CN103214500A - Functional monomer for preparing heavy metal ion imprinted polymer and preparation method - Google Patents

Functional monomer for preparing heavy metal ion imprinted polymer and preparation method Download PDF

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CN103214500A
CN103214500A CN2013101144138A CN201310114413A CN103214500A CN 103214500 A CN103214500 A CN 103214500A CN 2013101144138 A CN2013101144138 A CN 2013101144138A CN 201310114413 A CN201310114413 A CN 201310114413A CN 103214500 A CN103214500 A CN 103214500A
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function monomer
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acid
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马娟娟
朱彩艳
李金鹏
关云来
张田林
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Huaihai Institute of Techology
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Abstract

The invention provides a functional monomer for preparing a heavy metal ion imprinted polymer, which is a monomer with a molecular structure containing three functional units of quaternary ammonium salt, Schiff base complex and polymerizable double bond, can perform a self-polymerization reaction, also can perform a copolymerization reaction with styrene, acrylic ester, acrylonitrile, vinyl acetate or acrylamide, and is used for preparing an ion imprinted polymer material with a function of identifying, detecting and separating heavy metal ions.

Description

Be used to prepare the function monomer and the preparation method of heavy metal ion blotting polymkeric substance
Technical field
The present invention relates to a kind of function monomer, particularly contain the unitary function monomer of quaternary ammonium salt and title complex in the molecular structure, be used to prepare have identification, the ion imprinted polymer of detection and separation of heavy metal ions function, belong to functional high polymer material field.
Technical background
Molecularly imprinted polymer is meant that with a certain specific target molecule be template, combine with template by interact (coordinate bond, hydrogen bond, Van der Waals force, electrostatic interaction, hydrophobic interaction etc.) having complementary function monomer on the structure, add linking agent and carry out polyreaction, after reaction is finished, the template wash-out is come out, form a kind of have fixed cavitation size and shape, can highly selective identification adsorb the rigid polymer material of template.Molecularly imprinted polymer is widely used at aspects such as chemical sensor, natural antibody simulation, selectivity catalysis, medicine chiral separation, medicine sustained release, farming residual analysis, chromatographic stationary phase, solid extracting agents with its good performance.
Although the engram technology development rapidly, and obtain using more widely, but still have a lot of problems.One of them be present spendable function monomer kind very little, the function singleness of function monomer to such an extent as to can not satisfy the requirement of some templates identification, maybe can not satisfy the needs of practical application; Imprinted polymer can only carry out polymerization and application mostly in organic phase in addition, and natural template recognition system is carried out in the aqueous solution mostly, how can carry out template imprinting in the aqueous solution or in the polar solvent and identification is still a great problem.So synthetic more, the better function monomer of performance of kind, the trace of template and recognition process turn to water to have important and practical meanings from organic phase.
Ion imprinted polymer is branch of imprinted polymer, is template with the metal ion, interacts with having the unitary function monomer of chelating ligand by effects such as static, coordinations, and is got off by " memory " by polymerization process.Ionic linkage between function monomer and the transition metal ion and coordinate bond have stronger reactive force than hydrogen bond, Van der Waals force, electrostatic interaction, hydrophobic interaction etc., space structure is stable, directional property is strong, helps preparing imprinted polymer highly selective, the trace function-stable; Recognition process by coordination has in conjunction with quick and reversible advantage; In addition, the transition metal ion coordination can stable existence in polar system, and this just makes the preparation of water-soluble template and imprinted polymer and application become possibility; The metallic ion coordination effect has good thermodynamic stability, than being easier to reach kinetic balance, has wide range of applications; Moreover, because transition metal has different chemical propertys under the different states of oxidation, so function monomer is adapted to prepare the ion imprinted polymer material.
The function monomer that is used to prepare the heavy metal ion blotting polymkeric substance provided by the invention, be used to prepare have identification, the ion imprinted polymer of detection, separation of heavy metal ions function, contain quaternary ammonium salt, schiff bases complex and three functional units of polymerizable double bond in the described function monomer molecular structure:
1. the unsaturated C=C structural unit that participates in polyreaction comes from active acrylate, acrylamide, vinyl pyridine or allyl amine, all belongs to the commercial goods.
