CN1884323A - Cross-linked anion polymer containing tetramethylguanidine cation and its preparation method and uses - Google Patents
Cross-linked anion polymer containing tetramethylguanidine cation and its preparation method and uses Download PDFInfo
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- CN1884323A CN1884323A CN 200610050828 CN200610050828A CN1884323A CN 1884323 A CN1884323 A CN 1884323A CN 200610050828 CN200610050828 CN 200610050828 CN 200610050828 A CN200610050828 A CN 200610050828A CN 1884323 A CN1884323 A CN 1884323A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- -1 tetramethylguanidine cation Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 14
- 150000001450 anions Chemical class 0.000 title abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 60
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 23
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 125000000129 anionic group Chemical group 0.000 claims abstract description 14
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 81
- 125000002091 cationic group Chemical group 0.000 claims description 39
- 229920006318 anionic polymer Polymers 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000002612 dispersion medium Substances 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 238000007046 ethoxylation reaction Methods 0.000 claims description 4
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- GZBSIABKXVPBFY-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GZBSIABKXVPBFY-UHFFFAOYSA-N 0.000 claims description 2
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound 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 group CCCCCCCCCCCCCCCCCC(=O)OCC(O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XGKPLOKHSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000007686 potassium Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 21
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000000126 substance Substances 0.000 description 27
- 230000009102 absorption Effects 0.000 description 19
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 15
- 229920001577 copolymer Polymers 0.000 description 15
- 229920000554 ionomer Polymers 0.000 description 15
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 12
- SAXJVKAVLPPFLI-UHFFFAOYSA-N prop-2-enoic acid;1,1,3,3-tetramethylguanidine Chemical compound OC(=O)C=C.CN(C)C(=N)N(C)C SAXJVKAVLPPFLI-UHFFFAOYSA-N 0.000 description 9
- 239000003643 water by type Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 235000003599 food sweetener Nutrition 0.000 description 7
- 125000003010 ionic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003765 sweetening agent Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 231100000987 absorbed dose Toxicity 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000012267 brine Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 229920000831 ionic polymer Polymers 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KPZGDUQLAJIKQI-UHFFFAOYSA-N CN(C(N(C)C)=N)C.C(C(=C)C)(=O)O Chemical compound CN(C(N(C)C)=N)C.C(C(=C)C)(=O)O KPZGDUQLAJIKQI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229920000867 polyelectrolyte Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NNJPGOLRFBJNIW-HNNXBMFYSA-N (-)-demecolcine Chemical compound C1=C(OC)C(=O)C=C2[C@@H](NC)CCC3=CC(OC)=C(OC)C(OC)=C3C2=C1 NNJPGOLRFBJNIW-HNNXBMFYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010795 gaseous waste Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a cross-linked anion polymer containing tetramethylguanidine cation and it's preparing method and usage. The macrochain of said polymer comprises anionic construction unit and cross-linking construction unit, the molar ratio of which is 90: 10- 99.5: 0.5; the anion in anionic construction unit is carboxylate anion, contra-ion is 1, 1, 3, 3- tetramethylguanidine cation (tetramethylguanidine cation for abbreviation). The polymer is prepared through copolymerization of ionic vinyl monomer and cross-linking monomer with reversed phase suspending free radical, and the ionic vinyl monomer is got through neutralization of vinyl monomer containing carboxy group with 1, 1, 3, 3- tetramethylguanidine (tetramethylguanidine for abbreviation). Said polymer is porous particle, and can be used as desulfurizer to absorb sulfur dioxide, the absorption is characterized by high selectivity, large absorption capacity and rapid speed; said polymer can be reused. The method is characterized by simple process, soft condition, short reacting time and high productivity.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of cationic cross-linking type anionic polymer of tetramethyl guanidine and preparation method and purposes of containing.
Background technology
Ionomer (or claim ionic polymer) is meant linearity or the cross-linked polymer that contains negatively charged ion or positively charged ion and gegenion (positively charged ion or negatively charged ion) thereof on the side chain of polymkeric substance or the end group.Different according to the ionic group that directly links to each other with the main polymer chain skeleton, Ionomer is divided into anionic polymer and cation type polymer.With the ionic group that the main polymer chain skeleton directly links to each other is anionic, is called anionic polymer, and its gegenion is a positively charged ion; With the ionic group that the main polymer chain skeleton directly links to each other is cationic, is called cation type polymer, and its gegenion is a negatively charged ion.Different according to the content of ionic group and purposes, Ionomer can be divided into ionomer (or from aggressiveness), polyelectrolyte, super strength water absorbent, ionogenic surfactant etc. again.Ionomer only contains a small amount of ionic group, and generally its molar content is not more than 15%, can be used as coating, printing ink, dental prosthetic material, information material, environment-friendly materials, increase-volume material, also can be used for membrane technique.Polyelectrolyte contains a large amount of ionic groups, thereby has ionic conductivity, is applicable to materials such as electrochemical appliance such as battery, electrical condenser, transmitter.Super strength water absorbent has superpower water-retaining capacity and water retention capacity because the existence of a large amount of hydrophilic and ionic groups is arranged, and is widely used as water-absorbing-retaining materials such as diaper, soil water-retaining.Ionogenic surfactant has the surface tension of reduction, promotes functions such as dispersion, solubilising, emulsification, is widely used in fields such as chemical industry, food, makeup.In Ionomer, generally speaking, anionic polymer is used more extensive than cation type polymer.
