provide a kind of poly- benzotriazole-for the above problem existing for existing anti-fouling material
The marine anti-pollution material preparation method of ionic liquid.
To achieve the goals above, the technical solution that the application uses are as follows:
The structural formula of a kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, the copolymer is Formulas I:
Wherein, n=5~10, and be positive integer；
A is Formula II or formula III, the wherein structural formula of Formula II or formula III are as follows:
Wherein, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of；
R is C4~C12Saturated alkyl.
Above-mentioned poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group is additionally provided, including
Following steps:
After S1, benzotriazole compound and bromomethyl norbornene substitution reaction, vacuum distillation is obtained containing benzo
Triazole-ionic liquid structure monomer；
S2, it will be dissolved in methylene chloride obtained in S1 containing benzotriazole-ionic liquid structure monomer, then plus
After entering norbornene compound containing dopamine structure, Grubbs catalyst is added, is copolymerized at room temperature, obtains poly- containing anchoring group
Benzotriazole-ionic liquid copolymer；
Wherein, described to contain benzotriazole-ionic liquid structure monomer and the chemical combination of norbornene containing dopamine structure
The molar ratio of object is 10~50:1；
The molar concentration of the Grubbs catalyst contains benzotriazole-ionic liquid structure monomer concentration described in being
5 ‰~1%；
The methylene chloride is the methylene chloride newly distilled.
Further, the benzotriazole compound is benzotriazole or benzotriazole imidazoles；
When the benzotriazole compound is benzotriazole, benzotriazole-ion for being prepared in S1
The monomer of liquid structure is the compound of formula IV；
When the benzotriazole compound is benzotriazole imidazoles, the benzotriazole-that is prepared in S1
The monomer of ionic liquid structure is the compound of formula V；
The compound of the formula IV and the structural formula of the compound of the formula V are as follows:
Wherein, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of；
R is C4~C12Saturated alkyl；
The Grubbs catalyst is Grubbs Ru carbene complex；
The norbornene compound containing dopamine structure is the compound of formula VI, and structural formula is as follows:
Further, the preparation process of the compound of the formula IV, includes the following steps:
Into benzotriazole and the mixed mixed solution of tert-butyl, bromomethyl norbornene is added, inert gas is protected
It under shield, is placed at a temperature of 50 DEG C~100 DEG C, reacts 10h~18h, chromatograph, vacuum distillation obtains the first product；Again to being dissolved with
Alkylating reagent is added in the mixed solution of first product, is evaporated under reduced pressure, obtains the compound of formula IV, and in the compound of formula IV
X-For Cl-Or Br-；R is C4~C12Saturated alkyl.
The molar ratio of the bromomethyl norbornene and benzotriazole is 1~1.2:1.
The benzotriazole and the mixed mixed solution of tert-butyl are that benzotriazole and tert-butyl are dissolved in three
Obtained in chloromethanes, methylene chloride or dichloroethanes；
The mixed solution for being dissolved with the first product is that the first product is dissolved in petroleum ether, n-hexane, chloroform
Or 1, obtained in 2- dichloroethanes；
The alkylating reagent is C4~C12One of the halide of saturated alkane.
Further, the preparation process of the compound of the formula IV, further includes following steps:
After alkylating reagent is added into the mixed solution dissolved with the first product, ClO is added4 -、BF4 -Or N
(SO2CF3)2 -Salting liquid, at room temperature after anion exchange 36h~48h, filter, vacuum drying, obtain the compound of formula IV,
And X in the compound of formula IV-For ClO4 -、BF4 -Or N (SO2CF3)2 -, R C4~C12Saturated alkyl.
Further, the preparation process of the compound of the formula V, includes the following steps:
Bromomethyl norbornene is added into the mixed solution of benzotriazole imidazoles, and at 60 DEG C~100 DEG C, reaction
After 12h~48h, vacuum distillation obtains the second product, as obtains the compound of formula V, wherein X-For Cl-Or Br-；
The bromomethyl norbornene and the molar ratio of benzotriazole imidazoles are 1~1.5:1；
The mixed solution of the benzotriazole imidazoles be by benzotriazole imidazoles be dissolved in n-hexane, chloroform or
Obtained in 1,2- dichloroethanes.
