CN103965396A - Irradiation polymerization array device, application method and process for preparing polyacrylamide by irradiation method - Google Patents
Irradiation polymerization array device, application method and process for preparing polyacrylamide by irradiation method Download PDFInfo
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- CN103965396A CN103965396A CN201310032071.5A CN201310032071A CN103965396A CN 103965396 A CN103965396 A CN 103965396A CN 201310032071 A CN201310032071 A CN 201310032071A CN 103965396 A CN103965396 A CN 103965396A
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Abstract
The invention discloses an irradiation polymerization reaction array device, which can be used for simultaneously processing one irradiation polymerization reaction array. Meanwhile, the invention discloses a method for fast optimizing an irradiation polymerization process, optimized polyacrylamide irradiation polymerization process conditions and recipes are obtained, the relative molecular mass of the product is high, and the solubility is good. The irradiation polymerization reaction array device has the advantages that the structure is very simple, economical and practical effects are realized, the assembly is convenient, the operation and the control are flexible, the development speed can be greatly accelerated, and the market prospects are wide.
Description
Technical field
The present invention relates to a kind of radiation polymerization reaction array apparatus, application method, and irradiation method is prepared the Optimization Technology of High Molecular Weight Polyacrylamide.
Background technology
Radiation polymerization is that macromolecular compound is obtained in the polymerization that utilizes ionizing rays can cause organic monomer (being mainly vinyl monomer) under the effect of energetic ray (being mainly gamma-rays, rumbatron, X ray etc.).Its advantage is not add initiator, product is purer, can under normal temperature or low temperature, carry out, polymerization rate and molecular weight of product can be regulated by dosage, dose rate, reaction system is more even, can avoid local superheating and inhomogeneous reaction, thereby many performances of polymeric articles are improved.Difficult point is that traditional irradiation belongs to special industry, Working environment is special, once do an experiment, labour intensity is large, irradiation technique, formula technique tempo of development are slower, can not adapt to fossil energy worsening shortages, needs and develop the situation of new forms of energy, and current many irradiation specialty unit is basic or maintains by food, health product sterilization by irradiation, restrict the development of industry, therefore urgently development new technologies, product innovation.
Polyacrylamide (PAM) is very important synthetic complex polyelectrolyte particle, belong to typical radical polymerization mechanism, divide and can be divided into nonionic, negatively charged ion, positively charged ion and amphoteric Four types by ion characteristic, be widely used in the industries such as water treatment, papermaking, metallurgy, oil, have " all trades auxiliary agent " laudatory title.Year demand is huge, cause the attention of academia and industry member, domesticly do a large amount of work, obtain compared with much progress, but the problems such as relative molecular mass is not too high, poor stability that PAM product exists, high-end product still relies on a large amount of imports, accelerates research and development High Molecular Weight Polyacrylamide and has important theoretical and practical significance.
And the advantage of combinatorial chemistry, high-throughput techniques (HTS) can be synthesized a large amount of different samples exactly at short notice, and approach layer by layer target by quick optimization technique, in fields such as pharmacy, material, catalysis, obtain many achievements in recent years, developed very rapid.If use high-throughput techniques (HTS) and combinatorial chemistry principle, design a kind of radiation polymerization reaction array apparatus with combination high-throughput batch facility, by the tempo of development of raising radiation polymerization technology for modifying, product innovation highly significant.
Literature search at present shows, main research work concentrates on the aspects such as synthetic, biochemical synthetic, the catalysis of organic molecule, matrix material and finishing, general structure more complicated, and cost is high, complex operation, the reaction array apparatus or the parallel reaction device that have no radiation polymerization field are reported.
Summary of the invention
Design the problem that a kind of radiation polymerization reaction array apparatus with combination high-throughput batch facility need to solve is how to control temperature of reaction, how the how assurance device homogeneity of dosage field everywhere, solve the inhibition problem of some polymerization system.
The object of the invention is to be to provide a kind of radiation polymerization reaction array apparatus, and prepare high molecular weight polyacrylamide taking radiation polymerization and the application method of this device obtain the high molecular weight polyacrylamide irradiation technique of optimizing as example illustrates.
To achieve these goals, the radiation polymerization reaction array apparatus the present invention relates to, as shown in drawings, the thermostatic controller, n (n >=2) reactor or reaction chamber 9, rare gas element interface 1, vacuum interface 2, safe pressure relief device 4 and the pumping equipment 8 that comprise with closure 3, rear four are integrated on the sealing cover and casing of thermostatic controller.
