CN105622815A - Method for preparing nano-microsphere polyacrylamide by catalyzing acrylamide to perform emulsion polymerization via cobalt porphyrin - Google Patents
Method for preparing nano-microsphere polyacrylamide by catalyzing acrylamide to perform emulsion polymerization via cobalt porphyrin Download PDFInfo
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- CN105622815A CN105622815A CN201610001873.3A CN201610001873A CN105622815A CN 105622815 A CN105622815 A CN 105622815A CN 201610001873 A CN201610001873 A CN 201610001873A CN 105622815 A CN105622815 A CN 105622815A
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- polyacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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Abstract
The invention discloses a method for preparing nano-microsphere PAM (Polyacrylamide) by catalyzing AM (Acrylamide) to perform emulsion polymerization via cobalt porphyrin. The preparation method comprises the following steps: by means of an emulsion polymerization method, dissolving the AM and m-tetrahydroxyethyl(4-methoxyphenyl) cobalt porphyrin (II) in ethyl alcohol-water and DMF-water, and forming a uniform and stable PAM emulsion under the action of a dispersing agent PVP (Polyvinylpyrrolidone), wherein the relative molecular mass can reach 4.253*105, and the grain sizes of obtained PAM microspheres are minimal 150nm. Compared with a conventional PAM emulsion preparation method, the method disclosed by the invention has the beneficial effects that an emulsifier and an initiator are not used; only a monomer, a cobalt porphyrin catalyst and a stabilizer are used in a polymerization formula, a polymerization process is simple and easy to operate, and reaction conditions are mild; by using the cobalt porphyrin as a single catalyst, the AM can be polymerized within a short time, and the catalyst is low in usage, high in efficiency and great in economic benefit.
Description
Technical field
The preparation method that the present invention relates to a kind of methacrylamide homopolymer, particularly this is aggregated under the effect of the higher Cobalt Porphyrin catalyst of a kind of activity catalysis acrylamide and is carrying out, in alcohol-water and DMF (DMF)-aqueous systems, the method that Nano microsphere polyacrylamide (PAM) is prepared in emulsion polymerization.
Background technology
Cobalt Porphyrin is the lone pair electrons in the atom N by porphyrin part center and Co2+The Metalloporphyrins that coordination is formed. Metalloporphyrin all has very wide application prospect in fields such as materials chemistry, pharmaceutical chemistry, electrochemistry, optical physics and photochemistry, analytical chemistry, organic chemistry, biomimetic chemistries. Cobalt Porphyrin is one relatively conventional in porphyrin metallic compound, and this coordination compound can be good at catalysis to be had different dissolubility and carries out controllable polymerization containing the acrylate of different functional groups and acrylamide monomers. (Zhao, the Yaguang such as its active center is single, and reaction condition is gentle, and conversion ratio and selectivity are all higher, it is possible to effective control molecular weight and molecular weight distribution, Fu; Dong, Huilong; Li, YouyongFu, XuefengLivingradicalpolymerizationofacrylatesandacrylami desmediatedbyaversatilecobaltporphyrincomplex.Chem.Commu is n.2012,48,3506-3508.) with 5-(4-(10-hydroxyl-1-certain herbaceous plants with big flowers oxygen base) phenyl)-10,15,20-tri-(2,4,6-trimethylphenyl) Cobalt Porphyrin (TMP-OH) Co as catalyst, in polarity and apolar medium, carry out synthetic use respectively more extensively and the block copolymer of the acrylate of more difficult synthesis and acrylamide monomers.