Further, the preparation process of the compound of the formula V, further includes following steps:
ClO is added into the second product4 -、BF4 -Or N (SO2CF3)2 -Salting liquid, anion exchange 36h~48h at room temperature
Afterwards, it filters, vacuum drying obtains the compound of Formula V, wherein X-For ClO4 -、BF4 -Or N (SO2CF3)2 -。
Further, the preparation process of the benzotriazole imidazoles is as follows:
By the aqueous isopropanol of the aqueous isopropanol of imidazoles and 1- chloromethyl benzotriazole, after blending, inert gas is protected
It under shield, is placed at a temperature of 60 DEG C~80 DEG C, after reaction 12h~for 24 hours, vacuum distillation obtains benzotriazole imidazoles.
In addition, the present invention also provides above-mentioned poly- benzotriazole-ionic liquid copolymer containing anchoring group is in gold
Application in metal surface antifouling process.
Further, the metal surface antifouling process process are as follows:
Poly- benzotriazole-ionic liquid copolymer by solid containing anchoring group be dissolved in methylene chloride, chloroform,
In acetone or tetrahydrofuran, poly- benzotriazole-ionic liquid containing anchoring group that concentration is 0.2mg/mL~5mg/mL is obtained
The mixed solution of precursor copolymer；
Metallic substrates are put into poly- benzotriazole-ionic liquid copolymer mixed solution containing anchoring group again
In, after 12h~48h is kept in dark place at room temperature, then wash repeatedly after, obtain surface have anti-pollution function metal material substrate.
Further, the metallic substrates are iron-based bottom, copper-based bottom, titanium substrate, aluminium substrate or zinc-base bottom.
Compared with prior art, the beneficial effects of the invention are as follows easy to operate, at low cost, the polymer grafting densities of acquisition
Height, and have the effect of good marine anti-pollution.
Detailed description of the invention
Fig. 1 is the monomer containing benzotriazole-ionic liquid structure (formula IV) nucleus magnetic hydrogen spectrum of the embodiment of the present invention 11H；
Fig. 2 is the monomer containing benzotriazole-ionic liquid structure (formula V) nucleus magnetic hydrogen spectrum of the embodiment of the present invention 21H；
Fig. 3 is that the monomer containing benzotriazole-ionic liquid structure of embodiment 2 (formula V) resists staphylococcus aureus
Bacterium activity；Wherein A is blank control group；B is 0.2% concentration；C is 2% concentration.
Fig. 4 is the poly- benzotriazole containing anchoring group-ionic liquid copolymer modification substrate that embodiment 2 is prepared
Anti-pollution (A) blank control group；(B) 0.2% content；(C) 2% content.
Specific embodiment
Technological means of the invention, creation characteristic, achieving the goal is easy to understand with effect in order to make, below in conjunction with
Specific embodiments of the present invention and attached drawing, are clearly and completely described technical solution of the present invention.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Bromomethyl norbornene employed in following embodiment is according to document Ye, Q.；Gao,T.；Wan,F.；Yu,
B.；Pei,X.；Zhou,F.；Xue,Q.,Grafting poly(ionic liquid)brushes for anti-
bacterial and anti-biofouling applications.Journal of Materials Chemistry
2012,22 (26), what the method recorded in 13123. was prepared.
Used 1- chloromethyl benzotriazole is according to document Cai, M.；Liang,Y.；Zhou,F.；Liu,W.,
Functional ionic gels formed by supramolecular assembly of a novel low
molecular weight anticorrosive/antioxidative gelator.Journal of Materials
Chemistry 2011,21 (35), what the method recorded in 13399. was prepared.
The methylene chloride newly distilled is to pour into methylene chloride in three-necked flask, and dry oxidation is added into three-necked flask
Calcium, what last distillation under pressure obtained.