The purposes of Ionomer depends on the side chain of its polymkeric substance or the yin, yang ionic constitutional features on the end group.But existing Ionomer still can not satisfy the constantly progressive various new requirement that it is proposed of rapid economic development and technology on structure and performance.For example, more and more serious topsoil requires waste gas such as industrial gaseous waste, vehicle exhaust must carry out processings such as desulfurization to drop to below the permissible value with the pollutent elimination or with its concentration before discharging; Although the developing history that the gas sweetening technology was had an appointment 70 years, imperfection still up to the present, need exploitation new sulfurous gas is absorbed the renewable solid desulfurating agent with high selectivity, efficient and speed; Polymkeric substance is because of characteristics such as it has that structure can design, performance easy-regulating, synthetic simple, mechanical property height, be well suited for being used for sweetening agent, as " environmental science and technology " (1999, the 1st phase, 23-24 page or leaf) reported the porosu solid sweetening agent that a kind of crosslinked polystyrene polymer obtains after sintering processes; And Ionomer may more be applicable to gas absorbent because of easier introducing functional groups, still, existing Ionomer (CN 1680306A, CN1047601C) in, positively charged ion is generally Na
+, K
+, Mg
+, Ca
+, Fe
+Deng metallic cation, NH
4 +Ion and organic quaternary ammonium cation, negatively charged ion is generally carboxylate anion, azochlorosulfonate acid anion, does not see that these Ionomers can absorb gas, be used for gas absorption and isolating report.
Recent years, discover an organic micromolecule ionic compound---ionic liquid can dissolve or absorbing carbon dioxide (J.Am.Chem.Soc.2004,126,5300-5308; J.Chem.Eng.Data 2003,48,746-749; J.Am.Chem.Soc.2002,124,926-927; Ind.Eng.Chem.Res.2004,43,6855-6860), ethene (Ind.Eng.Chem.Res.2004,43,3049-3054; J.Phys.Chem.B2002,106,7315-7320), ethane (J.Phys.Chem.B2002.
106,7315-7320), sulfurous gas (Angew.Chem.Int.Ed.2004,43,2415-2417) wait gas, this will provide a new approach for the absorption and the isolation of purified (as desulfurization) of gas, also will for this small molecular ion compound of forming by the yin, yang ion of ionic liquid except as finding new purposes a kind of " green " solvent and the catalyzer.The research report is arranged, contain 1,1,3,3-tetramethyl guanidine cationic ionic liquid-1,1,3,3-tetramethyl guanidine lactic acid salt (Angew.Chem.Int.Ed., 43:2415-2417,2004) and alcoholamine carboxylate ion liquid (Chinese invention patent publication number CN 1698928A) can substitute traditional liquid amine desulfurizer and be used for wet desulphurization, and can avoid that amine desulfurizer is volatile, the deficiency of easy loss.But the own inherent shortcoming of viscosity that ionic liquid self is very high and wet desulphurization has limited its large-scale application.External existing miaow side class ionic liquid is introduced in the polymer architecture obtains report (Macromolecules, 2005, the 38:2037-2039 that Ionomer is used for carbon dioxide absorption; Journal of Polymer Science:Part A:Polymer Chemistry2005,43:1432-1443), still, this polymkeric substance is a kind of linear cationic polymkeric substance, synthetic cost height, and can only absorbing carbon dioxide, sulfurous gas there is not receptivity.Domestic literature (" environmental science and technology ", 1999, the 1st phase, the 23-24 page or leaf) although the porosu solid sweetening agent that the crosslinked polystyrene polymer of report obtains after sintering processes has the sulfurous gas receptivity, but it is non-ionic polyalcohol rather than Ionomer, and it whether reproducible utilization does not appear in the newspapers yet.Sum up prior art, Shang Weijian has pair sulfurous gas to have the line style of absorptive function or the report of cross-linking type ionic polymer, therefore, preparation has novel structure, absorbs the function of sulfurous gas, the novel cross-linking type ionic polymer of enough mechanical strength, is that Ionomer material and Application Areas thereof have technical problem to be solved.
Summary of the invention
The purpose of this invention is to provide a kind of cationic cross-linking type anionic polymer of tetramethyl guanidine and preparation method and purposes of containing.
Contain the cationic cross-linking type anionic polymer of tetramethyl guanidine, its macromolecular chain is made of anionic structural unit and crosslinking structure unit, it is characterized in that the negatively charged ion in the anionic structural unit is selected from the negatively charged ion shown in structural formula (1)～(3), wherein, and R
1Be selected from hydrogen atom (H) or methyl (CH
3), gegenion is 1,1,3,3-tetramethyl guanidine positively charged ion (being called for short the tetramethyl guanidine positively charged ion);
Structural formula (1) structural formula (2) structural formula (3)
The crosslinking structure unit has the general structure shown in the structural formula (4),
Structural formula (4)
Wherein, n is 2～4 integer, R
1Be selected from hydrogen atom (H) or methyl (CH
3), R
2Be selected from the group shown in structural formula (5)～(8),
Wherein, m is 1～6 integer,
Structural formula (5)
Structural formula (6)
Structural formula (7)
Structural formula (8).