Polyacrylamide is methacrylamide homopolymer and the general designation of the various copolymers with other monomers, owing to the side base of its molecular backbone containing a large amount of amide groups, there is significantly high polarity and good reactivity, it is widely used in oil field, water process, papermaking, mining and metallurgy, weaving, building materials, agricultural and medically, it is referred to as " all trades auxiliary agent ", " omnipotent product ". Polyacrylamide is one of kind of being most widely used in water-soluble high-molecular compound. Its microsphere owing to hydrophilic is strong, non-specific adsorption, be prone to surface-functionalized and good biocompatibility, be widely used in many fields. Prepare functionalized polypropylene amide microsphere, initial conventional emulsion polymerization configures with suspension polymerization, although but the theoretical comparative maturity of its polymerization, but kinds of surface activating agent and a large amount of emulsifying agent can be used, reduce the stability of system to a certain extent, and the microsphere monodispersity acquired is poor. And current used dispersin polymerization and emulsifier-free emulsion polymerization instead of traditional method gradually, it is possible to the stability and the operation that significantly promote system are very easy, and product is generally solid particle, and polymerization is different, and the particle diameter of product is also different. Present stage, polyacrylamide microsphere according to related needs, can introduce functional groups, also have the multiple performances such as pH value response, magnetic, Thermo-sensitive simultaneously, can be widely used in multiple field. Since in recent years, related researcher is effectively composited inorganic nano-particle and polyacrylamide organic and inorganic complex microsphere, thus expanding the application in magnetics, calorifics, the every field such as optically and electrically of the functionalized polypropylene amide-type microsphere. (the Xia Yanmin such as Xia Yanmin, Song Xiaofang, Song Xiaofang, in will province etc. the preparation method of polyacrylamide microsphere and the progress [J] of application in oil field profile control blocks thereof. petrochemical industry, 2014,43 (6): 729-734.) method analyzing the various microsphere preparing polyacrylamide, and the performance of the process conditions of impact polymerization and gained PAM microsphere. And describing polyacrylamide microsphere application in blocking at oil field profile control, the polyacrylamide microsphere of different-grain diameter is applicable to the oil reservoir of different permeability. Following research should strengthen numerical simulation and MOLECULE DESIGN to reduce the polyacrylamide microsphere gap in laboratory research with on-the-spot application.
In sum, the method for nowadays prepared functionalized polypropylene amide-type microsphere is more and more abundanter, and its different performance is widely used in multiple field such as medicine, industry gradually, but its mechanism of action and evaluation means still need to perfect further
Summary of the invention
It is an object of the invention to: using alcohol-water, DMF-water as disperse medium, with m-four ethoxys (4-anisyl) Cobalt Porphyrin (II) for catalyst, when heating, cause acrylamide monomer to carry out emulsion polymerization and prepare polyacrylamide microsphere. The preparation methods adopting microemulsion polymerization method and suspension emulsion polymerization at home and abroad currently, with respect to polyacrylamide microsphere more. This type of polymerization is mostly used azo azo-compound, persulfate, persulfate/sulphite, smells hydrochlorate/sulphite etc. initiator, this type of initiator is stronger in activity, molecular weight distribution and molecular weight control to polymer are poor in the course of the polymerization process, and the molecular weight distribution obtained is wider. This emulsion is polymerized compared with conventional emulsion polymerizations technique, and this polymerization process need not add any emulsifying agent, and directly by Cobalt Porphyrin as catalyst, catalysis acrylamide monomer carries out emulsion polymerization, and polymerization technique is simply easily operated, and cost is low. Reaction condition is gentle, and polymerization time is shorter. And the polyacrylamide microsphere of synthesis nano energy stable existence in disperse medium. Obtain the narrow diameter distribution of polymer microballoon, namely obtain the polymer microballoon of uniform particle sizes. The method is not only safety but also economical rationality aborning, is increasingly becoming the main production technology of polyacrylamide.
The present invention comprises the following steps: equipped with mechanical agitator, connect nitrogen protection device four mouthfuls of round-bottomed flasks in by the acrylamide monomer of certain mol proportion, m-four ethoxys (4-anisyl) Cobalt Porphyrin, polyvinylpyrrolidone (PVP); one alcohol-water reinstating proper proportion and DMF-water make it be completely dissolved, and ensure required monomer concentration and ammonium sulfate concentrations. Connect device, put it in water bath with thermostatic control, start to pass into nitrogen, after 30 minutes, treat that water-bath temperature rises to 55 DEG C, and in the atmosphere of nitrogen sustained response 10-80min, polyreaction completely after can obtain the polyacrylamide emulsion of stable homogeneous good fluidity.
Above-mentioned Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, and the mass fraction of monomer is 15��18%, and the molar ratio monomer/Cobalt Porphyrin of monomer is (2000��8911)/1.
Above-mentioned Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, and it is 5% that stabilizer accounts for the mass percent of monomer.
Above-mentioned Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, and described temperature of reaction system should control at 55 DEG C, polymerization time 10��80min.
Above-mentioned Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, and polyacrylamide with molecular weight can reach 4.253 �� 105��
Above-mentioned Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, preparation method compared to existing polyacrylamide microsphere amphiprotic polyacrylamide, the beneficial effects of the present invention is: the polyacrylamide with molecular weight obtained is higher, can reach 4.253 �� 105, the particle diameter of the minimum polyacrylamide microsphere obtained is 150nm, in whole emulsion polymerization process, it does not have use emulsifying agent, and operating process is simple, and free from environmental pollution, based environment close friend's production method; Use single catalyst, in whole polymerization process, not only simple to operate, and reaction temperature and, catalyst amount is few, and efficiency is high, and the application of gained emulsion polymeric product is simple, stores and convenient transportation, has huge economic benefit.
