CN100497401C - Fixation of ionic liquid using polymer - Google Patents
Fixation of ionic liquid using polymer Download PDFInfo
- Publication number
- CN100497401C CN100497401C CNB2005101074395A CN200510107439A CN100497401C CN 100497401 C CN100497401 C CN 100497401C CN B2005101074395 A CNB2005101074395 A CN B2005101074395A CN 200510107439 A CN200510107439 A CN 200510107439A CN 100497401 C CN100497401 C CN 100497401C
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- polymer
- bound
- proportioning
- polymkeric substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 152
- 239000002608 ionic liquid Substances 0.000 title claims description 303
- 239000000126 substance Substances 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 239000010931 gold Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 116
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 95
- 238000006243 chemical reaction Methods 0.000 claims description 92
- 229940059260 amidate Drugs 0.000 claims description 66
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 claims description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 58
- 125000000524 functional group Chemical group 0.000 claims description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 35
- 229920002125 Sokalan® Polymers 0.000 claims description 31
- 239000004584 polyacrylic acid Substances 0.000 claims description 29
- 150000002500 ions Chemical class 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 15
- 238000004528 spin coating Methods 0.000 claims description 13
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 12
- 238000001652 electrophoretic deposition Methods 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 229920002873 Polyethylenimine Polymers 0.000 claims 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 239000011159 matrix material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 230000009435 amidation Effects 0.000 abstract 1
- 238000007112 amidation reaction Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 57
- 239000007864 aqueous solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A method for fixing ion liquid from polymer is carried out by taking polymer as ion liquid carrier, grafting ion liquid into side chain of polymer from amidation, spinning coating, laminated assembling or electrophoretic depositing to fix it onto metal, glass or silicon solid matrix or metal and semiconductor nanometer particles or gold, platinum or glass carbon etc. electrode. It is fast and simple. It can be used for chemical catalysis, chemical separation and electrochemistry.
Description
Technical field
The present invention relates to a kind of polymkeric substance that utilizes and fix ion liquid method.
Background technology
Utilize polymkeric substance to fix ionic liquid, be as ion liquid carrier with polymkeric substance, with the ionic liquid grafting to polymer lateral chain, form a kind of ionic liquid of polymer-bound, by spin coating, layer assembly, electrophoretic deposition method the ionic liquid of this polymer-bound is fixed to a kind of method on the solid substrate then.The method of this non diffusible ion liquid has broad application prospects in chemical catalysis, chemical separation, electrochemical field, especially in the out-phase chemical catalysis important role is arranged.
Ionic liquid is because the controllability of its unique physicochemical property and physico-chemical property thereof, and enjoys people's attention in a plurality of fields, as catalysis, and chemical separation, electrochemical field.For example, ionic liquid has been widely used as the media of homogeneous chemistry catalyzed reaction.But because ion liquid polarity and rich electric charge, the polarity product is difficult to separate from the ionic liquid media.In addition, from the economic interests angle, people wish ion liquid usage quantity is reduced as far as possible; And in ion liquid use, people wish that the ionic liquid physical efficiency is easy to separate and the energy cycling and reutilization.It is a kind of effective ways that can satisfy the demand that ionic liquid is fixed on the solid substrate.This fixing means is intended to ion liquid superior character is transferred on the solid substrate.Fixing means can have covalency and non-covalent two kinds.People such as Mehnert and Moreau is used for the chemical catalysis reaction at Journal of The American Chemical Society magazine 2002 the 124th volume 44 phase 12932-12933 pages or leaves and Chemical Communications magazine 2004 the 15th phases 1768-1769 page or leaf report with the surface that the mode of ionic liquid by covalent bonding is fixed to silica gel respectively.The shortcoming of this method is that this fixing means needs ionic liquid that certain specific functional group is arranged, to ionic liquid and fixedly matrix lack universality.
Summary of the invention
The purpose of this invention is to provide a kind of polymkeric substance that utilizes and fix ion liquid method, promptly at first by amidate action with the ionic liquid grafting of carboxyl-functional to the polymer chain that contains amino functional group or with the ionic liquid grafting of amino functional to the polymer chain that contains carboxyl function group, form the ionic liquid of polymer-bound; Be fixed on metal, glass, the silicon solid substrate by spin coating, layer assembly or electrophoretic deposition method then or metal, semi-conductor nano particles on, also can be fixed on gold, platinum or the glassy carbon electrode.Utilize the method for this mode non diffusible ion liquid simply various, and be not subjected to the restriction of the quality, shape, size etc. of fixing matrix, fixed amount what can also regulate in addition as required.