2. described quaternary ammonium salt structure unit has strongly hydrophilic, and by its ion imprinted polymer surface hydrophilicity height that makes, described ion imprinted polymer can carry out at aqueous phase the absorption of metal ion, and reaches adsorption equilibrium rapidly.
3. described complex structure unit is the trace that constitutes ion imprinted polymer, " core " structural unit of recognition function, refer to the amino Q formic acid of salicylidene (Schiff base, Schiff's base) with such as Hg 2+, Pb 2+, Cr 3+, Cd 2+, Cu 2+, Fe 3+, Zn 2+, Ni 2+, Ag +, Pt 2+, Pd 2+, Mn 2+, UO 2 2+Or RE 3+Form Deng transition metal ion that color and luster is different, fluorescence strengthens or the title complex of fluorescent quenching.The amino Q formic acid of described salicylidene is a kind of Schiff's base of three tooth chelating ligands, has been used for the kind or the valence state of the described transition metal ion of analyzing and testing.
Summary of the invention
The invention provides a kind of function monomer that is used to prepare the heavy metal ion blotting polymkeric substance, its feature has general formula (I A), general formula (I B) or general formula (I C) shown in chemical structure:
Figure BSA00000873318000021
Or
Its formula of (I A), general formula (I B) or general formula (I C) in R choose H or methyl; Y chooses O or NH; N chooses a kind of in 2,3,4,5 or 6, R 1And R 2Choose C respectively 1～C 18A kind of in the alkyl, R 3Choose C 3～C 18Unsaturated alkyl; Q chooses C 6～C 12Aryl or ZCH, described Z chooses H, C 1～C 12Alkyl or C 6～C 12A kind of in the aryl; M refers to transition metal ion, and L is selected from one or more in water, methyl alcohol, ethanol, acetone, acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde; M is selected from a kind of in 0,1,2 or 3; X -Be selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of.
General formula (I A), general formula (I B) or general formula (I C) shown in the function monomer that is used to prepare the heavy metal ion blotting polymkeric substance of structure realize through following synthetic route and preparation process:
Figure BSA00000873318000032
Figure BSA00000873318000041
In described synthetic route, R chooses H or methyl; Y chooses O or NH; N chooses a kind of in 2,3,4,5 or 6, R 1And R 2Choose C respectively 1～C 18A kind of in the alkyl, R 3Choose C 3～C 18Unsaturated alkyl; Q chooses C 6～C 12Aryl or ZCH, described Z chooses H, C 1～C 12Alkyl or C 6～C 12A kind of in the aryl; MX pIn M be selected from a kind of in the transition metal ion, MX pIn X -Be selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of, MX pIn p choose a kind of in 1,2 or 3; L is selected from one or more in water, methyl alcohol, ethanol, acetone, acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde; M is selected from a kind of in 0,1,2 or 3.
