CN101104665A - AM/NaAA/allylcyclodextrin polymer with inclusion function and synthetic method thereof - Google Patents
AM/NaAA/allylcyclodextrin polymer with inclusion function and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to an AM/NaAA/ allyl cyclodextrin polymerization with a inclusion function and a synthesis method of the AM/NaAA/ allyl cyclodextrin (CD) polymerization, which comprises three structure units of acrylamide, sodium acrylate and allyl cyclodextrin. The synthesis method is as follow: the allyl cyclodextrin is synthesized with DMSO and DMF as solvent, CD as raw material and under the temperature of 0 to 10 DEG C. Then AM is put into the allyl-beta-cyclodextrin water solution, then initiator is added to prepare AM/ allyl-beta-cyclodextrin binary copolymer under the conditions that monomer concentration is 10 to 20 percent, initiation system concentration is 40 to 80 mg/l, the temperature is 30 to 50 DEG C, and the time is for 1 to 8 hours. NaOH solution is put into the binary copolymer to hydrolyze, then the AM/NaAA/ allyl cyclodextrin polymerization is obtained. The synthesis method of the polymer is processed under the mild condition with simple operation, the product is easy to be purified and separated. The AM/NaAA/ allyl cyclodextrin polymerization can be used in the fields such as petroleum exploitation, waste water treatment, chemistry and medicine.
Description
Technical field
The present invention relates to a kind of the AM/NaAA/ allyl group cyclodextrin and synthetic method thereof with inclusion function that can be used for fields such as oil production, sewage disposal, chemical industry and medicine.
Background technology
The polyacrylamide water-soluble polymers in oil displacement process because of showing good visco-elasticity, more and more be subjected to people and pay close attention to (Ahmad Rabiee, M.Ebrahim Zeynali, andHabibollah Baharvandl.Synthesis of High MolecularWeightPartially Hydrolyzed Polyacrylamide and Investigation on itsProperties.Iranian Polymer Journal, 14 (7), 2005,603-608).This base polymer owing to can not improve interfacial tension between oil-water-rock, thereby is introduced the focus that the surfactivity base has become domestic and international scientific worker's research as oil-displacing agent in the polyacrylamide base polymer.Acrylamide with contain unsaturated link(age) cationic copolymerization (Tao Youhe. preparation method of extra high molecular cation polyacrylamide, 200510037817.7; Xu Zhenju; Xue Xiuying; Xu Guangyu. the preparation method of cationic polyacrylamide, Chinese invention patent, 200610042600.X; Jos é R.Ochoa G., Franci sca R í o, Pedro M.Synthesis of cationic flocculants based on acrylamide and[2-(acryloyloxy) ethyl] trimethylammonium chloride co polymersby semicontinuous inverse microemulsion co polymerization.PartI:Criteria for selection of comonomer formulation, e-Polymers2006,25:1-14), and with the anionic copolymerization that contains unsaturated link(age) (Wang Hongyun. high molecular weight anionic polyacrylamide preparation method, Chinese invention patent, 96115823.9) etc. the aspect report is a lot.But, have electric charge owing to contain surfactivity base acrylamide polymer, easily adsorbed by the stratum clay mineral, be restricted aspect the raising oil recovery factor.Cyclodextrin has hydrophobic inner chamber and water-soluble outer wall, and it is used and is that mainly the inclusion function forms supramolecular system, has successfully prepared many polymkeric substance, and has used in fields such as environmental purification, chemical industry and medicines.
Summary of the invention
The objective of the invention is to: AM/NaAA/ allyl group cyclodextrin and synthetic method with inclusion function are provided.This polymkeric substance has the inclusion function, and anion surfactant that not only can the inclusion long-chain also can the inclusion cats product, makes belt surface active group acrylamide polymer avoid stratum absorption.
A kind of novel water-soluble and AM/NaAA/ allyl group cyclodextrin with inclusion function comprises acrylamide (AM), sodium acrylate (NaAA), three kinds of structural units of allyl group cyclodextrin, and its structural formula is as follows:
Wherein the molar percentage of X is 0.8%, the molar percentage of Y is 0-37.2%
Accompanying drawing is the infrared analysis spectrogram.