The thermostatic controller of described with closure is by heating and/or temperature cooling (attached not shown in FIG.), heat exchanging fluid, sealing cover 3, gasket 5, holding bolt 6 and thermostat casing 7 form.
Individual (n >=2) reactor of described n or reaction chamber 9 can be n independently reactor, reaction cup or reaction tubes, by sealing cover 3 push down or thermostat casing 7 in the reactor frame with n array hole fix, can be also that processing is at n reaction chamber of casing closed bottom on the whole.
Brief description of the drawings
The schematic diagram of radiation polymerization reaction array apparatus of the present invention.
Embodiment
Remove or supply with heat according to reaction heat effect size and the temperature controlled needs of step of reaction, maintain predetermined temperature of reaction.In the time that reaction heat effect is large or temperature of reaction is changed significantly, in order to prevent implode or superpressure, the heat exchanging fluid in described thermostatic controller can, by pump or fan pump circulation, can also arrange heat-exchanger rig outward at constant-temperature temperature-control case if desired again; In the time that reaction heat effect is little or reaction approaches room temperature, heat exchanging fluid also can not circulate, and even in thermostatic controller, does not add separately liquid heat exchange, directly in rare gas element or air, leaves standstill polymerization; Heat exchanging fluid can be water, mixture of ice and water, icy salt solution, mixing solutions, thermal oil, rare gas element or airborne at least one.
Whole polyreaction array apparatus should should be not more than according to irradiation source the width of irradiation object transport tape by rectangle, equilateral triangle, concentric(al) circles or arc symmetric offset spread and its width.
When desk study experiment and optimization experiment, adopt suitable big or small reactor according to the volume of material.Can adopt commercially available thin-walled test tube, centrifuge tube, sanitary cup or keg to make marks, complete whole influence factor level experiments, reduce reactor cost simultaneously, save starting material simultaneously, also reduced waste and polluted; The 2-3 group of also can each experimental point simultaneously placing same proportioning repeats experiment, once completes, and reduces experimental error;
When amplification test, single reactor diameter or width and feed liquid thickness are no more than 500mm, and the larger reactor of many groups should be evenly distributed along transport tape front and back, carries out successively irradiation.
The assurance device everywhere homogeneity of dosage field reaches 90-100%, is preferably and reaches 95-100%, and best is to reach 97-100%.Dosage field should be by special messenger's periodic calibrating.
The material of reactor or reaction chamber need select ray easily to penetrate, have certain thermal conductivity, not participate in reaction, not perishable or be difficult for thin-wall stainless steel, aluminium, copper, glass, pottery, graphite, timber or the plastics of irradiation-induced degradation, preferably thin-wall stainless steel, aluminium, graphite, plastics or glass.
The described factor that affects product relative molecular mass, solvability, stability indicator, comprises polymerization process, initiator system and consumption, dose rate, total dose, monomer concentration, reactant ratio, auxiliary agent and consumption, pH value, Dilution ratio, temperature of reaction, mix and blend intensity and time, removal of impurities, goes inhibition etc.
This device can be easily carries out shock processing optimization and formula improvement to the factor of the index such as relative molecular mass, solvability, stability that affects radiation polymerization product.Specific practice is the main index according to products perfection, first carries out elementary exploration experiment, then carries out serial optimization experiment, verifies finally by expanding test.
Described influence factor comprises polymerization process, initiator system and consumption, dose rate, total dose, monomer concentration, reactant ratio, auxiliary agent and consumption, pH value, Dilution ratio, temperature of reaction, material thickness, mixture strength and time, removal of impurities, goes the factors such as inhibition.
Whether described mixture strength refer to have in single reactor and stir and stirring velocity, or whether whole reaction array apparatus is placed in frequency and the amplitude of the vibration that is fixed on irradiation object conveying belt, rotation, rocking equipment.
Described polymerization process refers to water solution polymerization process, double water-phase copolymerization method, reversed emulsion polymerization, inverse suspension polymerization etc.
Described removal of impurities refers to the clarification of various starting material, initiator, auxiliary agent.
The described inhibition of going refers to and removes the stopper that in starting material or in operating process, system may exist.Can newly distill before use or chemical method removal stopper; Air (oxygen) inhibition that in operating process, system may exist, can take away by connecing vacuum pump at vacuum port 2, or at rare gas element interface 1 logical nitrogen, argon gas or helium replacement.