Concrete preparation process is as follows:
Step 1 general formula (III A), general formula (III B) or general formula (III C) preparation of function monomer
Take by weighing general formula (II respectively A), general formula (II B) or general formula (II C) shown in the tertiary amine monomers and the 5-chloromethyl salicylic aldehyde of structure be dissolved in the solvent, make described general formula (II A), general formula (II B) or general formula (II C) tertiary amine monomers solution and 5-chloromethyl salicylic aldehyde solution, under the room temperature, 5-chloromethyl salicylic aldehyde solution is added general formula (II A), general formula (II B) or general formula (II C) in the tertiary amine monomers solution, stirring reaction heated up 60～85 ℃ and continued stirring reactions 2～6 hours after 2～6 hours, and the reaction mass temperature is reduced to room temperature, filtered, and made white crystalline material, recrystallization, drying makes general formula (III respectively A), general formula (III B) or general formula (III C) shown in structure contain quaternary ammonium salt unit and the unitary function monomer of salicylic aldehyde;
Described solvent is selected from acetone, butanone, chloroform, 1, the 2-ethylene dichloride, tetracol phenixin, 1, one or more in 4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, ethyl acetate, methyl acetate, butylacetate or the methylcyclohexane; Described general formula (II A), general formula (II B) or general formula (II C) mass ratio of tertiary amine monomers/5-chloromethyl salicylic aldehyde/solvent is 1: 0.2～2.5: 2～20;
Solvent described in the preparation process one can be selected aprotic polar solvent for use, as acetone, butanone, chloroform, 1,4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, ethyl acetate, methyl acetate, butylacetate, also can select aproticapolar solvent for use, as 1, the 2-ethylene dichloride, tetracol phenixin, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, methylcyclohexane also can be selected the mixture of described aprotic polar solvent and aproticapolar solvent for use.The solvent purpose of choosing carefully is to guarantee mutual-through type (II A), general formula (II B) or general formula (II C) tertiary amine monomers and 5-chloromethyl salicylic aldehyde all have high solubleness in solvent, and for general formula (III A), general formula (III B) or general formula (III C) function monomer has low solubleness in solvent, so help improving reaction efficiency, by simple filtration, promptly can make highly purified general formula (III A), general formula (III B) or general formula (III C) function monomer.
5-chloromethyl salicylic aldehyde mole dosage phase mutual-through type (II described in the preparation process one A), general formula (II B) or general formula (II C) the excessive purpose of tertiary amine monomers is in order to prevent the dehydrochlorination polymerization side reactions of 5-chloromethyl salicylic aldehyde self, the excessive and too high situation of temperature of reaction at tertiary amine especially.Under the suitable reaction conditions, described general formula (II A), general formula (II B) or general formula (II C) tertiary amine groups in the tertiary amine monomers molecule and the nucleophilic substitution reaction between the 5-chloromethyl salicylic aldehyde be clearly, quaternary ammonium salinization reaction efficiency height.
Step 2 general formula (VI A), general formula (VI B) or general formula (VI C) preparation of function monomer
Take by weighing general formula (III respectively A), general formula (III B) or general formula (III C) contain quaternary ammonium salt unit and unitary function monomer of salicylic aldehyde and H 2NQCOOH is dissolved in the dehydrated alcohol, and Glacial acetic acid is as catalyzer and souring agent, and 60～90 ℃ of temperature controls, stirring reaction were cooled to-5～0 ℃ after 6～20 hours, filters, and drying makes general formula (VI respectively A), general formula (VI B) or general formula (VI C) shown in structure contain quaternary ammonium salt unit and the unitary function monomer of Schiff's base;
Wherein said Q chooses C 5～C 12Aryl or ZCH, described Z chooses H or C 1～C 12Alkyl or C 6～C 12A kind of in the aryl; Described Schiff's base unit refers to described general formula (III A), general formula (III B) or general formula (III C) aldehyde radical and H in the function monomer molecule 2Condensation reaction takes place in the amino in the NQCOOH molecule, generates to have-structural unit of C=N-;
General formula (III A), general formula (III B) or general formula (III C) function monomer and H 2The consumption mol ratio of NQCOOH is 1: 0.85～1: 1.1, and the consumption of dehydrated alcohol is general formula (III A), general formula (III B) or general formula (III C) function monomer and H 22～5 times of NQCOOH quality summation, the consumption of Glacial acetic acid is H 20.1～10% of NQCOOH quality;
General formula (the VI that makes in the step 2 A), general formula (VI B) or general formula (VI C) shown in contain quaternary ammonium salt unit and the unitary function monomer of Schiff's base of structure very easily to lose the hydrogenchloride molecular conversion be zwitterionic compound, suit so add Glacial acetic acid in the reaction solvent that uses.Glacial acetic acid both can be used as catalyzer, can ensure the slightly acidic of reaction system again, prevented general formula (VI A), general formula (VI B) or general formula (VI C) reaction of function monomer dehydrochlorination molecule.