The preparation method's step that contains the cationic cross-linking type anionic polymer of tetramethyl guanidine is as follows:
1) carboxylic vinyl monomer or its aqueous solution and 1,1,3,3-tetramethyl guanidine (abbreviation tetramethyl guanidine) or its aqueous solution carried out neutralization reaction 0.5～8 hour by the amount of mol ratios such as reactive functionality under 0 ℃～60 ℃ temperature, obtaining positively charged ion is 1,1,3, the cationic ionic vinyl monomer of 3-tetramethyl guanidine or its aqueous solution;
2) in dispersion medium, add the dispersion agent that accounts for dispersion medium weight 0.5%～3%wt%, stir and make its dissolving; In ionic vinyl monomer or its aqueous solution, add cross-linking monomer, and adding suitable quantity of water, the concentration of the mixed monomer solution of gained is allocated scope to 40wt%～70wt%, add the radical initiator of weight again, stir for 0.05～5wt% of mixed total monomer weight; Under agitation begin in the dispersion medium that is dissolved with dispersion agent, to drip mixed monomer solution then, form the water-in-oil inverse suspension system, under 20 ℃～80 ℃, carry out the copolyreaction of anti-phase suspension radical crosslinking, 2～8 hours reaction times, obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer of 3-tetramethyl guanidine particle suspension liquid;
3) with step 2) the cross-linking type anionic polymer particle suspension liquid that obtains carries out settlement separate, with methanol wash polymer beads after-filtration, vacuum-drying then, obtaining porous prilled gegenion is 1,1,3, the cationic cross-linking type anionic polymer of 3-tetramethyl guanidine promptly contains the cationic cross-linking type anionic polymer of tetramethyl guanidine.
Contain the desulfurization that the cationic cross-linking type anionic polymer of tetramethyl guanidine is used to contain the gas of sulfurous gas, or as water-retaining agent.
Absorption has highly selective, high absorptive capacity, high uptake rate to the cationic cross-linking type anionic polymer of tetramethyl guanidine that contains among the present invention to sulfurous gas, and sulfurous gas takes off to be inhaled and polymer recycled convenience, and the polymkeric substance after the regeneration can repeatedly recycle.In addition, be 1,1 with gegenion, 3, the cationic line style anionic polymer of 3-tetramethyl guanidine is compared, and this cross-linking type anionic polymer is owing to have crosslinking structure, mechanical property is good, is used for can not taking place when sulfurous gas absorbs the phenomenon of volumetric shrinkage and distortion, uses more convenient; Be porous prilled, bigger to the absorptive capacity of sulfurous gas.
During containing the cationic cross-linking type anionic polymer of tetramethyl guanidine and be used for water-retaining agent among the present invention, water regain is big, and water-retentivity is strong.
Among the present invention contain that the cationic cross-linking type anionic polymer of tetramethyl guanidine preparation technology is simple, mild condition, the reaction times is short, cost is low, productive rate is high, is fit to suitability for industrialized production.
Description of drawings
Fig. 1 is a vinylformic acid 1,1,3, the infrared spectrum of 3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer (polymer A);
Fig. 2 is a methacrylic acid 1,1,3, the infrared spectrum of 3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer (polymer B);
Fig. 3 is a vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer (polymer A) to the absorption of sulfurous gas with take off suction.
Embodiment
Still do not possess the function that absorbs sulfurous gas at above-mentioned existing Ionomer, can not be used for sulfurous gas absorbs and isolating technical problem, the invention provides a kind of gegenion is 1,1,3, the cationic cross-linking type anionic polymer of 3-tetramethyl guanidine, this polymkeric substance is porous prilled, surface-area is big, and contain can with 1,1,3 of sulfurous gas generation chemical bonding, 3-tetramethyl guanidine positively charged ion, thereby sulfurous gas had strong chemical absorption, physical adsorption and physical absorption effect can be used as a kind of solid-state sweetening agent that absorbs sulfurous gas from the gas that contains sulfurous gas, sulfurous gas are absorbed have high selectivity, absorptive capacity and speed, sulfurous gas takes off to be inhaled and polymer recycled convenience, and the polymkeric substance after the regeneration can repeatedly recycle.
Among the present invention, the mol ratio of anionic structural unit and cross-linking type structural unit is 90: 10～99.5: 0.5.Carboxylic vinyl monomer is selected from vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid.
Described cross-linking monomer is selected from the cross-linking monomer shown in the structural formula (9),
Structural formula (9)
Wherein, n is 2～4 integer, R
1Be selected from hydrogen atom (H) or methyl (CH
3), R
2Be selected from the group shown in structural formula (5)～(8), wherein, m is 0～6 integer,
Structural formula (5)
Structural formula (6)
Structural formula (7)
Structural formula (8).
