CN104084234A - Crosslinked polyethylene pyrrolidone based catalyst and preparation method thereof - Google Patents
Crosslinked polyethylene pyrrolidone based catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229920003020 cross-linked polyethylene Polymers 0.000 title abstract 7
- 239000004703 cross-linked polyethylene Substances 0.000 title abstract 7
- 239000000203 mixture Substances 0.000 claims abstract description 29
- -1 alkyl sulfonic acid Chemical compound 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims description 79
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims description 79
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 235000019394 potassium persulphate Nutrition 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 5
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 241000370738 Chlorion Species 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- HVUMOYIDDBPOLL-XGKPLOKHSA-N [2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XGKPLOKHSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000000977 initiatory effect Effects 0.000 abstract 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 230000010354 integration Effects 0.000 abstract 1
- 239000002352 surface water Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 231100000419 toxicity Toxicity 0.000 description 5
- 230000001988 toxicity Effects 0.000 description 5
- 239000011831 acidic ionic liquid Substances 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000007059 acute toxicity Effects 0.000 description 3
- 231100000403 acute toxicity Toxicity 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000006025 fining agent Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 231100001224 moderate toxicity Toxicity 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000007885 tablet disintegrant Substances 0.000 description 1
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Abstract
The invention relates to a crosslinked polyethylene pyrrolidone based catalyst and a preparation method thereof. The preparation method comprises the following steps of (1) preparation of crosslinked polyethylene pyrrolidone: mixing N-vinyl pyrrolidone, a cross-linking agent, a water-soluble initiating agent, a pore-foaming agent, a surface active agent and water, and adding the obtained mixture into a mixed solution of an oil-soluble initiating agent and an organic solvent under a stirring condition; (2) preparation of crosslinked polyethylene pyrrolidone bisexual intermediate, mixing the prepared crosslinked polyethylene pyrrolidone with alkyl sulfonic acid inner ester according to the weight ratio of 1: (1-3) so as to obtain a bisexual intermediate; (3) preparation of the crosslinked polyethylene pyrrolidone based catalyst: mixing the bisexual intermediate after drying with acid according to the weight ratio of 1:to (0.5-5) so as to obtain the crosslinked polyethylene pyrrolidone based catalyst. The preparation method provided by the invention has the advantage and beneficial effect that the integration of an ionic liquid positive ion centre and a carrier is realized.
Description
Technical field
The present invention relates to a kind of catalyst, relate in particular to a kind ofly can be recycled, the PVPP of environmental protection is catalyst based and preparation method thereof.
Background technology
Ionic liquid is made up of organic cation and inorganic/organic anion, near the organic salt being in a liquid state in room temperature or it, it has the physicochemical property of a lot of uniquenesses, as steam forces down, thermal capacity is large, ionic conductivity is high, electrochemical window is wide, ph stability is good etc.As a class novel " soft " functional material or medium, ionic liquid can be used as solvent and catalyst development and application in addition in fields such as electrochemistry, extract and separate, environment, food, biotechnology, materials.Particularly, along with the exploitation of functionalization acidic ionic liquid body, it has obtained certain application study in the field such as esterification, alkylation, has the potentiality that replace traditional industry acidic catalyst etc.China Patent No. is 200510035325.4 and 200710027283.9 to disclose respectively the application of pyrrolidonium ionic liquids in the reactions such as catalytic hydroxy acid esterifying.China Patent No. is 200610069862.5 also to mention and use ionic liquid to can be used for the synthetic of bialkyl ortho phthalate.At present, ionic-liquid catalyst exist subject matter be, under reaction temperature, it presents liquid state, viscosity own is larger, catalyst be difficult to is dispersed in reaction system completely, and then caused with catalyzed material contact area little, catalytic effect reduce problem.Particularly by these ionic liquids during for the larger system of reaction system viscosity, for example synthetic for tert-butyl catechol, after reaction finishes, catalyst and product mix, be difficult to realize catalyst and the effect that product out-phase separates, be unfavorable for recycling of catalyst.Simultaneously, prepare ionic liquid-catalyzed time, often use the nitrogen-containing compounds such as imidazoles, pyridines, pyrrolidinone compounds as cationic species, in these compounds quite a few, as: methylimidazole, pyridine, methyl pyrrolidone etc., all have certain toxicity.(the acute toxicity of imidazole type ion liquid to mouse such as Xu Hongmei, ACTA Scientiae Circumstantiae, 2011,31(2), 420-423) study the acute toxicity of imidazole type ion liquid to mouse, found that such ionic liquid is moderate toxicity, the side chain lengths section of having in its acute toxicity to mouse and imidazoles, in the time that carbon chain lengths is 14, toxicity is the strongest.Ke Ming etc. (toxicity of ionic liquid, chemical progress, 2007,19(5), 671-679) also report that different kinds of ions liquid has certain toxicity, their toxicity has larger associated with cationic core, cationic replacement side chain., there is the problem of catalyst contamination product in therefore this class ionic-liquid catalyst, will be restricted with product prepared by this class catalyst in fields such as medicine, food in practical application.