Embodiment 1
A kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, the structural formula of copolymer are as follows:
Wherein, n=5；X-For Br-；R is-C4H9。
Above-mentioned poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group is as follows:
S1, it is prepared containing benzotriazole-ionic liquid structure monomer:
(1) 1.19g, i.e. 0.01mol benzotriazole and 1.11g, i.e. uncle 0.011mol are added in the two mouth flask of 50ml
Butyl potassium adds 20mL chloroform after mixing, obtain the first mixed solution；
(2) 1.87g, i.e. 0.01mol bromomethyl norbornene, inert gas (i.e. nitrogen) are added into the first mixed solution
It in the state of protection, is placed at a temperature of 80 DEG C, after reacting 12h, column chromatography for separation, vacuum distillation removes solvent, obtains first
Product；
Wherein bromomethyl norbornene and the molar ratio of benzotriazole compound are 1:1；
(3) the first product is dissolved in 10ml 1, in 2- dichloroethanes, obtains the second mixed solution；
(4) 1.37g, that is, 0.01mol alkylating reagent (i.e. bromobutane) is added into the second mixed solution, at 70 DEG C, reaction
After 48h, vacuum distillation remove solvent, obtain containing benzotriazole-ionic liquid structure monomer-type (i.e. IV compound,
Wherein X-For Br-；R is-C4H9)；IV compound being prepared, wherein X-For Br-；R is-C4H9Nuclear magnetic spectrogram such as Fig. 1,
Can determine from Fig. 1 be successfully prepared described IV compound.
S2, poly- benzotriazole-ionic liquid copolymer preparation containing anchoring group:
In the round-bottomed flask of 100ml, sequentially add be prepared in 3.85g i.e. 0.01mol S1 containing three nitrogen of benzo
The methylene chloride that azoles-ionic liquid structure monomer, 50ml newly distill after stirring and dissolving, adds 0.27g, i.e. 0.001mol
Norbornene compound containing dopamine structure (compound of Formula IV), is then slowly added into Grubbs Ru carbene complex, stirring
After copolymer-1 0min, settle to get poly- benzotriazole-ionic liquid copolymer containing anchoring group is arrived.
Molar ratio containing benzotriazole-ionic liquid structure monomer Yu the norbornene compound containing dopamine structure
For 10:1；
It is added to the molar concentration of the Grubbs catalyst in reaction system and contains benzotriazole-ionic liquid to be described
The 5 ‰ of the monomer concentration of structure.
Embodiment 2
A kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, the structural formula of copolymer are as follows:
Wherein, n=5；X-For Br-；R is-C4H9。
Above-mentioned poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group is as follows:
S1, it is prepared containing benzotriazole-ionic liquid structure monomer:
(1) 0.75g will be entered, i.e. 0.011mol imidazoles is dissolved in 10ml isopropanol, obtains the 4th mixed solution；It will
1.67g, that is, 0.01mol 1- chloromethyl benzotriazole is dissolved in isopropanol, obtains the 5th mixed solution；
(2) the 4th mixed solution is mixed in 50ml there-necked flask with the 5th mixed solution, obtains the 6th mixed solution；To
It is passed through in 6th mixed solution inert gas (i.e. nitrogen), at 70 DEG C, after reacting 20h, vacuum distillation removes solvent, obtains white
Powder, as benzotriazole imidazoles.
(3) the above-mentioned benzotriazole imidazoles being prepared is dissolved in 20ml 1, in 2- dichloroethanes, it is mixed obtains third
Close solution；It is added 2.05g, i.e. 0.011mol bromomethyl norbornene into third mixed solution again, at 80 DEG C, after reaction for 24 hours,
Vacuum distillation removes solvent, obtains containing benzotriazole-ionic liquid structure monomer (the i.e. compound of formula V, wherein X-
For Br-).V compound being prepared, wherein X-For Br-Nuclear magnetic spectrogram such as Fig. 2, can determine from Fig. 2 and successfully prepare
The compound of formula V is obtained.
Wherein the molar ratio of the compound of bromomethyl norbornene and benzotriazole imidazoles is 1:1；
S2, poly- benzotriazole-ionic liquid copolymer preparation containing anchoring group:
In the round-bottomed flask of 100ml, sequentially add be prepared in 3.85g i.e. 0.010mol S1 containing three nitrogen of benzo
The methylene chloride that azoles-ionic liquid structure monomer, 50ml newly distill after stirring and dissolving, adds 0.27g, i.e. 0.001mol
Norbornene compound containing dopamine structure (compound of VI) is then slowly added into Grubbs Ru carbene complex, and stirring is altogether
After poly- 10min, settle to get poly- benzotriazole-ionic liquid copolymer containing anchoring group is arrived.
Molar ratio containing benzotriazole-ionic liquid structure monomer Yu the norbornene compound containing dopamine structure
For 10:1；
It is added to the concentration of the Grubbs catalyst in reaction system and contains benzotriazole-ionic liquid structure to be described
Monomer concentration 5 ‰.