The absworption peak ownership is such as table 1.
Table 1 infrared analysis (v stretching vibration, δ flexural vibrations)
| Go out peak position cm-1 | Ownership |
| 3447.43 | v(O-H)+v(N-H) |
| 2929.06 | v(CH 2) |
| 1655.02 | v(C＝O) |
| 1457.56 | δ(CH 2) |
| 1408 | δ (OH) plain bending |
| 1340 | δ(CCH)+δ(COH) |
| 1236 | V (CO)+δ (CCH)+δ (OOH) (O-H plain bending) |
| 1160 | v(C-O-C) |
| 1080 | v(co)+δ(COH)+v(CC) |
| 1026.22 | vCC+δ(CCH)+δ(OCH) |
| 960 | Contain α-Isosorbide-5-Nitrae-key in interior CD skeletal vibration |
| 880 | δ (CCH)+v (C-O)+v (C-C vibration) |
| 575.28 | Skeletal vibration (ring vibration) |
AM/NaAA/ pi-allyl cyclodextrin synthetic method may further comprise the steps successively:
Take dimethyl sulfoxide (DMSO) (DMSO) and DMF (DMF) mixture as reaction dissolvent, take cyclodextrin as raw material, reaction temperature is at 0-10 ℃, reaction time 1～8h, synthetic monomer pi-allyl cyclodextrin with inclusion function; In the pi-allyl cyclodextrin aqueous solution, add AM, add initiator ammonium persulfate solution, total monomer is 10-20% again, and pi-allyl cyclodextrin and AM weight ratio are 2.7: 100～13.2: 100, concentration of initiating system is 40-80mg/L, polymeric reaction temperature is at 30-50 ℃, and the reaction time is at 1～8h, inflated with nitrogen deoxygenation 20-40min, seal in the rearmounted water bath with thermostatic control and react, preparation AM/ pi-allyl cyclodextrin bipolymer. Add NaOH solution as hydrolytic reagent, its dosage is 1/125～1/10 (weight ratio) of polymer. Binary Aggregation substrate concentration 2-6%, hydrolysis temperature is 30-70 ℃, is uniformly dispersed to be placed on the reaction that is hydrolyzed in the water bath with thermostatic control, obtains the AM/NaAA/ pi-allyl cyclodextrin of 0-37.29%.
In the present invention, at first prepare allyl group cyclodextrin monomer, because cyclodextrin (CD) and allyl bromide 98 all are dissolved in DMSO, so adopt DMSO and DMF mixture as reaction solvent with inclusion function.Add NaOH in the reaction system reaction is accelerated, temperature of reaction can be between 0-10 ℃, and yield is the highest in the time of 2 ℃.Reaction times 1-48h, the 48h yield is the highest.After reaction stopped, vacuum filtration was removed DMSO and DMF, the white powder washing with acetone, and oven dry back calculated yield is 76.2%.
Take by weighing aequum allyl group cyclodextrin earlier, and the distilled water of adding aequum, after placing 40 ℃ water bath with thermostatic control to treat that the allyl group cyclodextrin dissolves fully then, the AM that adds aequum again, inflated with nitrogen deoxygenation 20-30min, add the initiator prepare then, sealing is placed in the temperature required water bath with thermostatic control down, reacts certain hour and gets final product.Initiator can adopt ammonium persulphate, Potassium Persulphate, Diisopropyl azodicarboxylate, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/tertiary amine etc.Concentration of initiating system is at 40-80mg/L, and polymeric reaction temperature is at 30-50 ℃, and better, all better in the polymer water dissolubility and the tackifying of 20% time preparation, the polymericular weight of preparation is more than 3,000,000 between 10-20% for total monomer.
Hydrolytic process mainly is to carry out in the NaOH of 40-45% solution, and hydrolysis temperature is at 50-70 ℃, and polymer concentration is about 1-4% during hydrolysis, and polymkeric substance hydrolysis degree is controlled by hydrolytic reagent consumption, concentration and hydrolysis time.The present invention obtains the AM/NaAA/ allyl group cyclodextrin ter-polymers that degree of hydrolysis is 0-37.2%.