Polyvinylpyrrolidone is a kind of water-soluble high-molecular compound, and it has good physiology inertia, does not participate in human body metabolism.Meanwhile, it also has good biocompatibility, and skin, mucous membrane, eye etc. are not formed to any stimulation.Therefore, polyvinylpyrrolidone is widely used in fields such as medical and health, food processing, cosmetics, can be used as PVP iodine disinfectant, grape wine food fining agent etc., after it is crosslinked, can also be used as tablet disintegrant etc.Nitrogen-atoms in polyvinylpyrrolidone, can be as the organic cation center of ionic liquid, for the preparation of functionalization acidic ionic liquid body class catalyst.Therefore as a kind of solid polymer, polyvinylpyrrolidone both can, as the carrier of ionic liquid, can provide again the cationic species in ion liquid system, and had insoluble not molten characteristic after crosslinked.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of PVPP catalyst based and preparation method thereof, catalyst by preparation taking PVPP as carrier, realize and reduce traditional function acidic ion liquid viscosity, raising catalytic effect, and improve catalyst separation and recycle the object of effect, and possesses the feature such as green, nonhazardous.
For reaching above-mentioned purpose, a kind of PVPP of the present invention is catalyst based, composition general structure:
Wherein X is the carrier of catalyst inside, and composition is PVPP, and Y is the catalyst surface structure of matter, and both connect by carbonnitrogen bond, and in the catalyst surface structure of matter, m is 3 or 4, A
-for chlorion, bisulfate ion, p-methyl benzenesulfonic acid root or phosphotungstic acid root.
The preparation method that a kind of PVPP is catalyst based, comprise the steps: 1), the preparation of PVPP: by NVP, crosslinking agent, water soluble starter, pore-foaming agent, after surfactant and water mix, under stirring state, join in the mixed solution of oil-soluble initiator and organic solvent, its mixed proportion is that NVP accounts for 10-30 part, crosslinking agent accounts for 0.5-5 part, oil-soluble initiator and water soluble starter account for 0.1-0.5 part altogether, pore-foaming agent accounts for 0.5-2 part, surfactant accounts for 0.5-2 part, water accounts for 10-30 part, organic solvent accounts for 50-70 part, mixed system is heated to 60-80 DEG C, and polymerisation 3-6 hour, treats that polymerisation finishes, and by product isolated by filtration, water is cleaned impurity, at 60-80 DEG C of vacuum drying 5-20 hour, obtains PVPP solid, 2), the preparation of PVPP both sexes intermediate: the PVPP of above-mentioned preparation and alkyl sulfonic acid lactone are mixed in toluene solution by weight the ratio of 1:1-3,50-80 DEG C of back flow reaction 8-24 hour, obtains both sexes intermediate, the washing of the both sexes intermediate ethyl acetate obtaining or ether is removed to unreacted alkyl sulfonic acid lactone, after filtration at 60-80 DEG C of vacuum drying 2-10 hour, 3), the catalyst based preparation of PVPP: dried both sexes intermediate mixes by weight the ratio of 1:0.5-5 with acid in methyl alcohol, in 0-80 DEG C of reaction 2-30 hour, filters, the product that this step is obtained falls unreacted acid by methanol wash, and 50-80 DEG C of vacuum drying 2-10 hour, obtains PVPP catalyst based.
Described crosslinking agent is N, N'-methylene-bisacrylamide.
Described oil-soluble initiator is dibenzoyl peroxide, and water soluble starter is potassium peroxydisulfate, and the weight ratio of dibenzoyl peroxide and potassium peroxydisulfate is 1:4-19.
Described pore-foaming agent is one or both the mixture in glucose, maltose.
Described surfactant is Span80 or Span60.
Described organic solvent is normal heptane or normal octane.
Described alkyl sulfonic acid lactone is PS or Isosorbide-5-Nitrae-butyl sultone.
Described acid is hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, phosphotungstic acid, and hydrochloric acid is that concentration is 37% hydrochloric acid, and sulfuric acid is that concentration is 92% sulfuric acid.