Detailed description of the invention
Embodiment 1
The present embodiment adopts emulsion polymerization, equipped with mechanical agitator, connect nitrogen protection device four mouthfuls of round-bottomed flasks in add acrylamide monomer 4.0000g, catalyst 0.005g, monomer/catalyst/initiator (VA-044) mol ratio is 8911/1/0; Dispersion stabilizer polyvinylpyrrolidone (PVP) (0.2g), it is 5% that PVP accounts for the mass fraction of monomer. With with DMF/H2The DMF-water of O=7/3 makes it be completely dissolved, and to make monomer mass mark be 15wt%, connect device, put it in water bath with thermostatic control, open stirring, start to pass into nitrogen, after 30 minutes, open water bath with thermostatic control pot temperature, treat that temperature is increased to 55 DEG C, and continuously stirred in the atmosphere of nitrogen, and 60min reacts the complete homogeneous latex emulsion namely obtaining polyacrylamide amine. Can obtain Polymer Molecular Weight through test is 3.703 �� 105, the mean diameter of microsphere is 240nm.
Embodiment 2
Except the polymerization time of reaction system becomes 10min, other condition is all identical with embodiment 1, and it is 2.260 �� 10 that result obtains the relative molecular mass of polymer5, the microspherulite diameter 190nm of polymer.
Embodiment 3
Except the polymerization time of reaction system becomes 30min, other condition is all identical with embodiment 1, and it is 1.152 �� 10 that result obtains the relative molecular mass of polymer5, the microspherulite diameter 150 of polymer is nm.
Embodiment 4
Except the polymerization time of reaction system becomes 90min, other condition is all identical with embodiment 1, and it is 3.703 �� 10 that result obtains the relative molecular mass of polymer5, the microspherulite diameter 240 of polymer is nm.
Embodiment 5
The mol ratio of demonomerization/catalyst/VA-044 is 8911/1/5, and the response time is 60min, and other condition is identical with embodiment 1, and it is 2.944 �� 10 that result obtains the relative molecular mass of polymer5, polymer sticks together, and does not form emulsion.
Embodiment 6
Except the mol ratio regulating reaction system monomer and catalyst is except 5000/1, namely keeping catalyst 0.005g constant, monomer is 2.244g, PVP is 0.112g. Other condition is all identical with embodiment 1, and it is 1.135 �� 10 that result obtains the relative molecular mass of polymer5, the mean diameter of microsphere is.
Embodiment 7
Except the mol ratio regulating reaction system monomer and catalyst is except 4000/1, namely keeping catalyst 0.005g constant, monomer is 1.7954g, PVP is 0.08977g. Other condition is all identical with embodiment 1, and it is 2.162 �� 10 that result obtains the relative molecular mass of polymer5, the mean diameter of microsphere is 230nm.
Embodiment 8
Being except 20min except regulating the reaction system response time, other condition is all identical with embodiment 6, and it is 1.610 �� 10 that result obtains the relative molecular mass of polymer5, microspherulite diameter is 180nm.
Embodiment 9
Being except 40min except regulating the reaction system response time, other condition is all identical with embodiment 6, and it is 1.420 �� 10 that result obtains the relative molecular mass of polymer5, microspherulite diameter is 170nm.
Embodiment 10
Being except 80min except regulating the reaction system response time, other condition is all identical with embodiment 6, and it is 1.300 �� 10 that result obtains the relative molecular mass of polymer5, microspherulite diameter is 590nm.
Embodiment 11
Except the mol ratio regulating reaction system monomer and catalyst is except 3000/1, namely keeping catalyst 0.005g constant, monomer is 1.35g, PVP is 0.067g. Other condition is all identical with embodiment 1, and it is 2.295 �� 10 that result obtains the relative molecular mass of polymer5��
Embodiment 12
Except the mol ratio regulating reaction system monomer and catalyst is except 2000/1, other condition is all identical with embodiment 4, and it is 230nm that result obtains polymer mean diameter.
Embodiment 13
Being except 17% except regulating reaction system monomer concentration, other condition is all identical with embodiment 6, and it is 260nm that result obtains the microspherulite diameter of polymer.