The separation of polymkeric substance and purification are adopted to add ethanol in the polymer reaction system, and redeposition goes out to have the method for the ter-polymers of inclusion function, collect the back drying under reduced pressure and get final product.
Compared with prior art, the present invention has following beneficial effect: the preparation method of AM/NaAA/ allyl group cyclodextrin is simple and feasible, the reaction conditions gentleness, and product is easy to purify and separate.The polymkeric substance of this method preparation can organically combine with tensio-active agent, forms super molecule inclusion compound, can be used for industries such as oil production and sewage disposal.
Embodiment:
Synthesizing of example 1 allyl group cyclodextrin
5.7g (5mmol) β-CD is placed beaker, add 30mL DMSO and 50mL DMF and make it dissolving, add 2.0gNaOH then, place abundant stir about 1h on the magnetic stirring apparatus.Solution colour is deepened gradually, becomes yellow, and this moment, the pH value was 9.In the time of 0 ℃～10 ℃, slow at twice dripping bromine propylene 8.0mL, and use magnetic stirrer, and the pH value reduces to 7, and solution colour becomes faint yellow, begins to occur precipitation behind the reaction 24h.Stopped reaction after 48 hours obtains white precipitate.Vacuum filtration is removed DMSO, with the washing with acetone precipitation, gets white powder 6.10g (yield is 72.6%), the sealing cooling preservation.
Example 2 has the binary polymer of inclusion function and forms
Take by weighing the allyl group cyclodextrin monomer and distilled water places the 100mL triangular flask in the ratio of table 2, put into after 40 ℃ of waters bath with thermostatic control make it to dissolve fully, take by weighing acrylamide again and add in the solution, treat its dissolving fully, logical N
2Behind about 20min, after the ammonium persulfate solution (8mg/mL) that adding prepares in advance continues logical nitrogen 10min, 45 ℃ of reactions of sealed thermostat 8h, with the dehydrated alcohol precipitation, 40 ℃ of following vacuum-dryings promptly get polymkeric substance.
The preparation of table 2 binary polymer
| Medicine | Dosage (g) |
| The allyl group cyclodextrin | 0.157 |
| Distilled water | 25 |
| AM | 5.0 |
| NH 4S 2O 8 | 2.9×10 -3 |
It is synthetic that example 3 copolymers are hydrolyzed into ter-polymers
In the triangular flask of 250mL, routine synthetic copolymer 0.5g and 100mL distilled water in the adding, after treating that polymkeric substance dissolves fully, press table 3 and add hydrolytic reagent NaOH, react 4h down at 50 ℃, go out polymkeric substance with acetone precipitation, then 40 ℃ of vacuum-dryings, promptly get the ter-polymers of different degree of hydrolysis, specifically see Table 3.
Table 3 ter-polymers degree of hydrolysis
| NaOH(g) | Degree of hydrolysis (%) |
| 0.04 | 6.5 |
| 0.12 | 13.7 |
| 0.24 | 24.0 |
| 0.32 | 30.0 |
| 0.50 | 35.0 |
The rheological of example 4AM/NaAA/ allyl group cyclodextrin
Table 4 for degree of hydrolysis be 13.7 polymkeric substance when concentration is lower than 0.001g/mL, the viscosity of this polymkeric substance is with the variation of concentration.As can be seen from Table 4, when polymer concentration was lower than 0.0015g/mL, the relative viscosity of this polymers soln slowly rose with the increase of polymer concentration; When polymer concentration surpassed 0.0015g/ml, the viscosity of solution significantly increased, the thickening property of performance partially hydrolyzed polyacrylamide.
The rheological of table 4AM/NaAA/ allyl group cyclodextrin
| Polymer concentration (g/mL) | 0.004 | 0.0008 | 0.0012 | 0.0016 | 0.002 | 0.0024 | 0.0028 |
| Relative viscosity (mPaS) | 16.76 | 33.66 | 108.63 | 160.71 | 237.45 | 314.56 | 378.4 |
The salt resistance of example 5AM/NaAA/ allyl group cyclodextrin
Table 5 is the polymer solution viscosity of degree of hydrolysis 13.7 adds situation with inorganic salt variation.As can be seen from Table 5, same hydrolysis degree polyacrylamide is 1.6 * 10 in salinity
5In the salt solution of mg/L, the viscosity conservation rate has only 10.6%, and the viscosity conservation rate of AM/NaAA/ allyl group cyclodextrin reaches 32.5%, has improved about 3 times.