Described both sexes intermediate has following composition general structure:
Wherein X is the carrier of both sexes intermediate inside, and composition is PVPP, and Y is both sexes intermediate surface mass structure, and both connect by carbonnitrogen bond, and in both sexes intermediate surface mass structure, m is 3 or 4.
Advantageous effect of the present invention: the present invention is the catalyst based on PVPP, below decomposition temperature (200-300 DEG C of left and right), present solid-state, and first taking nontoxic, with the PVPP of good biocompatibility as catalyst composition.PVPP both provided cationic species in this kind of catalyst, had ensured the formation of functionalization acidic ionic liquid body class catalyst, and again as the carrier of this kind of catalyst, had realized the integrated of ionic liquid cationic species and carrier.In the process of preparing PVPP, by adding oiliness initator and water-based initator, can improve the yield of PVPP, decomposition of initiator residue is nontoxic chemical substance simultaneously, has ensured the non-toxic and safe of goods; Add crosslinking agent can prepare insoluble not molten PVPP solid particle, make this kind of catalyst become heterogeneous catalysis, be conducive to and the separating of catalystic converter system; By regulating the addition of pore-foaming agent can realize the control of PVPP specific area, finally prepare high-specific surface area, heterogeneous catalyst, this is all conducive to improve the catalytic effect of catalyst.Pass through this method, preparation taking PVPP as carrier, and organic cation center taking the nitrogen-atoms in PVPP as ionic liquid, the heterogeneous functionalization acidic ionic liquid body class catalyst of preparing, solve too large its catalytic effect of reduction of conventional ion liquid catalyst viscosity, catalyst and product and be difficult to separate the problem such as can not recycle, can be widely used in the reaction such as esterification, alkylation.Simultaneously, the Main Ingredients and Appearance of this kind of catalyst is PVPP, in the process of preparation, alkyl sulfonic acid lactone carries out at its outer surface with only reacting of PVPP, this just can reduce the consumption of alkyl sulfonic acid lactone on the one hand, the Main Ingredients and Appearance that has ensured on the other hand catalyst is still PVPP, thereby guaranteed catalyst nonhazardous, environmental protection, advantage with good biocompatibility.What therefore, use prepared by this kind of method can be widely used in based on PVPP catalyst the field that biological medicine, food processing etc. are had relatively high expectations to Product Safety.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
1) preparation of PVPP: by 10gN-vinyl pyrrolidone, 0.5gN, after N'-methylene-bisacrylamide, 0.095g potassium peroxydisulfate, 0.5g glucose, 0.5gSpan80,10g water mix, under stirring state, join in the mixed solution of 0.005g dibenzoyl peroxide and 50g normal heptane; Mixed system is heated to 60 DEG C, and polymerisation 3 hours, treats that polymerisation finishes, and by product isolated by filtration, water is cleaned impurity, 60 DEG C of vacuum drying 5 hours, obtains PVPP solid;
2) preparation of PVPP both sexes intermediate: by the PVPP of above-mentioned preparation and 1,3-N-morpholinopropanesulfonic acid lactone is mixed in toluene solution by weight the ratio of 1:1,50 DEG C of back flow reaction 8 hours, obtain both sexes intermediate, the both sexes intermediate ethyl acetate washing obtaining is removed to unreacted 1,3-N-morpholinopropanesulfonic acid lactone, after filtration, 60 DEG C of vacuum drying 2 hours, both sexes intermediate composition general structure was:
, wherein m is 3;
3) preparation of PVPP catalyst: dried both sexes intermediate mixes by weight the ratio of 1:0.5 with 92% sulfuric acid in methyl alcohol, in 0 DEG C of reaction 2 hours, filters; The product that this step is obtained falls unreacted acid by methanol wash, and 50 DEG C of vacuum drying 2 hours, obtain PVPP catalyst based, and the catalyst based composition general structure of PVPP is:
Wherein m is 3, A
-for bisulfate ion.