Described cross-linking monomer is selected from N, N-methylene diacrylamine, glycol diacrylate, ethylene glycol dimethacrylate, glycol ether diacrylate, glycol ether dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylation tetramethylol methane tetraacrylate or ethoxylation tetramethylolmethane tetramethyl-acrylate.
The mol ratio of ionic vinyl monomer and cross-linking monomer is 90: 10～99.5: 0.5.
Dispersion medium is selected from hexanaphthene, hexane, heptane, sherwood oil, and the volume ratio of dispersion medium and monomer solution is 10: 1～1.5: 1; Described dispersion agent is selected from Span60, Span80 or Tween80.
Radical initiator is selected from Potassium Persulphate, ammonium persulphate, Potassium Persulphate-S-WAT, Potassium Persulphate-sodium bisulfite, Potassium Persulphate-Sodium Pyrosulfite, ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite or ammonium persulphate-Sodium Pyrosulfite.
The consumption of radical initiator is 0.05～5wt% of total monomer weight, preferred 0.1～2wt%.
Containing the cationic cross-linking type anionic polymer of tetramethyl guanidine is that 0 ℃～90 ℃ and pressure are under the condition of 0.1MPa～1MPa in temperature, make the gas stream that contains sulfurous gas through this cross-linking type anionic polymer, polymkeric substance optionally absorbs sulfurous gas, then, being 60 ℃～140 ℃ in temperature is under the condition of 0.1MPa～1Pa with pressure, the sulfurous gas that absorbs taken off from polymkeric substance suck out, absorbing and take off the circulation of suction process carries out, the polymkeric substance recycle, thereby isolate sulfurous gas, purifying gas.
When being used for purifying and containing the gas of sulfurous gas, preferred condition is, selectivity absorbs sulfurous gas in 20 ℃～60 ℃ temperature range and the pressure range of 0.1MPa～1MPa, in the pressure range of 80 ℃～120 ℃ temperature ranges and 1000Pa～10Pa, the sulfurous gas that is absorbed taken off suck out the polymkeric substance recycle.
Among the present invention, the described cationic cross-linking type anionic polymer of tetramethyl guanidine that contains can selectivity absorb sulfurous gas from the gas that contains sulfurous gas, gases such as oxygen, hydrogen, carbonic acid gas, nitrogen are not had obvious absorption.Absorptive capacity to sulfurous gas is big, and every gram sweetening agent can absorb 0.67 gram sulfurous gas at most, absorbs/takes off through one and inhale circulation, and recyclable at most 0.54 restrains sulfurous gas.Absorption rate to sulfurous gas is fast, can reach when absorbing pure sulfur dioxide gas to absorb and take off the suction balance in 1～2 hour.
Among the present invention, the described cationic cross-linking type anionic polymer of tetramethyl guanidine that contains can repeatedly recycle after inhaling regeneration through taking off, to the absorption of sulfurous gas and take off absorption can no considerable change after circulation is inhaled in a plurality of absorptions/take off.
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the situation of affiliated aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
Accurately weighing 1,1,3,3-tetramethyl guanidine 7.50 grams (65 mmole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing vinylformic acid 4.63 restrains (65 mmole), and adds 9 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed ice-water bath (0 ℃), and start stirring, beginning dropwise addition of acrylic acid solution.Dropwise in 15 minutes, continue under the room temperature to stir 7.5 hours, obtain ionic vinyl monomer vinylformic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To vinylformic acid 1,1,3, add cross-linking monomer N,N methylene bis acrylamide 0.2464 gram (1.6 mmole) and deionized water 4 grams in the 3-tetramethyl guanidine salt brine solution, form mixed monomer solution, concentration is 50wt%; Add again radical initiator Potassium Persulphate 0.1237 gram (for the monomer total mass 1%), stir and make its dissolving, place constant pressure funnel.
The 60mL hexanaphthene is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and, being warming up to 60 ℃ to wherein adding dispersion agent Span 600.4195 grams, stir speed (S.S.) is 500rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Drip mixed monomer solution then, drip off in 10 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, reaction times is 6 hours, and obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer-vinylformic acid 1,1,3 of 3-tetramethyl guanidine, 3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer particle suspension liquid.
Stop to stir, particles settling gets off, the hexanaphthene on upper strata is toppled over out, and the particle that obtains with methanol wash filters the back and vacuumizes under the condition dry at 80 ℃ then, obtain porous prilled vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt/N, N-methylene-bisacrylamide cross-linking copolymer is designated as polymer A.Its infrared spectra is seen Fig. 1.
Embodiment 2
Accurately weighing 1,1,3,3-tetramethyl guanidine 12.86 grams (0.11 mole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing methacrylic acid 9.46 restrains (0.11 mole), and adds 16 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed 60 ℃ of water-baths, and start stirring, beginning dropwise addition of acrylic acid solution.Dropwise in 15 minutes, continue under the room temperature to stir 15 minutes, obtain ionic vinyl monomer methacrylic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To methacrylic acid 1,1,3, add cross-linking monomer N,N methylene bis acrylamide 1.88 grams (12 mmole) and 20 gram deionized waters in the 3-tetramethyl guanidine salt brine solution, form mixed monomer solution, concentration is 40wt%; Add radical initiator ammonium persulphate 0.0122 gram again, stir and make its dissolving, place constant pressure funnel.