In order further to set forth the application method of this radiation polymerization reaction array apparatus, the technique, formulation optimization of preparing cationic polyacrylamide taking irradiation method is below described as example.
Desk study is tested and is shown, the principal element that affects its technique comprises initiator system and consumption, dose rate, total dose, pH value, functional additive, comonomer kind and consumption, acrylamide concentration, temperature of reaction, thickness, stir speed (S.S.) or vibrational frequency amplitude and time etc.
Starting material are commercial reagent, before use all through clarification processing, go inhibition.Press orthogonal test table design calculation weigh batching, cationic monomer (MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, dimethylin vinyl cyanide) monomer is mixed in the reactor i that the prior mark of rear immigration is good (total amount is no more than 40%) with deionized water, after the reactor dress that needs quantity is sequenced, put into gasket 4, gland 3 closes.First vacuum interface 4 is connect to vacuum power, maintain the vacuum tightness 30kPa 3-5 minute that bleeds, logical N
23-5 minute valve-off, array reaction unit enters through conveying belt
60co-gamma-ray irradiation device (130,000 Curie, Hunan Inst. of Atomic Energy Application in Agriculture).
After having reacted, material in total reactor or reaction chamber is taken out, after 80 DEG C of drying and crushing, obtain white cation PAM dry powder, measure multipolymer phase relative molecular mass, solid content and dissolution time according to GB12005-89 method.
To improve relative molecular mass and processable as target, every batch of desk study experiment can be processed specific temperature, total dose, mixture strength condition, all the other parameters can all be finished the experiment of its each level conditions, and each experimental point arranges 2 groups of the effects simultaneously, and stability is fine; Then after optimizing several times, obtained very soon the processing condition of relatively optimizing, verified finally by expanding test.Greatly shortened the construction cycle of radiation polymerization, and the residual single rate of product is very low.
Specific experiment result:
Adopt
60co-gamma-ray irradiation, pH value is 5.0-7.0.
Adopting combined oxidation-reduction initiator system is ammonium persulphate: sodium bisulfite: AIBN=1: 1: 0.8, cationic monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, acrylamide: cationic monomer=1.8: 1, acrylamide monomer accounts for 20% (wt%), allyl group block polyether PAB is as large monomer stablizer, initiator amount is 600ppm, pH value is 5.2, irradiation dose is 1.5kGy, when temperature of reaction is 15 DEG C, product relative molecular mass dissolves in 1,100 ten thousand, 20min.
Adopt combined oxidation-reduction initiator system to be selected from ammonium persulphate: sodium bisulfite: 2,2-azo (2-amidine propane) dihydroxide=1: 1: 0.7, cationic monomer is acrylyl oxy-ethyl-trimethyl salmiac, dimethylin vinyl cyanide, acrylamide and cationic monomer mass ratio are 2.5, acrylamide monomer accounts for 25%, initiator amount is 300ppm, pH value is 6.2, irradiation dose is that 3.2kGy temperature of reaction is while being 25 DEG C, product relative molecular mass dissolves in 1,480 ten thousand, 31min.
Adopt combined oxidation-reduction initiator system to be selected from ammonium persulphate: sodium bisulfite: 2,2-azo (2-amidine propane) dihydroxide=1.1: 1: 1, cationic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylamide and cationic monomer mass ratio are 3.0: 1, acrylamide monomer accounts for 35%, initiator amount is 100ppm, pH value is 6.8, irradiation dose is that 4.4kGy temperature of reaction is while being 40 DEG C, product relative molecular mass dissolves in 1,650 ten thousand, 65min.
Be the explanation of the present invention having been carried out to details by specific embodiment above, but the present invention is not limited only to these embodiment, without departing from the inventive concept of the premise, can also has more other embodiments.Protection scope of the present invention is determined by the scope of claim.
Claims (9)
1. a radiation polymerization array apparatus and methods for using them, its radiation polymerization array apparatus comprises thermostatic controller, n (n >=2) reactor or reaction chamber, rare gas element interface, vacuum interface, safe pressure relief device and the pumping equipment of with closure, and rear four are integrated on the sealing cover and casing of thermostatic controller.
2. radiation polymerization array apparatus according to claim 1, is characterized in that, the thermostatic controller of described with closure is by heating and/or temperature cooling, heat exchanging fluid, sealing cover, gasket, holding bolt and thermostat casing form.
