CN103772219B - Multi-claw cationic functional monomer - Google Patents
Multi-claw cationic functional monomer Download PDFInfo
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- CN103772219B CN103772219B CN201410032398.7A CN201410032398A CN103772219B CN 103772219 B CN103772219 B CN 103772219B CN 201410032398 A CN201410032398 A CN 201410032398A CN 103772219 B CN103772219 B CN 103772219B
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Abstract
The invention discloses a tri(dimethylamino)methyl-3-butenylether hydrochloride. The structural formula is disclosed as Formula I. The cationic functional monomer is prepared by the following steps: (1) reacting tetramethylurea with oxalyl chloride to obtain dimethylamino-N,N-dimethylchloromethyleneiminium chloride; (2) reacting dimethyl amine with the dimethylamino-N,N-dimethylchloromethyleneiminium chloride to obtain hexamethyl proguanil; (3) reacting 3-butenyl-1-ol with sodium hydroxide to obtain 3-butenyl-1-sodium alkoxide; and (4) reacting the hexamethyl proguanil and the 3-butenyl-1-sodium alkoxide to obtain the tri(dimethylamino)methyl-3-butenylether hydrochloride. The multi-claw cationic functional monomer can be used for preparing a cationic polymer; and the cationic polymer can be used as an organic flocculant, has the characteristics of favorable water solubility and the like, is convenient to use, and is especially suitable for solving the problem of low removal rate of emulsified oil and solid suspended substances in oily sewage produced by heavy oil oilfields. Besides, the flocculant has the advantages of low scum generation amount, and low water content and high oil content in scum.
Description
Technical field
The present invention relates to a kind of multijaw type cationic functional monomer.
Background technology
Increase containing poly-concentration along with in Bohai Bay Oil viscous oil recovery degree and Produced Liquid, the sewage water yield, change of water quality are large, and viscous crude density is comparatively large, acid number is higher, profit density difference is little, emulsification is serious, requires higher, be difficult to be effectively addressed with general inorganic flocculation agent to processing technological flow and medicament.Under existing sewage treatment process first grade subsides cascade filtration flow path conditions, want to improve wastewater treatment efficiency, then must screen or develop with strong points, and effective flocculation agent, to ensure condensed oil sewage process re-injection up to standard.
Organic floculant, compared with inorganic flocculating agent, has the features such as throwing amount is little, flocculation ability is strong, deoiling effect is good, the scum silica frost amount of generation is few.The Study and Development work of organic floculant is just set about by the U.S., Japan and the industrially developed country such as European as far back as the beginning of the sixties, the sewage disposal of many refinerys all uses organic floculant.There is hundreds of family in the factory of organic floculant, and its product category is various, trade names are complete, have wide range of applications, and the synthesis of organic polymer coargulator has become the important subject of field of fine chemical.Current domestic industry flocculation agent is based on cationic polyacrylamide, molecular weight is higher, from hundreds of thousands of to millions of, belong to low electric charge, high molecular type flocculation agent, flocculating effect is good, but dissolution rate is comparatively slow in water, and general merchandise is sold with pulvis and emulsion, use more difficult, need to solve more special administration apparatus.
Summary of the invention
The object of this invention is to provide a kind of multijaw type cationic functional monomer, cationic polymers prepared by this function monomer, can be used as organic floculant and use.
A kind of multijaw type cationic functional monomer provided by the present invention is three (dimethylamino) methyl-3-butenyl ether hydrochloride, its structural formula such as formula shown in I,
The cationic functional of multijaw type shown in formula I monomer is prepared by following method:
(1) tetramethyl-urea and oxalyl chloride carry out being obtained by reacting dimethylin-N, and N-dimethyl chloride is for chlorine alkene imonium;
(2) dimethyl amine and described dimethylin-N, N-dimethyl chloride carry out being obtained by reacting hexamethyl chloroguanide for chlorine alkene imonium;
(3) 3-butene-1-ol and sodium hydroxide carry out being obtained by reacting 3-butene-1-ol sodium;
(4) described hexamethyl chloroguanide and described 3-butene-1-ol sodium carry out being obtained by reacting cationic monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride.
In above-mentioned preparation method, in step (4), the mol ratio of described hexamethyl chloroguanide and described 3-butene-1-ol sodium can be 1:1;
The temperature of described reaction can be 10 ~ 25 DEG C, and the time can be 3 ~ 6 hours.