The 90mL hexanaphthene is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and, being warming up to 70 ℃ to wherein adding dispersion agent Span 600.14 grams, stir speed (S.S.) is 550rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Begin to drip mixed monomer solution then, dripped off in 15 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, the reaction times is 8 hours, obtains methacrylic acid 1,1,3,3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer particle suspension liquid.
Stop to stir, particles settling gets off, the hexanaphthene on upper strata is toppled over out, and the particle that obtains with methanol wash filters the back and vacuumizes under the condition dry at 80 ℃ then, obtain porous prilled methacrylic acid 1,1,3,3-tetramethyl-guanidinesalt/N, N-methylene-bisacrylamide cross-linking copolymer is designated as polymer B.Its INFRARED SPECTRUM is seen Fig. 2.
Embodiment 3
Accurately weighing 1,1,3,3-tetramethyl guanidine 7.70 grams (66 mmole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing vinylformic acid 2.4 restrains (33 mmole) and toxilic acids 1.914 (16.5 mmole), and adds 12.26 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed 30 ℃ of water-baths, and start stirring, the beginning dropwise addition of acrylic acid and the toxilic acid aqueous solution.Dropwise in 15 minutes, continue under the room temperature to stir 30 minutes, obtain ionic vinyl monomer vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt and toxilic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt and toxilic acid 1,1,3 add cross-linking monomer N,N methylene bis acrylamide 0.2486 gram (1.6 mmole) in the aqueous solution of 3-tetramethyl-guanidinesalt, form mixed monomer solution, and concentration is 50wt%; Add again radical initiator Potassium Persulphate 0.1252 gram (for the monomer total mass 1%), stir and make its dissolving, place constant pressure funnel.
The 80mL hexanaphthene is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and, being warming up to 50 ℃ to wherein adding dispersion agent Span 600.7334 grams, stir speed (S.S.) is 550rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Drip mixed monomer solution then, drip off in 10 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, the reaction times is 7 hours, and obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer-vinylformic acid 1 of 3-tetramethyl guanidine, 1,3,3-tetramethyl-guanidinesalt/toxilic acid 1,1,3, the cross-linking copolymer particle suspension liquid of 3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide.
Stop to stir, particles settling gets off, and the hexanaphthene on upper strata is toppled over out, the particle that obtains with methanol wash filters the back and vacuumizes drying under the condition at 80 ℃ then, obtains porous prilled vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt/toxilic acid 1,1,3,3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer is designated as polymkeric substance C.
Embodiment 4
Accurately weighing 1,1,3,3-tetramethyl guanidine 7.50 grams (65 mmole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing vinylformic acid 4.63 restrains (65 mmole), and adds 8.2 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed 30 ℃ of water-baths, and start stirring, beginning dropwise addition of acrylic acid solution.Dropwise in 15 minutes, continue under the room temperature to stir 3 hours, obtain ionic vinyl monomer vinylformic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To vinylformic acid 1,1,3, add cross-linking monomer glycol ether diacrylate 0.276 gram (1.32 mmole) in the 3-tetramethyl guanidine salt brine solution, form mixed monomer solution, concentration is 60wt%; Add again radical initiator Potassium Persulphate 0.1237 gram (for the monomer total mass 1%) and sodium bisulfite 0.15 gram, stirring makes its dissolving, places constant pressure funnel.
The 60mL hexanaphthene is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and restrain to wherein adding dispersion agent Span600.4 gram and Tween800.5,20 ℃ of constant temperature, stir speed (S.S.) is 500rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Drip mixed monomer solution then, drip off in 10 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, reaction times is 8 hours, obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer-vinylformic acid 1 of 3-tetramethyl guanidine, 1,3,3-tetramethyl-guanidinesalt/glycol ether diacrylate cross-linking copolymer particle suspension liquid.
Stop to stir, particles settling gets off, the hexanaphthene on upper strata is toppled over out, the particle that obtains with methanol wash filters the back and vacuumizes drying under the condition at 80 ℃ then, obtains porous prilled vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt/glycol ether diacrylate cross-linking copolymer is designated as polymkeric substance D.
Embodiment 5
Accurately weighing 1,1,3,3-tetramethyl guanidine 7.70 grams (66 mmole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing vinylformic acid 2.4 restrains (33 mmole) and methylene-succinic acids 2.145 (16.5 mmole), and adds 5.5 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed ice-water bath (0 ℃), and start stirring, the beginning dropwise addition of acrylic acid and the methylene-succinic acid aqueous solution.Dropwise in 15 minutes, continue under the room temperature to stir 1 hour, obtain ionic vinyl monomer vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt and methylene-succinic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt and methylene-succinic acid 1,1,3 add 142 milligrams of ethoxylated trimethylolpropane triacrylates of cross-linking monomer (0.33 mmole) in the aqueous solution of 3-tetramethyl-guanidinesalt, form mixed monomer solution, and concentration is 70wt%; Add radical initiator Potassium Persulphate 0.62 gram again, stir and make its dissolving, place constant pressure funnel.