Embodiment 3
A kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, the structural formula of copolymer are as follows:
Wherein, n=5；X-For BF4-；R is-C4H9。
Above-mentioned poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group is as follows:
S1, contain benzotriazole-ionic liquid structure monomer preparation process:
(1) 1.19g, i.e. 0.01mol benzotriazole and 1.11g, i.e. uncle 0.011mol are added in the two mouth flask of 50ml
Butyl potassium adds 20ml chloroform after mixing, obtain the first mixed solution；
(2) 1.87g, i.e. 0.01mol bromomethyl norbornene, inert gas (i.e. nitrogen) are added into the first mixed solution
In the state of protection at 80 DEG C, after reacting 12h, column chromatography for separation, vacuum distillation removes solvent, obtains the first product；
Wherein bromomethyl norbornene and the molar ratio of benzotriazole compound are 1:1；
(3) the first product is dissolved in 10ml 1, in 2- dichloroethanes, obtains the second mixed solution；
(4) 1.37g, that is, 0.01mol alkylating reagent (i.e. bromobutane) is added into the second mixed solution, at 70 DEG C, reaction
After 48h, vacuum distillation removes solvent, obtains X-For Br-Contain benzotriazole-ionic liquid structure monomer (wherein X-For
Br-；R is-C4H9)；IV compound being prepared, wherein X-For Br-；R is-C4H9Nuclear magnetic spectrogram such as Fig. 1, from Fig. 1
It can determine and the compound has successfully been prepared really.
(5) by 3.74g 0.010mol X obtained in step (4)-For Br-Contain benzotriazole-ionic liquid knot
The monomer of structure is dissolved in 20ml water, after dissolution completely, adds 1.32g, 0.012mol sodium tetrafluoroborate, at room temperature anion
36h is exchanged, it is vacuum dried to obtain containing X after reaction mixture filtering-For BF4-Benzotriazole-ionic liquid.
Contain remaining anion (such as X-For Cl-、ClO4 -Or N (SO2CF3)2 -) contain benzotriazole-ionic liquid knot
The monomer of structure can be used anion exchange methods and be prepared.
S2, poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group are same as Example 1.
Embodiment 4
A kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, the structural formula of copolymer are as follows:
Wherein, n=5；X-For BF4-；R is-C4H9。
Above-mentioned poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group is as follows:
S1, it is prepared containing benzotriazole-ionic liquid structure monomer:
(1) 0.75g will be entered, i.e. 0.011mol imidazoles is dissolved in 10ml isopropanol, obtains the 4th mixed solution；It will
1.67g, that is, 0.01mol 1- chloromethyl benzotriazole is dissolved in isopropanol, obtains the 5th mixed solution；
(2) the 4th mixed solution is mixed in 50ml there-necked flask with the 5th mixed solution, obtains the 6th mixed solution；To
It is passed through in 6th mixed solution inert gas (i.e. nitrogen), at 70 DEG C, after reacting 20h, vacuum distillation removes solvent, obtains white
Powder, as benzotriazole imidazoles.
(3) the above-mentioned benzotriazole imidazoles being prepared are dissolved in 20ml 1, in 2- dichloroethanes, obtain third
Mixed solution；It is added 2.05g, i.e. 0.011mol bromomethyl norbornene into third mixed solution again, at 80 DEG C, reaction is for 24 hours
Afterwards, vacuum distillation removes solvent, obtains X-For Br-Contain benzotriazole-ionic liquid structure monomer (wherein X-For
Br-).V compound being prepared, wherein X-For Br-Nuclear magnetic spectrogram such as Fig. 2, can determine from Fig. 2 and successfully make really
It is standby to have obtained the compound.
Wherein the molar ratio of the compound of bromomethyl norbornene and benzotriazole imidazoles is 1:1；
(4) by 3.85g, 0.010mol X-For Br-Be dissolved in containing benzotriazole-ionic liquid structure monomer
In 20ml water, after dissolution completely, 1.32g is added, 0.012mol sodium tetrafluoroborate, for 24 hours, reaction is mixed for anion exchange at room temperature
It is vacuum dried to obtain X after closing object filtering-For BF4-Containing benzotriazole-ionic liquid structure monomer.
Contain remaining anion (such as X-For Cl-、ClO4 -Or N (SO2CF3)2 -) contain benzotriazole-ionic liquid knot
The monomer of structure can be used ion-exchange process and be prepared.
S2, poly- benzotriazole-ionic liquid copolymer preparation process containing anchoring group are same as Example 2.