Multijaw type cationic functional monomer provided by the invention can be used for the cationic polymers shown in preparation formula II,
In formula I, when m is number-average degree of polymerization, being the natural number between 2888 ~ 4129, when n is number-average degree of polymerization, is the natural number between 7684 ~ 27280;
When m is weight average degree of polymerization, being the natural number between 4393 ~ 6397, when n is weight average degree of polymerization, is the natural number of 11686 ~ 44601.
The cationic degree of above-mentioned cationic polymers can be 10% ~ 30%, and intrinsic viscosity can be 855.9 ~ 983.4mL/g, and number-average molecular weight can be 1.484 × 10
6~ 2.931 × 10
6g/mol, weight-average molecular weight can be 2.257 × 10
6~ 4.792 × 10
6g/mol;
The molecular weight distribution of described cationic polymers can be 1.5 ~ 1.7, specifically can be 1.521,1.549 or 1.635.
The cationic degree of above-mentioned cationic polymers specifically can be 10.07%, and intrinsic viscosity specifically can be 855.9mL/g, and number-average molecular weight specifically can be 2.931 × 10
6g/mol, weight-average molecular weight specifically can be 4.792 × 10
6g/mol.
The cationic degree of above-mentioned cationic polymers specifically can be 18.76%, and intrinsic viscosity specifically can be 930.8mL/g, and number-average molecular weight specifically can be 2.612 × 10
6g/mol, weight-average molecular weight specifically can be 4.046 × 10
6g/mol.
The cationic degree of above-mentioned cationic polymers specifically can be 27.32%, and intrinsic viscosity specifically can be 983.4mL/g, and number-average molecular weight specifically can be 1.484 × 10
6g/mol, weight-average molecular weight specifically can be 2.257 × 10
6g/mol.
When multijaw type cationic functional monomer provided by the invention prepares cationic polymers shown in above-mentioned formula II, can carry out according to the method comprised the steps:
Under emulsifying agent and initiator existent condition, namely acrylamide and described three (dimethylamino) methyl-3-butenyl ether hydrochloride obtain the cationic polymers shown in formula II through inverse emulsion polymerization.
In above-mentioned preparation method, the mol ratio of described acrylamide and described three (dimethylamino) methyl-3-butenyl ether hydrochloride can be 63 ~ 85:15 ~ 37, specifically can be 75:25,63:37 or 85:15.
In above-mentioned preparation method, the solvent of described inverse emulsion polymerization reaction is the mixture of water and organic solvent, and described water can be deionized water, and described organic solvent can be hexanaphthene, and the mass ratio of described water and described organic solvent is 1:2.7;
Total add-on of described acrylamide and described three (dimethylamino) methyl-3-butenyl ether hydrochloride is 44% of the aqueous phase quality that described inverse emulsion polymerization reacts, and described aqueous phase is the mixture of described water, described acrylamide and described three (dimethylamino) methyl-3-butenyl ether hydrochloride.
In above-mentioned preparation method, described emulsifying agent can be sorbitol anhydride oleate (Span-80) and/or sorbitan monooleate Soxylat A 25-7 (Tween-80);
The add-on of described emulsifying agent can be 10% of the oil phase quality of described inverse emulsion polymerization reaction, and described oil phase is the mixture of described organic solvent and described emulsifying agent.
In above-mentioned preparation method, described initiator can be Potassium Persulphate/sodium bisulfite redox system, and the mass ratio of Potassium Persulphate and sodium bisulfite can be 3:1;
The add-on of described initiator can be 0.2% of described acrylamide and described three (dimethylamino) methyl-3-butenyl ether hydrochloride total mass.
In above-mentioned preparation method, the temperature of described inverse emulsion polymerization reaction can be 45 DEG C, and the time can be 4 hours.
In above-mentioned preparation method, described phase emulsion polyreaction is carried out in atmosphere of inert gases, and described rare gas element is preferably nitrogen.