The polyacrylamide of table 5 same hydrolysis degree and AM/NaAA/ allyl group cyclodextrin salt resistance are relatively
| Polymkeric substance | η distilled water/mPaS | η salt solution/mPaS | Viscosity conservation rate % |
| Hydro-polyacrylamide | 112.45 | 11.92 | 10.6 |
| AM/NaAA/ allyl group cyclodextrin | 108.63 | 35.3 | 32.5 |
The inclusion behavior of example 6 tensio-active agents in AM/NaAA/ allyl group cyclodextrin
Table 6 is the surface tension variations of tensio-active agent palmityl trimethyl ammonium chloride in polymers soln.As can be seen from Table 6, before the tensio-active agent dosage was 0.070mmol/L, the polymers soln surface tension descended hardly.Illustrate that added tensio-active agent has entered the cyclodextrin hydrophobic cavity in the polymkeric substance.When cyclodextrin content was close in dosage and the polymkeric substance, the surface tension of polymers soln began to descend.Illustrate that cyclodextrin assembling surfactant molecule has reached saturated.
The surface tension variations of table 6 polymkeric substance when tensio-active agent difference dosage
| Dosage mmol/L | 0 | 0.035 | 0.070 | 0.10 | 0.15 | 0.4 | 0.5 |
| Polymer surfaces tension force mN/m | 71.3 | 71.2 | 69.8 | 62.3 | 50.6 | 46.7 | 41.2 |
| Aqueous solution surface tension mN/m | 73.1 | 62.3 | 51.2 | 49.4 | 45.2 | 41.8 | 40.9 |
Claims (4)
1. the AM/NaAA/ allyl group cyclodextrin that has the inclusion function comprises acrylamide, sodium acrylate, three kinds of structural units of allyl group cyclodextrin, and its structural formula is as follows:
Wherein the molar percentage of X is 0.8%, the molar percentage of Y is 0-37.2%
2. the synthetic method with inclusion function AM/NaAA/ allyl group cyclodextrin as claimed in claim 1, it is characterized in that: with dimethyl sulfoxide (DMSO) (DMSO) and N, dinethylformamide (DMF) mixture is a reaction solvent, with the cyclodextrin is raw material, temperature of reaction is at 0-10 ℃, reaction times 1～8h, synthetic monomer allyl group cyclodextrin with inclusion function; In the allyl group cyclodextrin aqueous solution, add AM, add initiator ammonium persulfate solution again, total monomer is 10-20%, and allyl group cyclodextrin and AM weight ratio are 2.7: 100～13.2: 100, concentration of initiating system is 40-80mg/L, polymeric reaction temperature is at 30-50 ℃, and the reaction times is at 1～8h, inflated with nitrogen deoxygenation 20-40min, seal in the rearmounted water bath with thermostatic control and react, preparation AM/ allyl group cyclodextrin copolymer; Add NaOH solution as hydrolytic reagent, its dosage is 1/125～1/10 of a polymkeric substance, is weight ratio, binary polymer concentration 2-6%, hydrolysis temperature is 30-70 ℃, is uniformly dispersed to be placed on the reaction that is hydrolyzed in the water bath with thermostatic control, obtains the AM/NaAA/ allyl group cyclodextrin of 0-37.29%.
3. synthetic method according to claim 2 is characterized in that: the initiator ammonium persulphate, also can use Potassium Persulphate, Diisopropyl azodicarboxylate, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/tertiary amine.
4. synthetic method according to claim 2, it is characterized in that: hydrolytic process is to carry out in 40～45% NaOH solution, hydrolysis temperature is at 50～70 ℃, and polymer concentration is 1～4% during hydrolysis, and polymkeric substance hydrolysis degree is controlled by hydrolytic reagent consumption, concentration and hydrolysis time.
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