The method of utilizing polymkeric substance non diffusible ion liquid of the present invention comprises ion liquid fixedly two portions of the ion liquid synthetic and polymer-bound of polymer-bound.The ionic liquid of polymer-bound can by amidate action just the ionic liquid grafting of carboxyl-functional to the polymer chain that contains amino functional group, or with the ionic liquid grafting of amino functional to the polymer chain that contains carboxyl function group and obtain.Polymer-bound ion liquid fixedly has multiple mode, promptly can be fixed to the solid substrate surface by spin coating, electrophoretic deposition, layer assembly method.Solid substrate can be metal, glass, silicon etc.; Perhaps metal, semi-conductor nano particles; Also can be gold, platinum or glassy carbon electrode.This fixing means has solved the fixing difficult problem of conventional ion liquid, can control the ion liquid amount of fixed easily according to actual needs again simultaneously.
(1), be the ionic liquid of carboxylic acid functional to be fixed to reaction process on the polymkeric substance that contains amino functional group below by amidate action:
(2), be the ionic liquid of amino functional to be fixed to reaction process on the polymkeric substance that contains carboxyl function group by amidate action:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
Is the ionic liquid 1 of carboxylic acid functional the ionic liquid 2 that 1:10～1:15 back flow reaction generates chloride with thionyl chloride by proportioning, with 2 with polymine be that ° C reaction obtains the ionic liquid 3 of polymer-bound to 1:1.1～1:1.4 40 ° of C～50 by proportioning.
Then the method by electrophoretic deposition, spin coating or layer assembly be fixed to the ionic liquid 3 of the polymer-bound that obtains on metal, glass, the silicon solid substrate or metal, semi-conductor nano particles on, also can be fixed on gold, platinum or the glassy carbon electrode.
The method of the ionic liquid 3 by electrophoretic deposition fixed polymer bonding is as follows: use the potentiostatic method in the electrochemical workstation to deposit, with metal, glass, silicon solid substrate or gold, platinum, glassy carbon electrode is working electrode, with the platinum filament is counter electrode, the Ag/AgCl electrode is a reference electrode, operating voltage is 0.3V, and depositing time is 15min.
The process of the ionic liquid 3 by spin coating method fixed polymer bonding is as follows: be fixed to metal, glass, silicon solid substrate or gold, platinum, glassy carbon electrode on the spin coating instrument and drip ionic liquid 3 solution of going up polymer-bound, spin coating instrument rotating speed is transferred to 4000 rev/mins treats that solvent volatilizees fully.
The method of the ionic liquid 3 of the method fixed polymer bonding by layer assembly is as follows: with metal, glass, silicon solid substrate or metal, semi-conductor nano particles, or gold, platinum or glassy carbon electrode at first are immersed in 15min in the aqueous solution of polymine, then it is taken out and be dipped into 15min in the polyacrylic aqueous solution again, and then it is dipped into 15min in the aqueous solution of ionic liquid 3 of polymer-bound, repeating next two steps repeatedly just can be fixing with the ionic liquid 3 of polymer-bound.
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10～1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be that ° C reaction obtains the ionic liquid 7 of polymer-bound to 1:1.1～1:1.4 40 ° of C～50 by proportioning.
Then the ionic liquid 7 that will obtain polymer-bound of the method by electrophoretic deposition, spin coating or layer assembly be fixed on metal, glass, the silicon solid substrate or metal, semi-conductor nano particles on, also can be fixed on gold, platinum or the glassy carbon electrode.Concrete fixing means is with the fixing means of the ionic liquid 3 of polymer-bound.
The method of utilizing polymkeric substance non diffusible ion liquid of the present invention is compared with the method that ionic liquid is fixed on the silica gel, and fixing matrix is had universality, and method is simple and efficient; And the fixing means that the present invention provides can be regulated and control fixed amount as required.The method of this non diffusible ion liquid has broad application prospects in chemical catalysis, chemical separation, electrochemical field, especially in the out-phase chemical catalysis important role is arranged.
Further specify the present invention below by embodiment and embodiment.
Embodiment
Embodiment 1:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.
Then the ionic liquid 3 that will obtain polymer-bound of the method by electrophoretic deposition, spin coating or layer assembly be fixed on metal, glass, the silicon solid substrate or metal, semi-conductor nano particles on, also can be fixed on gold, platinum or the glassy carbon electrode.
The method of the ionic liquid 3 by electrophoretic deposition fixed polymer bonding is as follows: use potentiostatic method on electrochemical workstation, with metal solid matrix or gold, platinum, glassy carbon electrode is working electrode, with the platinum filament is counter electrode, the Ag/AgCl electrode is a reference electrode, operating voltage is 0.3V, and depositing time is 10min.