The 60mL hexanaphthene is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and to wherein adding dispersion agent Span601.4 gram, 60 ℃ of constant temperature, stir speed (S.S.) is 500rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Drip mixed monomer solution then, drip off in 10 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, the reaction times is 8 hours, and obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer-vinylformic acid 1 of 3-tetramethyl guanidine, 1,3,3-tetramethyl-guanidinesalt/methylene-succinic acid 1,1,3,3-tetramethyl-guanidinesalt/ethoxylated trimethylolpropane triacrylate cross-linking copolymer particle suspension liquid.
Stop to stir, particles settling gets off, and the hexanaphthene on upper strata is toppled over out, the particle that obtains with methanol wash then, filter the back and vacuumize drying under the condition, obtain porous prilled vinylformic acid 1,1 at 80 ℃, 3,3-tetramethyl-guanidinesalt/methylene-succinic acid 1,1,3,3-tetramethyl-guanidinesalt/ethoxylated trimethylolpropane triacrylate cross-linking copolymer is designated as polymkeric substance E.
Embodiment 6
Accurately weighing 1,1,3,3-tetramethyl guanidine 7.50 grams (65 mmole) join in three mouthfuls of round-bottomed flasks of band prolong and mechanical stirring device.Accurately weighing vinylformic acid 4.63 restrains (65 mmole), and adds 12.8 gram deionized waters, places in the constant pressure funnel.There-necked flask is placed ice-water bath (0 ℃), and start stirring, beginning dropwise addition of acrylic acid solution.Dropwise in 15 minutes, continue under the room temperature to stir 2 hours, obtain ionic vinyl monomer vinylformic acid 1,1,3, the aqueous solution of 3-tetramethyl-guanidinesalt.
To vinylformic acid 1,1,3, add cross-linking monomer N,N methylene bis acrylamide 0.2464 gram (1.6 mmole) in the 3-tetramethyl guanidine salt brine solution, form mixed monomer solution, concentration is 50wt%; Add radical initiator Potassium Persulphate 0.2476 gram again, stir and make its dissolving, place constant pressure funnel.
The 180mL sherwood oil is joined in the four-hole round-bottomed flask of band prolong, constant pressure funnel and mechanical stirring device, and, being warming up to 80 ℃ to wherein adding dispersion agent Span800.54 gram, stir speed (S.S.) is 500rpm, it is dissolved in the dispersion medium, logical nitrogen 0.5 hour.Drip mixed monomer solution then, drip off in 10 minutes, form the water-in-oil inverse suspension system, carry out the copolyreaction of anti-phase suspension radical crosslinking, reaction times is 2 hours, and obtaining gegenion is 1,1,3, the cationic cross-linking type anionic polymer-vinylformic acid 1,1,3 of 3-tetramethyl guanidine, 3-tetramethyl-guanidinesalt/N,N methylene bis acrylamide cross-linking copolymer particle suspension liquid.
Stop to stir, particles settling gets off, the hexanaphthene on upper strata is toppled over out, and the particle that obtains with methanol wash filters the back and vacuumizes under the condition dry at 80 ℃ then, obtain porous prilled vinylformic acid 1,1,3,3-tetramethyl-guanidinesalt/N, N-methylene-bisacrylamide cross-linking copolymer is designated as polymkeric substance F.
Embodiment 7
Polymer A 5.6 grams of embodiment 1 gained are joined in the U type pipe that a diameter is 12mm, and U type pipe is placed 50 ℃ of waters bath with thermostatic control.With the speed of 80mL/min, the pressure of 0.1MPa feeds sulfur dioxide gas to U type pipe.The weight of weighing U type pipe at regular intervals no longer changes up to the weight of U type pipe.Reach balance after about 2 hours, finally absorb sulfurous gas 2.56 grams, be equivalent to every gram polymkeric substance sweetening agent and absorb sulfurous gas 0.45 gram.Then, be warming up to 90 ℃ and vacuumize, the weight of weighing U type pipe at regular intervals, the weight of U type pipe no longer changes after 2.5 hours.The polymkeric substance sweetening agent also contains sulfurous gas 1.02 grams when reaching balance, removes sulfurous gas 1.54 grams.The polymkeric substance that removes sulfurous gas is inhaled sulphur/desulphurization circulating (see figure 4) again under these conditions, absorbs and takes off energy-absorbing and try hard to keep and hold constantly, and each every gram polymkeric substance that circulates removes sulfurous gas 0.28 gram.
Embodiment 8
According to the method for embodiment 7, under 20 ℃, normal pressure, carry out the absorption experiment of sulfurous gas, nitrogen, oxygen, hydrogen, carbonic acid gas, the mixed gas of nitrogen/hydrogen with polymer A.Polymer A reaches 0.58 gram sulfurous gas/gram polymkeric substance to the absorbed dose of sulfurous gas, and to the absorbed dose of other gases such as the mixed gas of nitrogen, carbonic acid gas, nitrogen/hydrogen, oxygen all seldom, be respectively 0.021,0.012,0.005,0.005 gram sulfurous gas/gram polymkeric substance, show sulfurous gas absorbed to have extraordinary selectivity, simultaneously also explanation with the absorption experiment result of sulfur dioxide gas can inference in the absorption experiment of the mixed gas that contains sulfurous gas.