Multijaw type cationic functional monomer provided by the invention can be used for preparing a kind of cationic polymers, this cationic polymers can be used as a kind of organic floculant, there is good water solubility, the feature such as easy to use, be specially adapted to solve due to oil in water emulsion in the oily(waste)water of viscous crude field output, problem that admittedly outstanding thing clearance is low.In addition, it is few that this flocculation agent also has scum silica frost growing amount, the advantage that in scum silica frost, water ratio is low, oil length is high.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of three (dimethylamino) methyl-3-butenyl ether hydrochloride.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of cationic polymers MCF-1.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of cationic polymers MCF-2.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of cationic polymers MCF-3.
Fig. 5 is the GPC spectrogram of cationic polymers MCF-1 ~ MCF-3.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
The preparation of embodiment 1, multijaw cationic functional monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride
(1) synthesis of hexamethyl chloroguanide
1. dimethylin-N, N-dimethyl chloride is for the synthesis of chlorine alkene imonium (C5H12Cl2N2,171.07g/mol)
Reaction equation is as follows:
Tetramethyl-urea (Chemical Reagent Co., Ltd., Sinopharm Group, the C of 1mol is added in two to 500mL there-necked flasks
5h
12n
2o, 116.16g/mol), the chloroform (Jinan chemical reagent work) of 200mL, under nitrogen protection, in reaction system, drip 2.1mol oxalyl chloride (Chemical Reagent Co., Ltd., Sinopharm Group, C
2h
2cl
2, 126.93g/mol) stir, oil bath reflux, react after 4 hours, be cooled to room temperature, underpressure distillation goes out concentrated solution, adds the anhydrous diethyl ether (Tianjin Bo Di Chemical Co., Ltd.) of 200mL, be cooled to 0 DEG C, the solid phase prod anhydrous diethyl ether of suction filtration gained repeatedly washs, vacuum-drying 24 hours, obtains white powder dimethylin-N, N-dimethyl chloride for chlorine alkene imonium, productive rate 83.9%.
2. hexamethyl chloroguanide (C
7h
18clN
3, 179.69g/mol) synthesis
Reaction equation is as follows:
In 250mL there-necked flask, add the dimethylin-N of 0.5mol, N-dimethyl chloride is for chlorine alkene imonium (C
5h
12cl
2n
2, 171.07g/mol), dimethyl amine (Chemical Reagent Co., Ltd., Sinopharm Group, the C of 0.6mol
2h
7n, 45.08g/mol) and 100mL anhydrous acetonitrile (Chemical Reagent Co., Ltd., Sinopharm Group, C
2h
3n, 41.05g/mol), after stirring at room temperature reacts 1 day, underpressure distillation obtains flaxen crude product, with anhydrous isopropyl alcohol (Tianjin chemical reagent one factory) washing, obtains white powdery solids, productive rate 78.6%.
(2) 3-butene-1-ol sodium (C
4h
7naO, 94.09g/mol) synthesis
Reaction equation is as follows:
3-butene-1-ol (Wuhan Fengfan Chemical Co., Ltd., the C of 2.1mol is added in the there-necked flask of 250mL
4h
8o, 72.11g/mol), the toluene (Chemical Reagent Co., Ltd., Sinopharm Group) of 150mL and the sodium hydroxide (Chemical Reagent Co., Ltd., Sinopharm Group, NaOH, 40.00g/mol) of 2.0mol, reflux divides water, goes out the water that reaction to the greatest extent generates.Reaction system concentrating under reduced pressure removing toluene, then with the unreacted 3-butene-1-ol of anhydrous diethyl ether washing removing, obtains white solid, yield 95.2%.
(3) three (dimethylamino) methyl-3-butenyl ether hydrochloride (C
11h
28cl
3n
3o, 324.72g/mol) synthesis
Reaction equation is as follows:
Under nitrogen protection, to the 3-butene-1-ol sodium (C of 0.5mol in the there-necked flask of 250mL
4h
7naO, 94.09g/mol), the ethylene dichloride (Ke Miou chemical reagent development centre, Tianjin) of 150mL and the hexamethyl chloroguanide (C of 0.5mol
7h
18clN
3179.69g/mol), stirring at room temperature reacts 6 hours, after reaction solution suction filtration, concentrating under reduced pressure is except desolventizing, and then add dehydrated alcohol (Tianjin chemical reagent two factory) suction filtration removing insolubles again, the crude product that underpressure distillation obtains, add tetrahydrofuran (THF) (Tianjin Bo Di Chemical Co., Ltd.) again, add concentrated hydrochloric acid (Yantai three and chemical reagent company limited) salify, suction filtration obtains white solid, vacuum-drying obtains monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride, and yield is 85.5%.