3. radiation polymerization array apparatus according to claim 2, it is characterized in that, heat exchanging fluid in described thermostatic controller can be by pump or fan pump circulation, also can not circulate, heat exchanging fluid can be water, mixture of ice and water, icy salt solution, mixing solutions, thermal oil, rare gas element or airborne at least one.
4. radiation polymerization array apparatus according to claim 1, it is characterized in that, described n (n >=2) reactor or reaction chamber can be n independently reactor, reaction cup or reaction tubes, by sealing cover push down or casing in the reactor frame with n array hole fix, can be also that processing is at n reaction chamber of casing closed bottom on the whole.
5. radiation polymerization array apparatus according to claim 1, it is characterized in that, described n (n >=2) reactor or reaction chamber array should be pressed rectangle, equilateral triangle, concentric(al) circles or arc symmetric offset spread according to irradiation source, and its width should be not more than the width of irradiation object transport tape, single reactor diameter or width and feed liquid thickness are no more than 500mm, the larger reactor of many groups should be evenly distributed along transport tape front and back, the assurance device everywhere homogeneity of dosage field reaches 90-100%, be preferably and reach 95-100%, best is to reach 97-100%.
6. radiation polymerization array apparatus according to claim 1, it is characterized in that, the material of described n (n >=2) reactor or reaction chamber array be selected from ray easily penetrate, have certain thermal conductivity, do not participate in reaction, not perishable or be difficult for thin-wall stainless steel, aluminium, copper, glass, pottery, graphite, timber or the plastics of irradiation-induced degradation, preferably thin-wall stainless steel, aluminium, graphite, plastics or glass.
7. radiation polymerization array apparatus according to claim 1, it is characterized in that, described application method can be on affecting radiation polymerization product relative molecular mass, solvability, the factor of stability indicator, comprise polymerization process, initiator system and proportioning consumption, dose rate, total dose, monomer concentration, reactant ratio, auxiliary agent and consumption, pH value, Dilution ratio, temperature of reaction, material thickness, mixture strength and time, removal of impurities, go the factors such as inhibition, according to the main index of products perfection, first carry out elementary exploration experiment, then carry out serial optimization experiment, verify finally by expanding test.
8. a technique for irradiation legal system polyacrylamide, is characterized in that, adopts
60co irradiation, adopt composite cation monomer and combined oxidation-reduction initiator system, described composite cation monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, at least 2 kinds of dimethylin vinyl cyanide, described combined oxidation-reduction initiator system is ammonium persulphate, sodium bisulfite, Diisopropyl azodicarboxylate, azo two isobutyl imidazoline salt hydrochlorates, 2, at least 3 kinds of 2-azo (2-amidine propane) dihydroxide, initiator amount is 100-600ppm, acrylamide and cationic monomer mass ratio are 1.5: 1-3.0: 1, acrylamide monomer mass fraction is 20-35%, polymerization system pH value 5.0-7.0, irradiation dose is 1.5-4.5kGy, temperature of reaction is 15-40 DEG C.
9. the technique of irradiation legal system polyacrylamide according to claim 8, it is characterized in that, described composite cation monomer is dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac, at least 2 kinds of dimethylin vinyl cyanide, described combined oxidation-reduction initiator system is ammonium persulphate, sodium bisulfite, azo two isobutyl imidazoline salt hydrochlorates, acrylamide and cationic monomer mass ratio are 2.0: 1-2.5: 1, acrylamide monomer mass fraction is 25-30%, initiator amount is 200-350ppm, pH value is 5.5-6.5, irradiation dose is 2.0-3.0kGy, temperature of reaction is 20-35 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD804653S1 (en) | 2015-06-12 | 2017-12-05 | Emd Millipore Corporation | Pressure vessel |
| US10088398B2 (en) | 2015-02-11 | 2018-10-02 | Emd Millipore Corporation | Stirred cell and method of using same |
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- 2013-01-29 CN CN201310032071.5A patent/CN103965396A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10088398B2 (en) | 2015-02-11 | 2018-10-02 | Emd Millipore Corporation | Stirred cell and method of using same |
| US10656060B2 (en) | 2015-02-11 | 2020-05-19 | Emd Millipore Corporation | Stirred cell and method of using same |
| USD804653S1 (en) | 2015-06-12 | 2017-12-05 | Emd Millipore Corporation | Pressure vessel |
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Application publication date: 20140806 |