embodiment 2
1) preparation of PVPP: by 30gN-vinyl pyrrolidone, 5gN, after N'-methylene-bisacrylamide, 0.4g potassium peroxydisulfate, 2g maltose, 2gSpan60,30g water mix, under stirring state, join in the mixed solution of 0.1g dibenzoyl peroxide and 70g normal octane; Mixed system is heated to 80 DEG C, and polymerisation 6 hours, treats that polymerisation finishes, and by product isolated by filtration, water is cleaned impurity, 80 DEG C of vacuum drying 20 hours, obtains PVPP solid;
2) preparation of PVPP both sexes intermediate: by the PVPP of above-mentioned preparation and 1,4-butyl sultone is mixed in toluene solution by weight the ratio of 1:3,80 DEG C of back flow reaction 24 hours, obtain both sexes intermediate, the both sexes intermediate ether washing obtaining is removed to unreacted 1,4-butyl sultone, after filtration, 80 DEG C of vacuum drying 10 hours, both sexes intermediate composition general structure was:
, wherein m is 4;
3) preparation of PVPP catalyst: dried both sexes intermediate mixes by weight the ratio of 1:5 with phosphotungstic acid in methyl alcohol, in 80 DEG C of reactions 30 hours, filters.The product that this step is obtained falls unreacted acid by methanol wash, and 80 DEG C of vacuum drying 10 hours, obtain PVPP catalyst based, and the catalyst based composition general structure of PVPP is:
Wherein m is 4, A
-for phosphotungstic acid root.
embodiment 3
1) preparation of PVPP: by 20gN-vinyl pyrrolidone, 3gN, after N'-methylene-bisacrylamide, 0.27g potassium peroxydisulfate, 1g glucose, 1g maltose, 1.5gSpan80,25g water mix, under stirring state, join in the mixed solution of 0.03g dibenzoyl peroxide and 60g normal heptane.Mixed system is heated to 70 DEG C, polymerisation 4 hours.Treat that polymerisation finishes, by product isolated by filtration, water is cleaned impurity, 70 DEG C of vacuum drying 10 hours, obtains PVPP solid;
2) preparation of PVPP both sexes intermediate: by the PVPP of above-mentioned preparation and 1,3-N-morpholinopropanesulfonic acid lactone is mixed in toluene solution by weight the ratio of 1:2,70 DEG C of back flow reaction 15 hours, obtain both sexes intermediate, the both sexes intermediate ethyl acetate washing obtaining is removed to unreacted 1,3-N-morpholinopropanesulfonic acid lactone, after filtration, 70 DEG C of vacuum drying 8 hours, both sexes intermediate composition general structure was:
, wherein m is 3;
3) preparation of PVPP catalyst: dried both sexes intermediate mixes by weight the ratio of 1:3 with 37% hydrochloric acid in methyl alcohol, in 30 DEG C of reactions 10 hours, filter, the product that this step is obtained falls unreacted acid by methanol wash, 60 DEG C of vacuum drying 7 hours, obtain PVPP catalyst based, the catalyst based composition general structure of PVPP is:
Wherein m is 3, A
-for chlorion.
embodiment 4
1) preparation of PVPP: by 25gN-vinyl pyrrolidone, 4gN, after N'-methylene-bisacrylamide, 0.4g potassium peroxydisulfate, 2g glucose, 1.8gSpan60,25g water mix, under stirring state, join in the mixed solution of 0.04g dibenzoyl peroxide and 65g normal octane.Mixed system is heated to 75 DEG C, and polymerisation 5 hours, treats that polymerisation finishes, and by product isolated by filtration, water is cleaned impurity, 80 DEG C of vacuum drying 15 hours, obtains PVPP solid;
2) preparation of PVPP both sexes intermediate: by the PVPP of above-mentioned preparation and 1,4-butyl sultone is mixed in toluene solution by weight the ratio of 1:2.5,75 DEG C of back flow reaction 12 hours, obtain both sexes intermediate, the both sexes intermediate ethyl acetate washing obtaining is removed to unreacted 1,4-butyl sultone, after filtration, 75 DEG C of vacuum drying 8 hours, both sexes intermediate composition general structure was:
, wherein m is 4;
3) preparation of PVPP catalyst: dried both sexes intermediate mixes by weight the ratio of 1:2.5 with p-methyl benzenesulfonic acid in methyl alcohol, in 30 DEG C of reactions 30 hours, filter, the product that this step is obtained falls unreacted acid by methanol wash, 50 DEG C of vacuum drying 2 hours, obtain PVPP catalyst based, the catalyst based composition general structure of PVPP is:
Wherein m is 4, A
-for p-methyl benzenesulfonic acid root.