The hydrogen nuclear magnetic resonance spectrogram of three (dimethylamino) methyl-3-butenyl ether hydrochloride of above-mentioned preparation as shown in Figure 1.
Analysis chart 1 is known, and structure is correct, obtains subject monomers.
Embodiment 2, monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride is utilized to prepare cationic polymers MCF-1
Reaction equation is as follows:
By 22g acrylamide (Chemical Reagent Co., Ltd., Sinopharm Group) (C
3h
5nO, 71.08g/mol) be dissolved in 50mL deionized water obtain monomer solution with 18g tri-(dimethylamino) methyl-3-butenyl ether hydrochloride monomer, then monomer solution is added to containing 8.25g Span-80(Jiangsu Hai'an Petrochemical Plant) and 6.75g Tween-80(Jiangsu Hai'an Petrochemical Plant) 135g hexanaphthene (Chemical Reagent Co., Ltd., Sinopharm Group) in, at the emulsified 15min of high-shear homogeneous emulsifying machine, obtain emulsion.Above-mentioned emulsion is added in the 500mL four-necked bottle that agitator, thermometer, dropping funnel, ventpipe be housed, after stirring lower letting nitrogen in and deoxidizing 20min, drip the aqueous solution 10mL containing 0.06g Potassium Persulphate (Chemical Reagent Co., Ltd., Sinopharm Group) and 0.02g sodium bisulfite (Chemical Reagent Co., Ltd., Sinopharm Group), controlling temperature of reaction is 45 DEG C, stopped reaction after constant temperature 4h.Then add acetone precipitation, decompress filter, and with washing with acetone 2 times, suction filtration obtains granular product, vacuum-drying 12h at 50 DEG C.
Product prepared by the present embodiment represents with MCF-1, and productive rate is 90.23%, and cationic degree is 10.07%.
As shown in Figure 2, analyze this figure known, structure is correct for the hydrogen nuclear magnetic resonance spectrogram of product MCF-1.
The mensuration of intrinsic viscosity is carried out with reference to National Standard of the People's Republic of China GB12005.1-1989 polyacrylamide For Intrinsic Viscosity Measurements method, and recording intrinsic viscosity is 983.4mL/g.
As shown in Figure 5, GPC characterization result and polymkeric substance form as shown in table 1 the GPC spectrogram of product MCF-1.
Embodiment 3, monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride is utilized to prepare cationic polymers MCF-2
16g acrylamide and 24g tri-(dimethylamino) methyl-3-butenyl ether hydrochloride monomer are dissolved in 50mL deionized water and obtain monomer solution, then monomer solution is added in the 135g hexanaphthene containing 8.25g Span-80 and 6.75gTween-80, at the emulsified 10min of high-shear homogeneous emulsifying machine, obtain emulsion.Above-mentioned emulsion is added in the 500mL four-necked bottle that agitator, thermometer, dropping funnel, ventpipe be housed, after stirring lower letting nitrogen in and deoxidizing 20min, drip the aqueous solution 10mL containing 0.06g Potassium Persulphate and 0.02g sodium bisulfite, controlling temperature of reaction is 45 DEG C, stopped reaction after constant temperature 4h.Add acetone precipitation, decompress filter, washing with acetone 2 times, suction filtration obtains Powdered or granular product, vacuum-drying 12h at 50 DEG C.
Product prepared by the present embodiment represents with MCF-2, and productive rate is 86.01%, and cationic degree is 18.76%.
As shown in Figure 3, analyze this figure known, structure is correct for the hydrogen nuclear magnetic resonance spectrogram of product MCF-2.
The mensuration of intrinsic viscosity is carried out with reference to National Standard of the People's Republic of China GB12005.1-1989 polyacrylamide For Intrinsic Viscosity Measurements method, and recording intrinsic viscosity is 930.8mL/g.
As shown in Figure 5, GPC characterization result and polymkeric substance form as shown in table 1 the GPC spectrogram of product MCF-2.