Embodiment 9
Under the condition identical with embodiment 7, be that 20% the mixed gas of nitrogen/sulfurous gas carries out the gas absorption experiment to polymer A with content of sulfur dioxide, reached absorption equilibrium in 6 hours, every gram polymkeric substance absorbs sulfurous gas 0.43 gram; 2.5 hour reach and to take off the suction balance, each circularly removing sulfurous gas 0.26 gram sees Table 1.Contain sulfurous gas mixed gas absorbed dose and take off the absorbed dose of suction amount and pure sulfur dioxide gas and take off the suction amount and slightly descend, the content of sulfur dioxide step-down slows down uptake rate in the gas because of mixing.
Embodiment 10～14
According to the identical method of embodiment 7, under the conditions shown in Table 1, the polymer B～F that makes among the embodiment 2～6 absorbed and take off inhale experiment, all can absorb sulfurous gas, polymkeric substance can be recycled, and the amount of each circularly removing sulfurous gas sees Table 1.
Table 1 contains 1,1,3, and the cationic cross-linking type anionic polymer of 3-tetramethyl guanidine is to gas absorption and the experimental result of taking off suction
| Embodiment | Polymkeric substance | Gas | Acceptance condition (℃/MPa) | Take off the suction condition (℃/mmHg) | Absorbed dose (gram/gram) | Each circulation SO 2Take off suction amount (gram/gram) |
| 7 8 8 8 8 8 9 10 11 12 13 14 | Polymer A polymer A polymer A polymer A polymer A polymer A polymer A polymer B polymer C polymer D polymer E polymer F | 2: 8 sulfur dioxide/2: 8 sulfur dioxide/nitrogen of nitrogen sulfur dioxide sulfur dioxide sulfur dioxide sulfur dioxide of 1: 1 nitrogen/hydrogen of sulfur dioxide sulfur dioxide nitrogen oxygen carbon dioxide | 50/0.1 20/0.1 20/0.1 20/0.1 20/0.1 20/0.1 50/0.1 50/0.1 0/0.1 90/0.1 50/0.1 20/1 | 90/80 / / / / / 90/80 90/80 90/80 140/80 130/0.0075 60/760 | 0.45 0.58 0.021 0.005 0.012 0.005 0.43 0.4 0.67 0.23 0.48 0.59 | 0.28 / / / / / 0.26 0.25 0.54 0.18 0.32 0.38 |
Embodiment 15
Polymer A 0.074 gram, the B0.089 of embodiment 1 gained are restrained in the beaker that adds two 100 milliliters respectively, add 50 ml deionized water, polymer A, B be water absorption and swelling gradually, and volume increases, reached the suction balance in about 3 hours, absorb multiplying power and be respectively 78ml/g, 74ml/g.
Claims (10)
1, a kind of cationic cross-linking type anionic polymer of tetramethyl guanidine that contains, its macromolecular chain is made of anionic structural unit and crosslinking structure unit, it is characterized in that the negatively charged ion in the anionic structural unit is selected from the negatively charged ion shown in structural formula (1)～(3), wherein, R
1Be selected from hydrogen atom (H) or methyl (CH
3), gegenion is 1,1,3,3-tetramethyl guanidine positively charged ion;
Structural formula (1) structural formula (2) structural formula (3)
The crosslinking structure unit has the general structure shown in the structural formula (4),
Structural formula (4)
Wherein, n is 2～4 integer, R
1Be selected from hydrogen atom (H) or methyl (CH
3), R
2Be selected from the group shown in structural formula (5)～(8), wherein, m is 1～6 integer,
Structural formula (5)
Structural formula (6)
Structural formula (7)
Structural formula (8).
2, a kind of cationic cross-linking type anionic polymer of tetramethyl guanidine that contains according to claim 1 is characterized in that the mol ratio of anionic structural unit and cross-linking type structural unit is 90: 10～99.5: 0.5.
3, a kind of a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine as claimed in claim 1, step is as follows:
1) carboxylic vinyl monomer or its aqueous solution and 1,1,3,3-tetramethyl guanidine or its aqueous solution carried out neutralization reaction 0.5～8 hour by the amount of mol ratios such as reactive functionality under 0 ℃～60 ℃ temperature, obtaining positively charged ion is 1,1,3, the cationic ionic vinyl monomer of 3-tetramethyl guanidine or its aqueous solution;
2) in dispersion medium, add the dispersion agent that accounts for dispersion medium weight 0.5%～3%wt%, stir and make its dissolving; In ionic vinyl monomer or its aqueous solution, add cross-linking monomer, and adding suitable quantity of water, the concentration of the mixed monomer solution of gained is allocated scope to 40wt%～70wt%, add the radical initiator of weight again, stir for 0.05～5wt% of mixed total monomer weight; Under agitation begin in the dispersion medium that is dissolved with dispersion agent, to drip mixed monomer solution then, form the water-in-oil inverse suspension system, under 20 ℃～80 ℃, carry out the copolyreaction of anti-phase suspension radical crosslinking, in 2～8 hours reaction times, obtain containing the cationic cross-linking type anionic polymer of tetramethyl guanidine particle suspension liquid;
3) with step 2) the cross-linking type anionic polymer particle suspension liquid that obtains carries out settlement separately, and with methanol wash polymer beads after-filtration, vacuum-drying then obtains containing the cationic cross-linking type anionic polymer of tetramethyl guanidine.
4, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3 is characterized in that described carboxylic vinyl monomer is selected from vinylformic acid, methacrylic acid, toxilic acid, fumaric acid or methylene-succinic acid.
5, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3 is characterized in that, described cross-linking monomer is selected from the cross-linking monomer shown in the structural formula (9),
Structural formula (9)
Wherein, n is 2～4 integer, R
1Be selected from hydrogen atom (H) or methyl (CH
3), R
2Be selected from the group shown in structural formula (5)～(8), wherein, m is 0～6 integer,
Structural formula (7)
Structural formula (8).
6, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3, it is characterized in that, described cross-linking monomer is selected from N, N-methylene diacrylamine, glycol diacrylate, ethylene glycol dimethacrylate, glycol ether diacrylate, glycol ether dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylation tetramethylol methane tetraacrylate or ethoxylation tetramethylolmethane tetramethyl-acrylate.
7, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3 is characterized in that, the mol ratio of described ionic vinyl monomer and cross-linking monomer is 90: 10～99.5: 0.5.
8, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3, it is characterized in that, described dispersion medium is selected from hexanaphthene, hexane, heptane, sherwood oil, and the volume ratio of dispersion medium and monomer solution is 10: 1～1.5: 1; Described dispersion agent is selected from Span60, Span80 or Tween80.
9, a kind of preparation method who contains the cationic cross-linking type anionic polymer of tetramethyl guanidine according to claim 3, it is characterized in that described radical initiator is selected from Potassium Persulphate, ammonium persulphate, Potassium Persulphate-S-WAT, Potassium Persulphate-sodium bisulfite, Potassium Persulphate-Sodium Pyrosulfite, ammonium persulphate-S-WAT, ammonium persulfate-sodium bisulfite or ammonium persulphate-Sodium Pyrosulfite.
10, a kind of purposes that contains the cationic cross-linking type anionic polymer of tetramethyl guanidine as claimed in claim 1 is characterized in that, is used to contain the desulfurization of the gas of sulfurous gas, or as water-retaining agent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979128A (en) * | 2010-09-09 | 2011-02-23 | 王传良 | Tetramethyl guanidine hydroxy-acid salt composite desulfurizing agent and preparation method thereof |
| CN102657999A (en) * | 2012-05-31 | 2012-09-12 | 北京化工大学 | Poly (tetramethylguandium acrylate) aqueous solution desulfurization agent and preparation method thereof |
| CN106111086A (en) * | 2016-06-22 | 2016-11-16 | 江南大学 | A kind of absorption Pd2+ion-type polymeric sorbent of metal ion and preparation method thereof |
| CN109999608A (en) * | 2018-01-05 | 2019-07-12 | 浙江大学 | The method of sulfur dioxide is removed in depth in a kind of gaseous mixture |
| CN115322078A (en) * | 2022-08-19 | 2022-11-11 | 浙江巨圣氟化学有限公司 | Preparation method of perfluoro-n-propyl vinyl ether |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312032C (en) * | 2004-06-08 | 2007-04-25 | 中国科学院化学研究所 | Prepn process of composite material of metal or metal oxide and carbon nanotube |
| CN1709553A (en) * | 2005-06-02 | 2005-12-21 | 中国科学院过程工程研究所 | Amino acid ion liquid for acidic gas absorption |
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2006
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101979128A (en) * | 2010-09-09 | 2011-02-23 | 王传良 | Tetramethyl guanidine hydroxy-acid salt composite desulfurizing agent and preparation method thereof |
| CN101979128B (en) * | 2010-09-09 | 2013-01-30 | 王传良 | Tetramethyl guanidine hydroxy-acid salt composite desulfurizing agent and preparation method thereof |
| CN102657999A (en) * | 2012-05-31 | 2012-09-12 | 北京化工大学 | Poly (tetramethylguandium acrylate) aqueous solution desulfurization agent and preparation method thereof |
| CN106111086A (en) * | 2016-06-22 | 2016-11-16 | 江南大学 | A kind of absorption Pd2+ion-type polymeric sorbent of metal ion and preparation method thereof |
| CN106111086B (en) * | 2016-06-22 | 2018-06-08 | 江南大学 | A kind of absorption Pd2+Ionic polymeric sorbent of metal ion and preparation method thereof |
| CN109999608A (en) * | 2018-01-05 | 2019-07-12 | 浙江大学 | The method of sulfur dioxide is removed in depth in a kind of gaseous mixture |
| CN109999608B (en) * | 2018-01-05 | 2020-12-15 | 浙江大学 | Method for deeply removing sulfur dioxide from mixed gas |
| CN115322078A (en) * | 2022-08-19 | 2022-11-11 | 浙江巨圣氟化学有限公司 | Preparation method of perfluoro-n-propyl vinyl ether |
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| CN100366651C (en) | 2008-02-06 |
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