Step 3 general formula (I A), general formula (I B) or general formula (I C) preparation of function monomer
Take by weighing the general formula (VI that step 2 makes respectively A), general formula (VI B) or general formula (VI C) shown in structure contain the quaternary ammonium salt unit and the unitary function monomer of Schiff's base, soda-lime and L are dissolved in the solvent, 10～20 ℃ of temperature controls stir reaction down 1～2 hour, filter and remove the insoluble solid thing, it is standby that gained filtrate is called filtrate (1); Take by weighing MX pBe dissolved in the solvent, filter and remove the insoluble solid thing, make filtrate and be called filtrate (2), described filtrate (2) is added in the described filtrate (1), 20～80 ℃ of temperature controls, stir reaction down after 2～10 hours, distillation is concentrated, reaction system is cooled to-5～0 ℃, separate out crystallization, filter, drying makes general formula (I respectively A), general formula (I B) or general formula (I C) shown in structure contain quaternary ammonium salt and the unitary function monomer of title complex;
Wherein said soda-lime be by yellow soda ash or salt of wormwood and calcium oxide (being also referred to as unslaked lime) according to 1: 3 composite making of mass ratio, the consumption of soda-lime is general formula (VI A), general formula (VI B) or general formula (VI C) 0.5～5 times of function monomer quality;
Described L refers to one or more in acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde, and the consumption of described L is general formula (VI A), general formula (VI B) or general formula (VI C) 1～2 times of function monomer molar weight;
Described solvent is selected from one or more in water, acetone, ethanol or the methyl alcohol, and described solvent load is general formula (VI A), general formula (VI B) or general formula (VI C) 3～8 times of function monomer quality;
Described MX pIn M be selected from a kind of in the transition metal ion, X is selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of, p is selected from a kind of in 1,2 or 3; MX pMole dosage be equal to general formula (VI A), general formula (VI B) or general formula (VI C) mole dosage of function monomer.
The professional knows the step 3 operating process and can finish in water, acetone, ethanol or methanol solvate, when not adding acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or 5-vinyl salicylic aldehyde, general formula (I A), general formula (I B) or general formula (I C) L in the function monomer structure then is selected from water, acetone, ethanol or methyl alcohol; Carry out in water, acetone, ethanol or methanol solvate as the step 3 operating process, when adding and general formula (VI A), general formula (VI B) or general formula (VI C) etc. during in acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde of mole dosage one or more, general formula (I A), general formula (I B) or general formula (I C) L in the function monomer structure then is selected from one or more in acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde.
The inventor discovers that the step 3 operating process carries out in water solvent, not easily separated between complex reaction product and the raw material.Use the reaction of sodium hydroxide, potassium hydroxide too violent, use the reacting balance of yellow soda ash or salt of wormwood, but the moisture that produces in the reaction process is not easily separated.For this reason, finding to select for use methyl alcohol, ethanol, acetone as solvent through experiment, select for use soda-lime to be used for step 3, is preparation general formula (I A), general formula (I B) or general formula (I C) optimal conditions of function monomer.
General formula (VI A), general formula (VI B) or general formula (VI C), MX pWith the very easily dissolving in methyl alcohol, ethanol or acetone solvent of acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or 5-vinyl salicylic aldehyde, and general formula (VI A), general formula (VI B) or general formula (VI C) react the oxidized calcium absorption of moisture that produces with yellow soda ash or salt of wormwood, yellow soda ash, salt of wormwood, sodium-chlor, Repone K, calcium oxide or calcium hydroxide do not dissolve in methyl alcohol, ethanol or acetone solvent, can conveniently remove yellow soda ash, salt of wormwood, sodium-chlor, Repone K, calcium oxide, calcium hydroxide after filtration, for improving reaction efficiency, simplifying general formula (I A), general formula (I B) or general formula (I C) the function monomer purification technique all is preferable methods.
Beneficial effect of the present invention:
1. described general formula (I A), general formula (I B) or general formula (I C) function monomer can carry out self-polymeric reaction or copolyreaction, can be used for preparing water-soluble or hydrophilic polymers or ion imprinted polymer material as function monomer.
2. described general formula (I A), general formula (I B) or general formula (I C) function monomer is solid matter, stores the transportation stability height, and is safe and convenient to use.
3. prepare described general formula (I A), general formula (I B) or general formula (I C) the function monomer method is simple, starting material are the commercial goods, and the source is abundant, and each step reaction product yield height does not have three-waste pollution.
4. described general formula (I A), general formula (I B) or general formula (I C) the function monomer colour-change multiterminal that are, the color and the fluorescent characteristic of being produced title complex by its ion imprinted polymer made or transition metal ion chelatropic reaction change various.Change according to color and luster, can indicate kind, valence state, absorption degree of saturation that the heavy ion imprinted polymer adsorbs described transition metal ion.
5. by general formula (I provided by the invention A), general formula (I B) or general formula (I C) the prepared heavy metal ion imprinted polymer material of function monomer also has the anionresin function.
6. by general formula (I provided by the invention A), general formula (I B) or general formula (I C) the prepared heavy ion imprinted polymer material of function monomer, when the wash-out template, not only can use hydrochloric acid as elutriant, also can use the Sodium Sulphide aqueous solution as elutriant.
Specific embodiment
By following embodiment to general formula (I provided by the invention A), general formula (I B) or general formula (I C) shown in the function monomer and the preparation method of structure further specify, its purpose is to understand better content of the present invention.Therefore, unlisted general formula (I among the embodiment A), general formula (I B) or general formula (I C) shown in the function monomer and preparation method thereof of structure should not be considered as limiting the scope of the invention.Anyly all belong to the intellecture property aggressive behavior at improvement of the present invention.
Embodiment 1 function monomer MI AThe preparation of-1-Cu-1
Step 1, MI AThe preparation of-1-CS
Taking by weighing methacrylic acid-2-(dimethylamino) ethyl ester (DMA) 78 grams and 5-chloromethyl salicylic aldehyde (5-CS) 80 grams is dissolved in respectively in the 100 gram ethyl acetate, make the ethyl acetate solution of described methacrylic acid-2-(dimethylamino) ethyl ester and the ethyl acetate solution of 5-chloromethyl salicylic aldehyde, under the room temperature, the ethyl acetate solution of 5-chloromethyl salicylic aldehyde is added in the ethyl acetate solution of methacrylic acid-2-(dimethylamino) ethyl ester, behind the stirring reaction 4 hours, heat up 60～65 ℃ and continued stirring reaction 6 hours.Reaction system leaves standstill and naturally cools to room temperature, filters and obtains shallow white crystalline material, recrystallization, drying, makes 151 gram MI A-1-CS, yield 95.6%, 62～63 ℃ of fusing points.
Step 2, MI AThe preparation of-1-CS-AA
Figure BSA00000873318000092
Take by weighing 65 gram MI respectively A-1-CS and 28 gram anthranilic acids are dissolved in 100 milliliters of dehydrated alcohols, add 2 gram Glacial acetic acid again, 80～85 ℃ of temperature controls, stirring and refluxing was reacted 6 hours, and constantly steamed compound 60 grams of part second alcohol and water, after finishing reaction, the reaction product system is cooled to-5～0 ℃, separates out the orange crystal, filter, drying makes MI A-1-CS-AA.
Step 3, MI AThe preparation of-1-Cu-1
Figure BSA00000873318000093
Take by weighing 85 gram MI A-1-CS-AA is dissolved in 200 milliliters of anhydrous methanols, stirs slowly to add soda-lime 100 grams down, reacts after 2 hours, filters and removes solid matter, gained filtrate for later use; Get cupric chloride 32 grams and be dissolved in 100 milliliters of dehydrated alcohols, the filtering insoluble impurities adds gained cupric chloride absolute methanol solution in the filtrate, 60～65 ℃ of temperature controls, stirring reaction was got propylene hydrazides 25 grams and is also dropped in the reaction system after half an hour, continued 60～65 ℃ of stirring reactions of temperature control 2 hours, after distillation concentrates, reaction system is cooled to-5～0 ℃, separates out crystallization, filter, drying makes 111 gram yellow-green colour MI A-1-Cu-1, yield 90.2%, 51～55 ℃ of fusing points.
Ultimate analysis (theoretical value) C 25H 43ClCuN 4O 6: C54.77 (55.04), H6.59 (6.62), N8.54 (8.56), Cl5.39 (5.42).
IR (KBr, compressing tablet, cm -1): 3415,3017,2937,2868,1710,1689,1615,1548,1326,1137,887.
H 1-NMR(DMSO-d 6，δ)：1，91(s，3H)，3.30(s，6H)，3.53(t，2H)，4.53(m，4H)，5.54～5.87(m，8H)，6.58～7.37(m，7H)，8.13(s，1H)。
Embodiment 2 MI AThe preparation of-1-Cr-1
Figure BSA00000873318000101
According to method and the operation steps of embodiment 1, it is chromium chloride that the cupric chloride in embodiment 1 step 3 is changed, and the propylene hydrazides changes and is 4-vinylpridine and vinylformic acid, makes the MI of greyish-green A-1-Cr-1.
Embodiment 3 MI AThe preparation of-2-Zn-1
Figure BSA00000873318000102
Method and operation steps according to embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) of embodiment 1 step 1 is changed methacrylic acid-2-(diethylin) ethyl ester (DEA), the step 3 cupric chloride changes and is zinc chloride, the propylene hydrazides changes and is 4-vinylpridine, makes red MI A-2-Zn-1.
Embodiment 4 MI AThe preparation of-2-Ni-1
Figure BSA00000873318000111
Method and operation steps according to embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) of embodiment 1 is changed methacrylic acid-2-(diethylin) ethyl ester (DEA), cupric chloride change and to be that nickelous chloride, propylene hydrazides change and to be the 1-vinyl imidazole, make dun MAI A-2-Ni-1.
Embodiment 5 DMAI BThe preparation of-1-Cu-1
According to method and the operation steps of embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) of embodiment 1 step 1 changed be N, the N-dimethyl allylamine makes green-yellow DMAI B-1-Cu-1,73～75 ℃ of fusing points.
Embodiment 6 VBDMI BThe preparation of-1-Zn-1
Method and operation steps according to embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) change of embodiment 1 step 1 is N, and N-dimethyl-4-vinyl benzylamine, the cupric chloride of step 3 change and are zinc chloride, the propylene hydrazides changes and is the 1-vinyl imidazole, makes red VBDMI B-1-Zn-1.
Figure BSA00000873318000121
Embodiment 7 PY-I CThe preparation of-Cu-1
Figure BSA00000873318000122
According to method and the operation steps of embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) of embodiment 1 step 1 changed be that 4-vinylpridine, propylene hydrazides change and be 4-vinylpridine, make yellow-green colour PY-I C-Cu-1.
Embodiment 8 PY-I CThe preparation of-Cu-2
Figure BSA00000873318000123
According to method and the operation steps of embodiment 1, methacrylic acid-2-(dimethylamino) ethyl ester (DMA) of embodiment 1 step 1 changed be that 4-vinylpridine, propylene hydrazides change and be the 1-vinyl imidazole, make yellow PY-I C-Cu-2.
Embodiment 9 contains the characteristic of quaternary ammonium salt and the unitary function monomer of title complex
Table 1 has been listed the MI of embodiment 1 A-1-Cu-1, MI A-1-Cr-1, DMAI B-1-Cu-1, PY-I CThe solvability of-Cu-2 function monomer in water, methyl alcohol, ethanol, chloroform, ethyl acetate, toluene solvant; Table 1 has also been listed MI A-1-Cu-1, MI A-1-Cr-1, DMAI B-1-Cu-1, PY-I C-Cu-2 function monomer and mass concentration are the response feature of 2.5% sodium sulfide solution:
Table 1. contains the character of the function monomer of quaternary ammonium salt and title complex
Figure BSA00000873318000131
Easily dissolving of v representative in the table 1, s represents dissolving, and i represents micro dissolution, and u does not dissolve
Judge according to containing unitary function monomer of quaternary ammonium salt and title complex and sodium sulfide solution response feature in the table 1, contain the preparation that quaternary ammonium salt and the unitary function monomer of title complex both can be used for the ion imprinted polymer material by provided by the invention, and also can use sodium sulfide solution wash-out template ion, with MI A-1-Cu-1 is the reaction result that the reaction formula of example illustrates itself and sodium sulphite:

Claims (2)

1. function monomer that is used to prepare the heavy metal ion blotting polymkeric substance, its feature has general formula (I A), general formula (I B) or general formula (I C) shown in structure:
Its formula of (I A), general formula (I B) or general formula (I C) in R choose H or methyl; Y chooses O or NH; N chooses a kind of in 2,3,4,5 or 6, R 1And R 2Choose C respectively 1～C 18A kind of in the alkyl, R 3Choose C 3～C 18Unsaturated alkyl; Q chooses C 6～C 12Aryl or ZCH, described Z chooses H, C 1～C 12Alkyl or C 6～C 12A kind of in the aryl; M refers to transition metal ion, and L is selected from one or more in water, methyl alcohol, ethanol, acetone, acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde; M is selected from a kind of in 0,1,2 or 3; X -Be selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of.
2. according to the described preparation method who is used to prepare the function monomer of heavy metal ion blotting polymkeric substance of claim 1, it is characterized in that being realizing according to following synthetic route and preparation process:
Figure FSA00000873317900021
Figure FSA00000873317900031
In described synthetic route, R chooses H or methyl; Y chooses O or NH; N chooses a kind of in 2,3,4,5 or 6, R 1And R 2Choose C respectively 1～C 18A kind of in the alkyl, R 3Choose C 3～C 18Unsaturated alkyl; Q chooses C 6～C 12Aryl or ZCH, described Z chooses H, C 1～C 12Alkyl or C 6～C 12A kind of in the aryl; MX pIn M be selected from a kind of in the transition metal ion, MX pIn X -Be selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of, MX pIn p choose a kind of in 1,2 or 3; L is selected from one or more in water, methyl alcohol, ethanol, acetone, acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde; M is selected from a kind of in 0,1,2 or 3;
Concrete preparation process is as follows:
Step 1 general formula (III A), general formula (III B) or general formula (III C) preparation of function monomer
Take by weighing general formula (II respectively A), general formula (II B) or general formula (II C) shown in the tertiary amine monomers and the 5-chloromethyl salicylic aldehyde of structure be dissolved in respectively in the solvent, make described general formula (II A), general formula (II B) or general formula (II C) tertiary amine monomers solution and 5-chloromethyl salicylic aldehyde solution, under the room temperature, 5-chloromethyl salicylic aldehyde solution is added general formula (II A), general formula (II B) or general formula (II C) in the tertiary amine monomers solution, stirring reaction heated up 60～85 ℃ and continued stirring reactions 2～6 hours after 2～6 hours, and the reaction mass temperature is reduced to room temperature, filtered, and made crystalline material, recrystallization, drying makes general formula (III respectively A), general formula (III B) or general formula (III C) shown in structure contain quaternary ammonium salt unit and the unitary function monomer of salicylic aldehyde;
Described solvent is selected from acetone, butanone, chloroform, 1, the 2-ethylene dichloride, tetracol phenixin, 1, one or more in 4-dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, toluene, dimethylbenzene, methyl-phenoxide, chlorobenzene, ethyl acetate, methyl acetate, butylacetate or the methylcyclohexane; Described general formula (II A), general formula (II B) or general formula (II C) the consumption mass ratio of tertiary amine monomers/5-chloromethyl salicylic aldehyde/solvent is 1: 0.2～2.5: 2～20;
Step 2 general formula (VI A), general formula (VI B) or general formula (VI C) preparation of function monomer
Take by weighing general formula (III respectively A), general formula (III B) or general formula (III C) function monomer and H 2NQCOOH is dissolved in the dehydrated alcohol, and Glacial acetic acid is as catalyzer and souring agent, and 60～90 ℃ of temperature controls, stirring reaction were cooled to-5～0 ℃ after 6～20 hours, filters, and drying makes general formula (VI respectively A), general formula (VI B) or general formula (VI C) shown in structure contain quaternary ammonium salt unit and the unitary function monomer of Schiff's base;
Wherein said Q chooses C 5～C 12Aryl or ZCH, described Z chooses H, C 1～C 12Alkyl or C 6～C 12A kind of in the aryl;
Described Schiff's base unit refers to described general formula (III A), general formula (III B) or general formula (III C) contain aldehyde radical and H in quaternary ammonium salt unit and the unitary function monomer molecule of salicylic aldehyde 2Amino generation condensation reaction in the NQCOOH molecule generates and to have-structural unit of C=N-;
General formula (III A), general formula (III B) or general formula (III C) function monomer and H 2The consumption mol ratio of NQCOOH is 1: 0.85～1: 1.1, and the consumption of dehydrated alcohol is general formula (III A), general formula (III B) or general formula (III C) function monomer and H 22～5 times of NQCOOH quality summation, the consumption of Glacial acetic acid is H 20.1～10% of NQCOOH quality;
Step 3 general formula (I A), general formula (I B) or general formula (I C) preparation of function monomer
Take by weighing the general formula (VI that step 2 makes respectively A), general formula (VI B) or general formula (VI C) shown in structure contain the quaternary ammonium salt unit and the unitary function monomer of Schiff's base, soda-lime and L are dissolved in the solvent, 10～20 ℃ of temperature controls stir reaction down 1～2 hour, filter and remove the insoluble solid thing, it is standby that gained filtrate is called filtrate (1); Take by weighing MX pBe dissolved in the solvent, filter and remove the insoluble solid thing, make filtrate and be called filtrate (2), described filtrate (2) is added in the described filtrate (1), 20～80 ℃ of temperature controls, stir reaction down after 2～10 hours, distillation is concentrated, reaction system is cooled to-5～0 ℃, separate out crystallization, filter, drying makes general formula (I respectively A), general formula (I B) or general formula (I C) shown in structure contain quaternary ammonium salt and the unitary function monomer of title complex;
Wherein said soda-lime be by yellow soda ash or salt of wormwood and calcium oxide according to 1: 3 composite making of mass ratio, the consumption of soda-lime is general formula (VI A), general formula (VI B) or general formula (VI C) 0.5～5 times of function monomer quality;
Described L refers to one or more in water, methyl alcohol, ethanol, acetone, acrylamide, 2-Methacrylamide, propylene hydrazides, 2-methacrylic hydrazides, vinylformic acid, 2-methacrylic acid, 1-vinyl imidazole, 1-allyl imidazole, 4-vinylpridine, 2-vinyl pyridine, N-(4-ethenylphenyl) imines diacetic acid, allyl sulphonic acid or the 5-vinyl salicylic aldehyde, and the consumption of described L is general formula (VI A), general formula (VI B) or general formula (VI C) 1～2 times of function monomer molar weight;
Described solvent is selected from one or more in water, acetone, ethanol or the methyl alcohol, and described solvent load is general formula (VI A), general formula (VI B) or general formula (VI C) 3～8 times of function monomer quality;
Described MX pIn M be selected from a kind of in the transition metal ion, X is selected from F -, Cl -, Br -, I -, HSO 4 -, H 2PO 4 -Or CH 3COO -In a kind of, p is selected from a kind of MX in 1,2 or 3 pMole dosage be equal to general formula (VI A), general formula (VI B) or general formula (VI C) mole dosage of function monomer.
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