Embodiment 4, monomer three (dimethylamino) methyl-3-butenyl ether hydrochloride is utilized to prepare cationic polymers MCF-3
11g acrylamide and 29g tri-(dimethylamino) methyl-3-butenyl ether hydrochloride monomer are dissolved in 50mL deionized water and obtain monomer solution, then monomer solution is added in the 135g hexanaphthene containing 8.25g Span-80 and 6.75gTween-80, at the emulsified 15min of high-shear homogeneous emulsifying machine, obtain emulsion.Above-mentioned emulsion is added in the 500mL four-necked bottle that agitator, thermometer, dropping funnel, ventpipe be housed, after stirring lower letting nitrogen in and deoxidizing 20min, drip the aqueous solution 10mL containing 0.06g Potassium Persulphate and 0.02g sodium bisulfite, controlling temperature of reaction is 45 DEG C, stopped reaction after constant temperature 4h.Add acetone precipitation, decompress filter, washing with acetone 2 times, suction filtration obtains Powdered or granular product, vacuum-drying 12h at 50 DEG C.
Product prepared by the present embodiment represents with MCF-3, and productive rate is 81.95%, and cationic degree is 27.32%.
As shown in Figure 4, analyze this figure known, structure is correct for the hydrogen nuclear magnetic resonance spectrogram of product MCF-3.
The mensuration of intrinsic viscosity is carried out with reference to National Standard of the People's Republic of China GB12005.1-1989 polyacrylamide For Intrinsic Viscosity Measurements method, and recording intrinsic viscosity is 855.9mL/g.
As shown in Figure 5, GPC characterization result and polymkeric substance form as shown in table 1 the GPC spectrogram of product MCF-3.
The GPC characterization result of table 1 cationic polymers and polymkeric substance composition
(4) flocculation agent waste water dam
Weigh in the balance and get a certain amount of cationic polymers MCF-1-MCF-3(and be accurate to 0.01g), be placed in volumetric flask, shake up after being settled to scale, preparing massfraction is respectively the solution of 1% ~ 10%.The Wastewater Sample prepared is added, preheating 15min under 60 DEG C of waters bath with thermostatic control in the tool plug graduated centrifuge tube of 100 milliliters.The flocculant solution that quantitatively prepares is drawn in tool plug graduated centrifuge tube with microsyringe, put back to again after dandle 20 times in water bath with thermostatic control and leave standstill 15min, to measure before and after cationic polymers process oleaginousness and solid suspension content in water, result is as shown in table 3, and in table, the consumption of flocculation agent represents the amount of the flocculation agent added in every L Wastewater Sample.
Result shows, because oil-in-water drips with suspended solid all electronegative, along with the raising of cationic degree consumption, the flocculation ability of product increases, and oil removing and the effect except suspended solid strengthen.
Oleaginousness before and after table 3 sewage disposal and solid suspension content
The cationic polymers prepared by multijaw type cationic functional monomer of the present invention has introducing that is hydrophobic and the multijaw type function monomer of high steric hindrance effect simultaneously, hydrophobicity makes the interaction of cationic polymers and oil droplet and suspended solids stronger on the one hand, on the other hand, high steric hindrance effect makes the chain rigidity of this polymkeric substance strengthen, structure in water is more unfolded, and bridging action increases.Above-mentioned reason enables cationic polymers and the non-polar component effect in sewage, strengthens the deoiling effect of polymkeric substance, thus enhances the application of flocculation agent in oily water treatment.
Claims (1)
1. three (dimethylamino) methyl-3-butenyl ether hydrochloride, its structural formula such as formula shown in I,
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| US4506081A (en) * | 1982-09-02 | 1985-03-19 | Buckman Laboratories, Inc. | Polymeric quaternary ammonium compounds and their uses |
| US4898684A (en) * | 1983-10-26 | 1990-02-06 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| FR2758825A1 (en) * | 1997-01-24 | 1998-07-31 | Atochem Elf Sa | AQUEOUS DISPERSION BASED ON WATER-SOLUBLE POLYMERS |
| CN101397351A (en) * | 2007-09-30 | 2009-04-01 | 中国科学院理化技术研究所 | Hydrophobic modified cationic polyacrylamide, preparation method and use thereof |
| CN101575132B (en) * | 2009-06-11 | 2011-04-20 | 吴江市恒茂电子科技有限公司 | Dication polyacrylamide flocculating agent and preparation method thereof |
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