The process of the ionic liquid 3 by spin coating method fixed polymer bonding is as follows: be fixed to metal, glass, silicon solid substrate or gold, platinum, glassy carbon electrode on the spin coating instrument and drip ionic liquid 3 solution of going up polymer-bound, spin coating instrument rotating speed is transferred to 4000 rev/mins volatilizees fully until solvent.
The method of the ionic liquid 3 of the method fixed polymer bonding by layer assembly is as follows: with metal, glass, silicon solid substrate or metal, semi-conductor nano particles, or gold, platinum or glassy carbon electrode at first are immersed in 15min in the aqueous solution of polymine, then it is taken out and be dipped into 15min in the polyacrylic aqueous solution again, and then it is dipped into 15min in the aqueous solution of ionic liquid 3 of polymer-bound, repeating next two steps repeatedly just can be fixing with the ionic liquid 3 of polymer-bound.
Embodiment 2:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 3:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 4:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 5:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 6:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 7:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 8:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 9:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.1 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 10:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 11:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 12:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 13:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 14:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 15:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 16:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 17:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 18:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.2 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 19:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 20:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 21:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 40 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 22:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 23:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 24:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 45 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 25:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:10 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 26:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:15 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 27:
Shown in above-mentioned (1), the ionic liquid of polymer-bound can contain the ionic liquid grafting of carboxylic acid functional on the amino polymkeric substance to side chain by amidate action and obtains:
The ionic liquid 1 of carboxylic acid functional and thionyl chloride are generated the ionic liquid 2 of chloride by proportioning for the 1:12 back flow reaction, with 2 with polymine be that 1:1.4 reacts at 50 ° of C by proportioning, obtain the ionic liquid 3 of polymer-bound.Fixing means is with embodiment 1.
Embodiment 28:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 29:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 30:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 31:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 32:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 33:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 34:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 35:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 36:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.1 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 37:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 38:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 39:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 40:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 41:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 42:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 43:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 44:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 45:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.2 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 46:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 47:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 48:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 40 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 49:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 50:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 51:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:12 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 45 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 52:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:10 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 53:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Embodiment 54:
Shown in above-mentioned (2), the ionic liquid of polymer-bound also can be fixed on the polymkeric substance that contains carboxyl function group by the ionic liquid with amino functional with amidate action:
Polyacrylic acid 4 and thionyl chloride are generated the polymkeric substance 5 of chloride by proportioning 1:15 back flow reaction, with 5 with the ionic liquid 6 that contains amino functional group be 1:1.4 obtains polymer-bound 50 ° of C reactions ionic liquid 7 by proportioning.Fixing means is with embodiment 1.
Claims (3)
1. method of utilizing polymkeric substance non diffusible ion liquid, comprise the ionic liquid that the ionic liquid grafting is formed polymer-bound to the polymer chain by amidate action, be fixed to metal, glass or silicon solid substrate by spin coating, layer assembly or electrophoretic deposition method then, on metal or the semi-conductor nano particles, perhaps be fixed on gold, platinum or the glassy carbon electrode; It is characterized in that, the described ionic liquid that the ionic liquid grafting is formed polymer-bound to the polymer chain by amidate action, be to utilize polymkeric substance as ion liquid carrier, the ionic liquid that the ionic liquid that will contain carboxyl function group maybe will contain amino functional group to the polyethyleneimine polymers chain that contains amino functional group by the amidate action grafting by the amidate action grafting to the acrylic acid polymer that contains carboxyl function group.
2. a kind of polymkeric substance that utilizes as claimed in claim 1 fixes ion liquid method, it is characterized in that the described ionic liquid grafting that will contain carboxyl function group by amidate action to step and condition on the polyethyleneimine polymers chain that contains amino functional group is:
Is the ionic liquid of carboxylic acid functional (1) ionic liquid (2) that 1:10～1:15 back flow reaction generates chloride with thionyl chloride by proportioning, with (2) and polymine by proportioning be 1:1.1～1:1.4 40 ℃～50 ℃ reactions, obtain the ionic liquid (3) of polymer-bound.