It should be noted that poly- benzotriazole-ionic liquid copolymer containing anchoring group of the application, copolymer
Structural formula is Formulas I:
Wherein, n may be 6,7,8,9 or 10；
When A is Formula II, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of；And R is C4~C12Saturation
Alkane.
Above-mentioned n and X-, R being capable of any combination.
When A is Formula II, and X-For Cl-Or Br-When, the obtained poly- benzotriazole containing anchoring group-ionic liquid is copolymerized
The preparation method of object is identical as the preparation method of embodiment 1.
When A is Formula II, and X-For ClO4 -Or N (SO2CF3)2 -When, the obtained poly- benzotriazole-containing anchoring group from
The preparation method of sub- liquid copolymer is identical as the preparation method of embodiment 3.Difference is only to be replaced with sodium tetrafluoroborate
NaClO4Or NaN (SO2CF3)2。
When A is formula III, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of when, n with also can be any with R
Combination.
When A is formula III, and X-For Cl-Or Br-When, obtained poly- benzotriazole-ionic liquid containing anchoring group is total
The preparation method of polymers is identical as the preparation method of embodiment 2.
When A is formula III, and X-For ClO4 -Or N (SO2CF3)2 -When, the obtained poly- benzotriazole-containing anchoring group from
The preparation method of sub- liquid copolymer is identical as the preparation method of embodiment 4.Difference is only to be replaced with sodium tetrafluoroborate
NaClO4Or NaN (SO2CF3)2。
Poly- benzotriazole-ionic liquid the copolymer containing anchoring group being prepared in above-described embodiment can be used in
In the antifouling process of metal surface.
We are by taking poly- benzotriazole-ionic liquid copolymer containing anchoring group that embodiment 2 is prepared as an example, in detail
Describe bright metal surface antifouling process process in detail, as follows:
In order to verify poly- benzotriazole-ionic liquid copolymer containing anchoring group with anti-fouling effect, we are advanced
Benzotriazole-ionic liquid monomer (the i.e. obtained compound of formula V of embodiment 2, wherein X are gone-For Br-) antifouling and antibiosis
Experiment, as a result as shown in Figure 3.
Firstly, preparing staphylococcus aureus suspension.Aseptically, will contain staphylococcus aureus 3.8 ×
106The bacterium piece of cfu is put into the test tube equipped with 4ml PBS buffer solution, is vibrated about 20 seconds, is made golden yellow through vortex mixer
Color staphylococcus suspension suspension.
A is control group in Fig. 3.Bacteria suspension is diluted to a certain concentration (about 10 with PBS buffer solution4cfu/mL).It draws mixed
It closes uniform bacteria suspension 1ml to be added in sterilized petri dishes, adds the PBS buffer solution of 4ml.40 DEG C of nutrition fine jade will be cooled to after fusing
Rouge culture medium is poured into the plate of sample adding liquid, every plate 15ml~20ml.After agar solidification, plate is overturn, is inverted in
(37 DEG C, 48 hours) are cultivated in biochemical cultivation case.Visually observe the colony count grown on plate.
B is the first experimental group in Fig. 3.It draws uniformly mixed bacteria suspension 1ml to be added in sterilized petri dishes, adds 4ml benzene
And triazole-ionic liquid monomer concentration is the PBS buffer solution of 0.2mg/mL.Remaining step is same as above.
The C of Fig. 3 is the second experimental group.It draws uniformly mixed bacteria suspension 1ml to be added in sterilized petri dishes, adds 4ml benzene
And triazole-ionic liquid monomer concentration is the PBS buffer solution of 2mg/mL.Remaining step is same as above.
From, it can be seen that agar is more muddy in culture dish in A, this shows have a large amount of bacterium colony to be formed in Fig. 3.B's and C
Agar is more limpid in culture dish, shows that benzotriazole-ionic liquid monomer has good anti-fouling effect.
In order to verify the anti-pollution of substrate, we have also carried out antifouling anti-algae experiment, as a result as shown in Figure 4.
A is control group in Fig. 4.The silicon wafer (copper facing) of 5cm × 5cm is put into 20ml tetrahydrofuran, is protected from light guarantor at room temperature
After depositing for 24 hours, then respectively washed 3 times by acetone, ethyl alcohol.Then, being put into concentration is about 105It is quiet in the bead algae culturing liquid of a/mL
It sets three days.It is washed with distilled water after taking-up three times, obtains control group substrate.