embodiment 5
1) preparation of PVPP: by 15gN-vinyl pyrrolidone, 2gN, N'-methylene-bisacrylamide, 0.27g potassium peroxydisulfate, 0.5g glucose, 1.5g maltose, after 1.7gSpan80,18g water mix, under stirring state, join in the mixed solution of 0.03g dibenzoyl peroxide and 65g normal octane, mixed system is heated to 80 DEG C, polymerisation 5 hours, treat that polymerisation finishes, by product isolated by filtration, water is cleaned impurity, 80 DEG C of vacuum drying 18 hours, obtain PVPP solid;
2) preparation of PVPP both sexes intermediate: by the PVPP of above-mentioned preparation and 1,3-N-morpholinopropanesulfonic acid lactone is mixed in toluene solution by weight the ratio of 1:2.5,65 DEG C of back flow reaction 23 hours, obtain both sexes intermediate, the both sexes intermediate ethyl acetate washing obtaining is removed to unreacted 1,3-N-morpholinopropanesulfonic acid lactone, after filtration, 80 DEG C of vacuum drying 8 hours, both sexes intermediate composition general structure was:
, wherein m is 3;
3) preparation of PVPP catalyst: dried both sexes intermediate mixes by weight the ratio of 1:0.8 with 92% sulfuric acid in methyl alcohol, in 0 DEG C of reaction 24 hours, filters.The product that this step is obtained falls unreacted acid by methanol wash, and 55 DEG C of vacuum drying 3 hours, obtain PVPP catalyst based, and the catalyst based composition general structure of PVPP is:
Wherein m is 3, A
-for bisulfate ion.
Claims (10)
1. a PVPP is catalyst based, and composition general structure is:
Wherein X is the carrier of catalyst inside, and composition is PVPP, and Y is the catalyst surface structure of matter, and both connect by carbonnitrogen bond, and in the catalyst surface structure of matter, m is 3 or 4, A
-for chlorion, bisulfate ion, p-methyl benzenesulfonic acid root or phosphotungstic acid root.
2. the preparation method that PVPP is catalyst based, comprise the steps: 1), the preparation of PVPP: by NVP, crosslinking agent, water soluble starter, pore-foaming agent, after surfactant and water mix, under stirring state, join in the mixed solution of oil-soluble initiator and organic solvent, its mixed proportion is that NVP accounts for 10-30 part, crosslinking agent accounts for 0.5-5 part, oil-soluble initiator and water soluble starter account for 0.1-0.5 part altogether, pore-foaming agent accounts for 0.5-2 part, surfactant accounts for 0.5-2 part, water accounts for 10-30 part, organic solvent accounts for 50-70 part, mixed system is heated to 60-80 DEG C, and polymerisation 3-6 hour, treats that polymerisation finishes, and by product isolated by filtration, water is cleaned impurity, at 60-80 DEG C of vacuum drying 5-20 hour, obtains PVPP solid, 2), the preparation of PVPP both sexes intermediate: the PVPP of above-mentioned preparation and alkyl sulfonic acid lactone are mixed in toluene solution by weight the ratio of 1:1-3,50-80 DEG C of back flow reaction 8-24 hour, obtains both sexes intermediate, the washing of the both sexes intermediate ethyl acetate obtaining or ether is removed to unreacted alkyl sulfonic acid lactone, after filtration at 60-80 DEG C of vacuum drying 2-10 hour, 3), the catalyst based preparation of PVPP: dried both sexes intermediate mixes by weight the ratio of 1:0.5-5 with acid in methyl alcohol, in 0-80 DEG C of reaction 2-30 hour, filters, the product that this step is obtained falls unreacted acid by methanol wash, and 50-80 DEG C of vacuum drying 2-10 hour, obtains PVPP catalyst based.
3. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described crosslinking agent is N, N'-methylene-bisacrylamide.
4. the catalyst based preparation method of a kind of PVPP according to claim 2, it is characterized in that described oil-soluble initiator is dibenzoyl peroxide, water soluble starter is potassium peroxydisulfate, and the weight ratio of dibenzoyl peroxide and potassium peroxydisulfate is 1:4-19.
5. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described pore-foaming agent is one or both the mixture in glucose, maltose.
6. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described surfactant is Span80 or Span60.
7. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described organic solvent is normal heptane or normal octane.
8. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described alkyl sulfonic acid lactone is PS or Isosorbide-5-Nitrae-butyl sultone.
9. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described acid is hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, phosphotungstic acid; Described hydrochloric acid is that concentration is 37% hydrochloric acid, and described sulfuric acid is that concentration is 92% sulfuric acid.
10. the catalyst based preparation method of a kind of PVPP according to claim 2, is characterized in that described both sexes intermediate has following chemical structure of general formula:
Wherein X is the carrier of both sexes intermediate inside, and composition is polyvinylpyrrolidone, and Y is both sexes intermediate surface mass structure, and both connect by carbonnitrogen bond, and in both sexes intermediate surface mass structure, m is 3 or 4.
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