3. a kind of polymkeric substance that utilizes as claimed in claim 1 fixes ion liquid method, it is characterized in that describedly by amidate action with the ionic liquid grafting of amino functional to step and condition on the acrylic acid polymer that contains carboxyl function group being:
Polyacrylic acid (4) and thionyl chloride are generated the polymkeric substance (5) of chloride by proportioning 1:10～1:15 back flow reaction, with (5) and the ionic liquid (6) that contains amino functional group by proportioning be 1:1.1～1:1.4 40 ℃～50 ℃ reactions, obtain the ionic liquid (7) of polymer-bound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101074395A CN100497401C (en) | 2005-09-30 | 2005-09-30 | Fixation of ionic liquid using polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101074395A CN100497401C (en) | 2005-09-30 | 2005-09-30 | Fixation of ionic liquid using polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1746196A CN1746196A (en) | 2006-03-15 |
| CN100497401C true CN100497401C (en) | 2009-06-10 |
Family
ID=36165932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101074395A Expired - Fee Related CN100497401C (en) | 2005-09-30 | 2005-09-30 | Fixation of ionic liquid using polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100497401C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100467548C (en) * | 2006-12-14 | 2009-03-11 | 浙江工业大学 | Use and dosage of ioonic liquid as tower filler surface treating agent |
| CN102173865B (en) * | 2011-01-10 | 2012-10-10 | 武汉工程大学 | Method for fixing noble metal nano particles on single-crystal silicon surface polymer brush |
-
2005
- 2005-09-30 CN CNB2005101074395A patent/CN100497401C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Chemical Communications. Mehnert & Moreau,第1768－1769页. 2004 * |
| Journal of The American Chemical Society. Mehnert & Moreau,第12932－12933页. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1746196A (en) | 2006-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7238536B1 (en) | Controlled transport through multiple reversible interaction point membranes | |
| Sowerby et al. | Self-assembly at the prebiotic solid− liquid interface: Structures of self-assembled monolayers of adenine and guanine bases formed on inorganic surfaces | |
| Qu et al. | Stable microstructured network for protein patterning on a plastic microfluidic channel: strategy and characterization of on-chip enzyme microreactors | |
| Wang et al. | Interfacing cytochrome c to electrodes with a DNA–carbon nanotube composite film | |
| AU777000B2 (en) | Permeation layer attachment chemistry and method | |
| Gutierrez Moreno et al. | Computational study of APTES surface functionalization of diatom-like amorphous SiO2 surfaces for heavy metal adsorption | |
| CN102391947B (en) | Preparation method for porous monolithic column immobilized enzyme micro-reactor | |
| CN101078026A (en) | DNA electrochemical sensor and preparation method thereof | |
| CN103357452B (en) | The preparation method of poly-dopamine/graphene oxide/BSA | |
| EP1504085A4 (en) | Conductive microplate | |
| Seidi et al. | Electrochemically assisted solid based extraction techniques: a review | |
| CN100497401C (en) | Fixation of ionic liquid using polymer | |
| CN101140257A (en) | Biologic sensor enzyme functional susceptivity film containing nickel and aluminum hydrotalcite nano piece and method of producing the same | |
| CN105907844B (en) | Electrochemical DNA biosensor based on three-dimensional graphene-dendritic nanogold and preparation method thereof | |
| CN108535343A (en) | The preparation method and applications of methylene blue-gold composite nano particle modified electrode | |
| Li et al. | Single molecule catch and release: potential-dependent plasmid DNA adsorption along chemically graded electrode surfaces | |
| Kertesz et al. | Electrochemical detection of surface hybridization of oligodeoxynucleotides bearing anthraquinone tags at gold electrodes | |
| Zhang et al. | Deposition/adsorption of colloids to surface-modified granules: effect of surface interactions | |
| Hsu et al. | Electrochemical epinephrine sensor using artificial receptor synthesized by sol–gel process | |
| CN1291777C (en) | Positive charged organic-inorganic hybrid membrane preparing method | |
| EP1794181A2 (en) | Methods and materials for optimization of electronic transportation and hybridization reactions | |
| US7195908B2 (en) | Supports treated with triamine for immobilizing biomolecules | |
| CN108726641A (en) | A kind of boron antimony codope tin oxide electrode and preparation method thereof | |
| CN102505041A (en) | Preparation method of biological chip | |
| CN107213858A (en) | The preparation of shell core molecule trace silica/golden nanometer particle composite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY HINESE ACADEMY OF SCIENCES Effective date: 20121231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20121231 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS & DEVICES Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161123 Address after: 130022 Changchun people's street, Jilin, No. 5625 Patentee after: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES Address before: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee before: Changzhou Institute of Energy Storage Materials & Devices |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20171101 Address after: 528000, No. 4, No. 301, trading center of Xingye Road 4, Xingye Road, Beijiao Town, Shunde District, Foshan, Guangdong Patentee after: FOSHAN ZHONGKE XIANCHUANG ELECTRONIC TECHNOLOGY Co.,Ltd. Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINESE ACADEMY OF SCIENCES |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090610 Termination date: 20210930 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |