CN101906186A - Method for preparing fatty acid molecular imprinted polymer - Google Patents
Method for preparing fatty acid molecular imprinted polymer Download PDFInfo
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- CN101906186A CN101906186A CN 201010251004 CN201010251004A CN101906186A CN 101906186 A CN101906186 A CN 101906186A CN 201010251004 CN201010251004 CN 201010251004 CN 201010251004 A CN201010251004 A CN 201010251004A CN 101906186 A CN101906186 A CN 101906186A
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- fatty acid
- imprinted polymer
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- molecular imprinted
- acid molecular
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- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 32
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 27
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 27
- 239000000194 fatty acid Substances 0.000 title claims abstract description 27
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 26
- 150000002632 lipids Chemical class 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 15
- 229960004232 linoleic acid Drugs 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- 235000021355 Stearic acid Nutrition 0.000 claims description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008117 stearic acid Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000004817 gas chromatography Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- NPSSWQJHYLDCNV-UHFFFAOYSA-N prop-2-enoic acid;hydrochloride Chemical compound Cl.OC(=O)C=C NPSSWQJHYLDCNV-UHFFFAOYSA-N 0.000 claims description 4
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 4
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 241001465754 Metazoa Species 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 239000004971 Cross linker Substances 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 230000008961 swelling Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000005477 standard model Effects 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003822 preparative gas chromatography Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- -1 aluminum stearate cadmium stearate Chemical compound 0.000 description 2
- 230000002579 anti-swelling effect Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 206010020466 Hunger Diseases 0.000 description 1
- 240000006474 Theobroma bicolor Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 235000014121 butter Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000004626 essential fatty acids Nutrition 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001537 neural effect Effects 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing fatty acid molecular imprinted polymer, which comprises the following steps of: introducing a covalent bond to form a functional monomer of the molecular imprinted polymer; mixing template solution with certain concentration and the functional monomer according to a proportion, fully stirring, and refluxing to prepare precursor solution; and adding an initiator and a crosslinker, performing water bath for 24 h, grinding the product, sieving with a screen of 200 meshes, refluxing and extracting by using methanol-acetic acid solution for a long time, fully washing the obtained product by using ethanol, and drying to constant weight by using an oven at 60 DEG C to prepare the fatty acid molecular imprinted polymer. The fatty acid molecular imprinted polymer prepared by the method has the advantages of regular shape, high mechanical strength, high physiochemical performance, swelling resistance, good selective adsorption effect and the like, can be used under extreme conditions such as acid, alkali, high temperature and the like, is suitable for separating, purifying and enriching the fatty acid from complex matrixes such as water-soluble media, animal derived foods and the like, and has wide application prospect.
Description
Technical field
The invention belongs to separation and purification polymer mould material preparation field, relate to a kind of preparation method of fatty acid molecular imprinted polymer.
Background technology
Polyunsaturated fatty acid refers to contain two or more pairs key and carbon chain lengths is the straight chain fatty acid of 18～22 carbon atoms, is divided into omega-3 and omega-6 usually.Close in the fatty acid molecule in many insatiable hungers, on the 3rd carbon atom reciprocal, be called omega-3 apart from two keys of carboxyl distal-most end; On six carbon atom, then be called omega-6.
Linolic acid is an essential fatty acid, but often edible vessel softening reduces the absorption of gi tract to cholesterol, and it is excreted.It is reported, linoleic main pharmacological is to keep brain and essential factor antithrombotic of neural function and reducing blood-fat, prevent atherosclerosis, the prevention canceration, suppress tumour cell and shift and the abnormalism disease that life-time service can enhance immunity power, prolong life.Linolic acid is added in protective foods or the medicine, remedy the deficiency that human body is taken in, strengthen the ability of human body resist the disease, bring into play its important physiological action human body.Along with the development of medicine industry, linoleic pharmaceutical use improves constantly, and meanwhile, also is subjected to people's favor day by day as a kind of functional grease, is necessary the mixed fatty acid in the plant and animal material is separated, and obtains polyunsaturated fatty acid.The polyunsaturated fatty acid enriching method of having reported at present has several different methods such as urea adduct method, supercritical extraction, freeze crystallization, lipase-catalyzed hydrolysis, these method separation and purification unsaturated fatty acids problems such as all there is the cost height in one, and the finished product yield is low.
Stearic acid is a kind of lipid acid that nature extensively exists, the stearic acid that all has content not wait in nearly all grease, content in animal tallow is higher, can reach 24% as content in the butter, content is less in the vegetables oil, tea oil is 0.8%, and plam oil is 6%, and the content in the theobroma oil is then up to 34%.Stearic acid is mainly used in the production stearate: sodium stearate, Magnesium Stearate, calcium stearate, lead stearate, aluminum stearate cadmium stearate, iron stearate, potassium stearate.Be widely used in and produce makeup, plastics cold resistant plasticizer, releasing agent, stablizer, tensio-active agent, thiofide, water-resisting agent, rumbling compound, metallic soap, metalliferous mineral flotation agent, tenderizer, medical supplies and other organic chemicals.
The stearic production method of industry mainly contains fractionating process and milling process.Add decomposition agent in winterized stearin, hydrolysis gets croude fatty acids, gets product through washing, distillation, decolouring again.There are masty problems such as step complexity in conventional production methods.
At present, the standard model domestic market of unsaturated fatty acids methyl esters does not have sale, from external import price costliness, some purity is not high yet, and, standard model is reaction and reduction purity such as generation oxidation easily, decomposition, polymerization in the preservation process, and therefore, grease analytical work person Chang Yin lacks standard model and feels difficulty.With the lipid acid such as linolic acid in the molecular imprinting method purifying vegetables oil, the purifying that can be the fatty acid standard model has been opened up a new direction.
Molecular imprinting is the technology of the preparation high-selectivity adsorbing material that grows up over nearly 20 years, and it has imitated the action principle of organic sphere lock and key theory, can carry out selective separation to separated portion from the molecule rank.The molecular imprinting isolation technique has characteristics such as environmental friendliness, green non-pollution, has wide development space in fields such as separation and Extraction lipid acid.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of preparation process simple, the preparation method of the fatty acid molecular imprinted polymer that the molecularly imprinted polymer physical strength height that makes, good physical and chemical properties, anti-swelling and selection fractionation by adsorption ability are strong.
The present invention realizes that the technical scheme of purpose is as follows:
A kind of preparation method of fatty acid molecular imprinted polymer, the step of preparation is as follows:
(1) initiator is added in the ethanol, heating in water bath with the rapid suction filtration of solution, gets white crystals, drying near boiling after the cooling.
(2) preparation of imprinted polymer: lipid acid and function monomer be dissolved in stir 1-5h in the acetonitrile; form the template molecule monomer complex; add initiator, linking agent; the degassing; under nitrogen protection in 40-70 ℃ of water-bath thermopolymerization 20-30h; get the white blocks shaped polymer, in mortar, fully grind the back and cross 200 order sub-sieves, obtain fines shape product.
(3) remove template molecule: with acetate-methanol mixed solution extracting template molecule, repeatable operation can not detect in gas-chromatography till the template molecule, and vacuum-drying obtains fatty acid molecular imprinted polymer to constant weight.
Lipid acid wherein: function monomer: the mol ratio of linking agent is 1: 2-16: 6-30.
And described initiator is a Diisopropyl azodicarboxylate.
And described function monomer is 2,6-diamino pyrrolidone or acrylamide.
And, described 2, the preparation method of 6-diamino pyrrolidone is: the chloroformic solution with the diamino-pyridine and the triethylamine of equimolar amount is made into the 3%-6% weight ratio, and place the rare gas element flask to stir, at room temperature acrylate chloride and the 2 times of amount chloroformic solutions with 2 times of amounts dropwise splash into flask, stirring at room 30min, 60 ℃ are stirred 40min down, filter, and filtrate gets the yellow-green colour semisolid through underpressure distillation, promptly get function monomer 2 through recrystallization, 6-diamino pyrrolidone.
And described linking agent is an Ethylene glycol dimethacrylate.
And described lipid acid is saturated and unsaturated fatty acids.
And described lipid acid is linolic acid or stearic acid.
Advantage of the present invention and positively effect are:
1, the molecularly imprinted polymer that makes of the method among the present invention has regular shape, physical strength height, good physical and chemical properties, anti-swelling, selects advantage such as advantages of good adsorption effect, can be used for extreme conditions such as acid, alkali and high temperature, be applicable to from water-soluble medium and complex matrices such as animal derived food separate, purifying and enrichment is saturated and polyunsaturated fatty acid, have broad application prospects.
2, molecularly imprinted polymer Static Adsorption capacity Q to target molecule lipid acid under 25-60 ℃ of temperature of the present invention's preparation reaches 7-9.2mg/g, on the molecule rank, realize selective adsorption, in strong polar solution, target molecule is still had good selection fractionation by adsorption ability target molecule.
3, the preparation method of polymkeric substance is simple among the present invention, and craft science is with low cost, and is simple to operate, and reaction conditions is gentle and be easy to control, and the polymkeric substance of the saturated and unsaturated fatty acids of a kind of high efficiency extraction can be provided.
4, the present invention has also synthesized function monomer 2 first, 6-diamino pyrrolidone, and the purity height, effect is obvious, and also the development for the Ben Guan field provides help.
Embodiment
The present invention is further described below in conjunction with specific embodiments, and its specific embodiments only is construed as to illustrating, and is not determinate, can not limit protection scope of the present invention with following illustrating.
Invention thought of the present invention is: by introducing the function monomer that covalent linkage can form molecularly imprinted polymer, certain density template solution and function monomer are mixed in proportion, fully stir, make precursor solution after the backflow; Add initiator, linking agent again, water-bath 24h; Product is ground, cross 200 mesh sieves, put into apparatus,Soxhlet's, with the long-time refluxing extraction of methyl alcohol-acetic acid solution; Products therefrom is put into baking oven after fully cleaning with ethanol, dries to constant weight for 60 ℃, promptly obtains saturated fatty acid or polyunsaturated fatty acid are had the molecularly imprinted polymer material of special selection adsorptivity.
Embodiment 1
Lipid acid is linolic acid in the present embodiment.
A kind of preparation method of fatty acid molecular imprinted polymer, step is as follows:
(1) in the triangular flask of reflux condensing tube is housed initiator Diisopropyl azodicarboxylate (AIBN) is added in the 100mL ethanol, heating in water bath is to approaching boiling, and the rapid suction filtration of hot solution gets white crystals after the cooling, carry out drying in vacuum drier.
(2) triethylamine of diamino-pyridine and equimolar amount is made into the chloroformic solution (wherein the triethylamine of diamino-pyridine and equimolar amount altogether 3%-6%) of 3%-6% weight ratio, place the noble gas flask to stir, at room temperature acrylate chloride, chloroform (wherein the weight of acrylate chloride, chloroform is that 2-4 doubly measures) solution are dropwise splashed into flask, stirring at room 30min, 60 ℃ are stirred 40min down, filter, filtrate gets the yellow-green colour semisolid through underpressure distillation, obtain function monomer through recrystallization: 2,6-diamino pyrrolidone.
(3) linolic acid 0.284g and function monomer 0.217g are dissolved in stir 4h in the acetonitrile; form stable template molecule monomer complex; add initiator Diisopropyl azodicarboxylate 60mg, linking agent Ethylene glycol dimethacrylate (EDMA) 4.95g; ultrasonic degas 5min; logical nitrogen 5min, under nitrogen protection in 60 ℃ of water-baths thermopolymerization 24h, the white blocks shaped polymer; in mortar, fully grind the back and cross 200 order sub-sieves, obtain fines shape product.
Lipid acid wherein: function monomer: the mol ratio of linking agent is 1: 2-16: 6-30.
(4) with volume ratio be acetate-methanol solution extracting template molecule in apparatus,Soxhlet's of 1: 9, repeatable operation can not detect in gas-chromatography till the template molecule, and vacuum-drying obtains the linolic acid molecularly imprinted polymer to constant weight.
Test experiments:
Take by weighing 100mg exsiccant linolic acid molecularly imprinted polymer and put into volumetric flask, each adds 6.0mL 10mmolL
-1The linolic acid hexane solution, 20h vibrates under the room temperature, with the centrifugal 15min of 4000r/min, getting the 1mL supernatant liquor moves in the 10mL centrifuge tube, add 1% sulfuric acid methanol solution with the fatty acid esterification that does not adsorb in the supernatant liquor, with the composition of vapor-phase chromatography detection lipid acid, calculate linoleic equilibrium concentration in the solution of absorption back, calculate the adsorptive capacity Q=8.43mg/g of polymkeric substance according to combination front and back change in concentration to microsphere.
Embodiment 2
Lipid acid is linolic acid in the present embodiment.
A kind of preparation method of fatty acid molecular imprinted polymer, step is as follows:
(1) in the triangular flask of reflux condensing tube is housed, initiator Diisopropyl azodicarboxylate (AIBN) 120g is added in the 100mL ethanol, be heated in the water-bath near boiling, the rapid suction filtration of hot solution gets white crystals after the cooling, dry in vacuum drier;
(2) adopt mass polymerization, carry out the synthetic of MIPs (molecular engram material), target molecule 0.284g and function monomer 0.284g are dissolved in stir 4h in the solvent, form stable template molecule monomer complex with the ratio after optimizing; Add initiator A IBN, linking agent EDMA 2.475g, ultrasonic degas 5min, logical nitrogen 5min, under nitrogen protection in 60 ℃ of water-baths thermopolymerization 24h, the white blocks shaped polymer; It is fully ground the back cross 200 order sub-sieves in mortar, obtain fines shape product;
The function monomer of using in this step is the monomer of preparation among the embodiment 1.
(3) with volume ratio be acetate-methanol solution extracting template molecule in apparatus,Soxhlet's of 4: 6, repeatable operation can not detect in gas-chromatography till the template molecule, and vacuum-drying promptly obtains the linolic acid molecularly imprinted polymer to constant weight.
Test experiments:
Take by weighing 100mg exsiccant linolic acid molecularly imprinted polymer and put into volumetric flask, each adds 6.0mL 10mmolL
-1The linolic acid hexane solution, 20h vibrates under the room temperature, with the centrifugal 15min of 4000r/min, getting the 1mL supernatant liquor moves in the 10mL centrifuge tube, add 1% sulfuric acid methanol solution with the fatty acid esterification that does not adsorb in the supernatant liquor, with the composition of vapor-phase chromatography detection lipid acid, calculate linoleic equilibrium concentration in the solution of absorption back, calculate the adsorptive capacity Q=7.59mg/g of polymkeric substance according to combination front and back change in concentration to microsphere.
Embodiment 3
Lipid acid is stearic acid in the present embodiment.
A kind of preparation method of fatty acid molecular imprinted polymer, step is as follows:
(1) in the triangular flask of reflux condensing tube is housed, initiator Diisopropyl azodicarboxylate (AIBN) 120g is added in the 100mL ethanol, be heated in the water-bath near boiling, the rapid suction filtration of hot solution gets white crystals after the cooling, dry in vacuum drier;
(2) adopt mass polymerization; carry out the synthetic of MIPs (molecular engram material); 0.288g stearic acid and function monomer acrylamide 0.568g are dissolved in dark reaction 4h in the solvent; form stable template molecule monomer complex; add 10mg initiator A IBN, linking agent EDMA 2.475g, ultrasonic degas 5min, logical nitrogen 5min; under nitrogen protection in 60 ℃ of water-baths thermopolymerization 24h, the white blocks shaped polymer.It is fully ground the back cross 200 order sub-sieves in mortar, obtain fines shape product.
(3) with volume ratio be acetate-methanol solution extracting template molecule in apparatus,Soxhlet's of 1: 4, repeatable operation can not detect in gas-chromatography till the template molecule, and vacuum-drying promptly obtains the stearic acid molecularly imprinted polymer to constant weight.
Test experiments:
Take by weighing 100mg exsiccant stearic acid molecularly imprinted polymer and put into volumetric flask, each adds 6.0mL 10mmolL
-1The linolic acid hexane solution, 8h vibrates under the room temperature, with the centrifugal 5min of 4000r/min, getting the 1mL supernatant liquor moves in the 10mL centrifuge tube, add 4% sulfuric acid methanol solution with the not stearic acid esterification of absorption in the supernatant liquor, with the composition of vapor-phase chromatography detection lipid acid, calculate stearic equilibrium concentration in the solution of absorption back, calculate the adsorptive capacity Q=9.14mg/g of polymkeric substance according to combination front and back change in concentration to microsphere.
Claims (7)
1. the preparation method of a fatty acid molecular imprinted polymer, it is characterized in that: the step of preparation is as follows:
(1) initiator is added in the ethanol, heating in water bath with the rapid suction filtration of solution, gets white crystals, drying near boiling after the cooling;
(2) preparation of imprinted polymer: lipid acid and function monomer be dissolved in stir 1-5h in the acetonitrile, form the template molecule monomer complex, add initiator, linking agent, the degassing, under nitrogen protection in 40-70 ℃ of water-bath thermopolymerization 20-30h, get the white blocks shaped polymer, in mortar, fully grind the back and cross 200 order sub-sieves, obtain fines shape product;
(3) remove template molecule: with acetate-methanol mixed solution extracting template molecule, repeatable operation can not detect in gas-chromatography till the template molecule, and vacuum-drying obtains fatty acid molecular imprinted polymer to constant weight;
Lipid acid wherein: function monomer: the mol ratio of linking agent is 1: 2-16: 6-30.
2. the preparation method of fatty acid molecular imprinted polymer according to claim 1, it is characterized in that: described initiator is a Diisopropyl azodicarboxylate.
3. the preparation method of fatty acid molecular imprinted polymer according to claim 1, it is characterized in that: described function monomer is 2,6-diamino pyrrolidone or acrylamide.
4. according to the preparation method of claim 1 or 3 described fatty acid molecular imprinted polymers, it is characterized in that: described 2, the preparation method of 6-diamino pyrrolidone is: the chloroformic solution that the diamino-pyridine and the triethylamine of equimolar amount is made into the 3%-6% weight ratio, place the rare gas element flask to stir, at room temperature acrylate chloride that 1-3 is doubly measured and 1-3 doubly measure chloroformic solution and dropwise splash into flask, stirring reaction stage by stage, filter, filtrate obtains the yellow-green colour semisolid through underpressure distillation, promptly get function monomer 2 through recrystallization, 6-diamino pyrrolidone.
5. the preparation method of fatty acid molecular imprinted polymer according to claim 1, it is characterized in that: described linking agent is an Ethylene glycol dimethacrylate.
6. the preparation method of fatty acid molecular imprinted polymer according to claim 1, it is characterized in that: described lipid acid is saturated and unsaturated fatty acids.
7. the preparation method of fatty acid molecular imprinted polymer according to claim 1, it is characterized in that: described lipid acid is linolic acid or stearic acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675506A (en) * | 2012-06-12 | 2012-09-19 | 福州大学 | 6-kinetin molecularly imprinted polymer and application thereof |
| CN104870482A (en) * | 2012-12-26 | 2015-08-26 | 莱雅公司 | Molecularly imprinted polymers and their use as antidandruff agents |
| CN104870525A (en) * | 2012-12-26 | 2015-08-26 | 莱雅公司 | Molecularly imprinted polymers of sol-gel type and their use as antidandruff agent |
| CN115970664A (en) * | 2023-02-28 | 2023-04-18 | 浙江工业大学 | Magnetic silvered molecularly imprinted polymer microsphere, preparation thereof and application thereof in enriching polyunsaturated fatty acid |
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| WO2014178081A2 (en) * | 2013-04-30 | 2014-11-06 | Zim Laboratories Limited | Molecular traps for certain undesirable materials |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6660176B2 (en) * | 2001-01-24 | 2003-12-09 | Virginia Commonwealth University | Molecular imprinting of small particles, and production of small particles from solid state reactants |
| CN1718593A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院化学研究所 | A kind of preparation method of molecularly imprinted polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6660176B2 (en) * | 2001-01-24 | 2003-12-09 | Virginia Commonwealth University | Molecular imprinting of small particles, and production of small particles from solid state reactants |
| CN1718593A (en) * | 2004-07-06 | 2006-01-11 | 中国科学院化学研究所 | A kind of preparation method of molecularly imprinted polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675506A (en) * | 2012-06-12 | 2012-09-19 | 福州大学 | 6-kinetin molecularly imprinted polymer and application thereof |
| CN102675506B (en) * | 2012-06-12 | 2013-12-11 | 福州大学 | 6-kinetin molecularly imprinted polymer and application thereof |
| CN104870482A (en) * | 2012-12-26 | 2015-08-26 | 莱雅公司 | Molecularly imprinted polymers and their use as antidandruff agents |
| CN104870525A (en) * | 2012-12-26 | 2015-08-26 | 莱雅公司 | Molecularly imprinted polymers of sol-gel type and their use as antidandruff agent |
| CN104870525B (en) * | 2012-12-26 | 2017-09-19 | 莱雅公司 | The molecularly imprinted polymer of sol-gel type and its purposes as anti-dandruff agent |
| CN115970664A (en) * | 2023-02-28 | 2023-04-18 | 浙江工业大学 | Magnetic silvered molecularly imprinted polymer microsphere, preparation thereof and application thereof in enriching polyunsaturated fatty acid |
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