Embodiment 14
Being except 18% except regulating reaction system monomer concentration, other condition is all identical with embodiment 6, and it is 280nm that result obtains the microspherulite diameter of polymer.
Embodiment 15
The present embodiment adopts emulsion polymerization, equipped with mechanical agitator, connect in four mouthfuls of round-bottomed flasks of nitrogen protection device and add acrylamide monomer 2.244g, catalyst 0.005g, the mol ratio of monomer and catalyst is 5000/1; Dispersion stabilizer polyvinylpyrrolidone (PVP) (0.112g), it is 5% that PVP accounts for the mass fraction of monomer. With EtOH: H2The alcohol-water of O=7: 3 makes it be completely dissolved, and to make monomer mass mark be 15wt%, connect device, put it in water bath with thermostatic control, open stirring, start to pass into nitrogen, after 30 minutes, open thermostat water bath, treat that temperature is increased to 55 DEG C, and continuously stirred in the atmosphere of nitrogen, and 60min reacts the complete homogeneous latex emulsion namely obtaining polyacrylamide amine. The mean diameter that can obtain polymer microballoon through test is 270nm
Embodiment 16
Except regulating reaction system EtOH: H2Outside O=5: 5, other condition is all identical with embodiment 13, and it is 650nm that result obtains the microspherulite diameter of polymer.
Embodiment 17
Except regulating reaction system EtOH: H2Outside O=6: 4, other condition is all identical with embodiment 7, and it is 280nm that result obtains the microspherulite diameter of polymer.
Embodiment 18
Except regulating reaction system DMF: H2Outside O=8: 2, other condition is all identical with embodiment 7, and result obtains the microsphere of polymer and sticks together.
Claims (3)
1. a Cobalt Porphyrin catalysis acrylamide carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, it is characterized in that: equipped with mechanical agitator, connect in four mouthfuls of round-bottomed flasks of nitrogen protection device, m-four ethoxys (4-anisyl) Cobalt Porphyrin (II) are as catalyst, by the acrylamide monomer of certain mol proportion, initiator (VA-044), the a certain proportion of alcohol-water of dispersion stabilizer kollidon, DMF-water makes it be completely dissolved, and ensure required monomer concentration, put it into again in water bath with thermostatic control, pass into nitrogen 30min, it is stirred. when water-bath temperature is increased to 55 DEG C, namely obtain the emulsion system of polyacrylamide after reaction 10��80min, it is characterised in that monomer mass mark is 15��18%, and it is 5% that polyvinylpyrrolidone accounts for the mass fraction of monomer, initiator mass fraction is 0��5%.
2. Cobalt Porphyrin catalysis acrylamide according to claim 1 carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, it is characterized in that: the mol ratio of monomer and catalyst is (2000��8911)/1, it is preferable that (4000-5000)/1; .
3. Cobalt Porphyrin catalysis acrylamide according to claim 1 carries out the method that Nano microsphere polyacrylamide is prepared in emulsion polymerization, it is characterised in that: disperse medium alcohol-water, DMF-water ratio be 5/5,6/4,7/3,8/2; Preferably 7/3.
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Cited By (3)
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| CN109627365A (en) * | 2018-12-04 | 2019-04-16 | 内蒙古工业大学 | The method of metallic cobalt complex catalysis Dispersion Polymerization of Acrylamide preparation nanosphere |
| CN114950554A (en) * | 2022-04-21 | 2022-08-30 | 浙江恒逸石化研究院有限公司 | Catalyst for preparing 2-alkyl anthraquinone by oxidizing oxygen-containing gas and application thereof |
| CN116536036A (en) * | 2023-05-09 | 2023-08-04 | 胜利油田华滨化工有限责任公司 | Development method of nano microsphere water shutoff agent |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109627365A (en) * | 2018-12-04 | 2019-04-16 | 内蒙古工业大学 | The method of metallic cobalt complex catalysis Dispersion Polymerization of Acrylamide preparation nanosphere |
| CN109627365B (en) * | 2018-12-04 | 2021-07-23 | 内蒙古工业大学 | Method for preparing nano microspheres by catalyzing acrylamide dispersion polymerization through metal cobalt complex |
| CN114950554A (en) * | 2022-04-21 | 2022-08-30 | 浙江恒逸石化研究院有限公司 | Catalyst for preparing 2-alkyl anthraquinone by oxidizing oxygen-containing gas and application thereof |
| CN116536036A (en) * | 2023-05-09 | 2023-08-04 | 胜利油田华滨化工有限责任公司 | Development method of nano microsphere water shutoff agent |
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