B is the first experimental group in Fig. 4.By the copper-based bottom of 5cm × 5cm, i.e., copper-plated silicon wafer is put into 20ml, and concentration is
In above-mentioned poly- benzotriazole-ionic liquid copolymer solution of 0.2mg/mL, after being kept in dark place for 24 hours at room temperature, then pass through third
Ketone, ethyl alcohol respectively wash 3 times.Then, being put into concentration is about 105In the bead algae culturing liquid of a/mL, three days are stood.It is used after taking-up
It distills water washing three times, obtains the first experimental group substrate.
C is the second experimental group in Fig. 4.By the copper-based bottom of 5cm × 5cm, i.e., copper-plated silicon wafer is put into 20ml, and concentration is
In poly- benzotriazole-ionic liquid copolymer solution of 2mg/mL, remaining process is same as above, and obtains the second experimental group substrate.
The process for preparation of above-mentioned poly- benzotriazole-ionic liquid copolymer solution: in 100ml volumetric flask, drying is taken
The poly- benzotriazole containing the anchoring group-ionic liquid copolymer 200mg that is prepared of embodiment 2, tetrahydro is then added
Furans dissolves, and after constant volume, obtains poly- benzotriazole-ionic liquid copolymer solution of 2mg/mL.
There are a large amount of chlorellas to adhere to from Fig. 4, it can be seen that surface in control group A.When surface is through ionic liquid copolymer
After modification, the attachment quantity of chlorella is significantly reduced.In particular, when surface is in poly- benzotriazole-ionic liquid of 2mg/mL
After copolymer solution impregnates, the attachment quantity of chlorella is further reduced, and shows as more excellent anti-pollution.
It is to be appreciated that substrate used in above-mentioned antifouling anti-algae experiment is also possible to iron-based bottom, titanium substrate, aluminium substrate or zinc-base
Bottom.
In conclusion the poly- benzotriazole containing anchoring group of the application-ionic liquid copolymer grafted density is high,
Preparation process is simple, and it can be used to the antifouling process of metal surface, and poly- benzotriazole-ionic liquid through the application is total
Treated that metal surface has the effect of good antibacterial and algae-resistant for copolymer solution.
Disclosed above is only presently preferred embodiments of the present invention, and still, the embodiment of the present invention is not limited to this, Ren Heben
What the technical staff in field can think variation should all fall into protection scope of the present invention.
Claims (10)
1. a kind of poly- benzotriazole-ionic liquid copolymer containing anchoring group, which is characterized in that the structure of the copolymer
Formula is Formulas I:
Wherein, n=5~10, and be positive integer；
A is Formula II or formula III, the wherein structural formula of Formula II or formula III are as follows:
Wherein, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of；
R is C4~C12Saturated alkyl.
2. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as described in claim 1, special
Sign is, includes the following steps:
S1, benzotriazole compound and bromomethyl norbornene take generation substitution reaction, obtain containing benzotriazole-from
The monomer of sub- liquid structure；
S2, it will be dissolved in methylene chloride obtained in S1 containing benzotriazole-ionic liquid structure monomer, add and contain
After the norbornene compound of dopamine structure, Grubbs catalyst is added, is copolymerized at room temperature, obtains the polyphenyl containing anchoring group
And triazole-ionic liquid copolymer；
Wherein, described to contain benzotriazole-ionic liquid structure monomer and the norbornene compound containing dopamine structure
Molar ratio is 10~50:1；
The molar concentration of the Grubbs catalyst contains benzotriazole-ionic liquid structure monomer molar concentration described in being
5 ‰~1%.
3. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 2, special
Sign is,
The benzotriazole compound is benzotriazole or benzotriazole imidazoles；
When the benzotriazole compound is benzotriazole, benzotriazole-ionic liquid for being prepared in S1
The monomer of structure is the compound of formula IV；
When the benzotriazole compound is benzotriazole imidazoles, benzotriazole-ion for being prepared in S1
The monomer of liquid structure is the compound of formula V；
The compound of the formula IV and the structural formula of the compound of the formula V are as follows:
Wherein, X-For Cl-、Br-、ClO4 -、BF4 -Or N (SO2CF3)2 -One of；
R is C4~C12Saturated alkyl；
The Grubbs catalyst is Grubbs Ru carbene complex；
The norbornene compound containing dopamine structure is the compound of formula VI, and structural formula is as follows:
4. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 3, special
Sign is,
The preparation process of the compound of the formula IV, includes the following steps:
Into benzotriazole and the mixed mixed solution of tert-butyl, bromomethyl norbornene is added, under inert gas shielding,
It is placed at a temperature of 50 DEG C~100 DEG C, reacts 10h~18h, chromatograph, vacuum distillation obtains the first product；Again to dissolved with first
Alkylating reagent is added in the mixed solution of product, is evaporated under reduced pressure, obtains the compound of formula IV, and X in the compound of formula IV-For
Cl-Or Br-；
The molar ratio of the bromomethyl norbornene and benzotriazole is 1~1.2:1；
The benzotriazole and the mixed mixed solution of tert-butyl are that benzotriazole and tert-butyl are dissolved in three chloromethanes
Obtained in alkane, methylene chloride or dichloroethanes；
The mixed solution for being dissolved with the first product is that the first product is dissolved in petroleum ether, n-hexane, chloroform or 1,
Obtained in 2- dichloroethanes；
The alkylating reagent is C4~C12One of the halide of saturated alkyl.
5. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 4, special
Sign is that the preparation process of the compound of the formula IV, further includes following steps:
After alkylating reagent is added into the mixed solution dissolved with the first product, ClO is added4 -、BF4 -Or N (SO2CF3)2 -'s
Salting liquid, at room temperature after anion exchange 36h~48h, is filtered, and vacuum drying obtains the compound of formula IV, and the chemical combination of formula IV
X in object-For ClO4 -、BF4 -Or N (SO2CF3)2 -。
6. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 3, special
Sign is,
The preparation process of the compound of the formula V, includes the following steps:
Bromomethyl norbornene is added into the mixed solution of benzotriazole imidazoles, and at 60 DEG C~100 DEG C, reacts 12h
After~48h, vacuum distillation obtains the second product, the as compound of formula V, wherein X-For Cl-Or Br-；
The bromomethyl norbornene and the molar ratio of benzotriazole imidazoles are 1~1.5:1；
The mixed solution of the benzotriazole imidazoles is that benzotriazole imidazoles is dissolved in n-hexane, chloroform or 1,2-
Obtained in dichloroethanes.
7. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 6, special
Sign is that the preparation process of the compound of the formula V, further includes following steps:
ClO is added into the second product4 -、BF4 -Or N (SO2CF3)2 -Salting liquid, at room temperature after anion exchange 36h~48h,
Filtering, vacuum drying, obtains the compound of formula V, wherein X-For ClO4 -、BF4 -Or N (SO2CF3)2 -。
8. poly- benzotriazole-ionic liquid copolymer preparation method containing anchoring group as claimed in claim 7, special
Sign is that the preparation process of the benzotriazole imidazoles is as follows:
By the aqueous isopropanol of the aqueous isopropanol of imidazoles and 1- chloromethyl benzotriazole, after blending, under inert gas shielding,
It is placed at a temperature of 60 DEG C~80 DEG C, after reaction 12h~for 24 hours, vacuum distillation obtains benzotriazole imidazoles.
9. poly- benzotriazole-ionic liquid copolymer as described in any one of claims 1 to 8 containing anchoring group is in metal
Application in surface soiling processing.
10. poly- benzotriazole-ionic liquid copolymer containing anchoring group is antifouling in metal surface as claimed in claim 9
Application in processing, which is characterized in that the metal surface antifouling process process are as follows:
Poly- benzotriazole-ionic liquid copolymer by solid containing anchoring group is dissolved in methylene chloride, chloroform, acetone
Or in tetrahydrofuran, it is total to obtain poly- benzotriazole-ionic liquid containing anchoring group that concentration is 0.2mg/mL~5mg/mL
The mixed solution of polymers；
Metallic substrates are put into poly- benzotriazole-ionic liquid copolymer mixed solution containing anchoring group again,
After 12h~48h is kept in dark place at room temperature, then wash repeatedly after, obtain surface have anti-pollution function metal material substrate.
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| CN103785975A (en) * | 2014-02-20 | 2014-05-14 | 苏州龙腾万里化工科技有限公司 | Soldering flux for improving corrosion inhibition |
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| CN103785975A (en) * | 2014-02-20 | 2014-05-14 | 苏州龙腾万里化工科技有限公司 | Soldering flux for improving corrosion inhibition |
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