CN1237082C - AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method - Google Patents
AM/NaAA/AHAC trielement hylrophobic association polymer and its synthesis method Download PDFInfo
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- CN1237082C CN1237082C CN 03135507 CN03135507A CN1237082C CN 1237082 C CN1237082 C CN 1237082C CN 03135507 CN03135507 CN 03135507 CN 03135507 A CN03135507 A CN 03135507A CN 1237082 C CN1237082 C CN 1237082C
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Abstract
The present invention relates to a non-ion ternary hydrophobic association polymer and a synthesis method thereof. The AM/NaAA/AHAC ternary hydrophobic association polymer contains three structure units, acrylamide, sodium acrylate and allyl hexadecanoic alkylamine. The synthesis method of the present invention comprises that (1) ethanol as solvent is synthesized with allyl chloride and hexadecanoic alkylamine as raw materials at 40 to 70 DEG C; (2) AM and an initiating agent are added in the AHAC water solution, the total concentration of the monomer is from 10 to 20 %, the concentration of an initiation system is from 40 to 120 mg/L, the temperature is from 40 to 60 DEG C, the time is from 2 to 8 hours, and an AM/AHAC binary copolymer is prepared; (3) NaOH solution is added into the binary copolymer to be hydrolyzed to obtain the AM/NaAA/AHAC ternary polymer. The polymer of the present invention has the advantages of good viscosity increase properties and salt resistance properties, and the synthesis method of the present invention has the advantages of simple, convenient and feasible operation, mild conditions and high yield, and furthermore, the polymer of the present invention is easy to purify and separate.
Description
Technical field
The present invention relates to a kind of non-ionic type ternary hydrophobic associated polymer and synthetic method thereof.
Background technology
In order to improve viscosity in aqueous solution, usually in water, add water-soluble polymers (" water-soluble polymer ", Yan Rui Xuan work, Chemical Industry Press, 1999.6), polymkeric substance commonly used at present mainly is polyacrylamide series product, some biological polymer (as xanthan gum) and derivative thereof etc.These traditional polymkeric substance mainly rely on the stretching, extension of polymer chain and physical entanglement to come tackify.Wherein, partially hydrolyzed polyacrylamide (HPAM) thus cause the stretching, extension of main chain to have higher viscosity mainly due to the electrostatic repulsion between carboxyl.Soltion viscosity increases along with the increase of polymericular weight, so the oil field often uses high-molecular weight HPAM, but high-molecular weight HPAM easily degraded under the high shear forces of pumping and pipe stream.Molecular weight is high more, and shear degradation is more violent, and in addition, the viscosity of HPAM solution sharply descends with the raising of salt concn or salinity.This is that shielding effect owing to mineral ion makes the repulsion between carboxyl reduce to cause polymer chain to shrink.Carboxyl on the HPAM is prone in the presence of the divalent ion of high density and is separated in addition.In order to improve the performance of these aspects of polyacrylamide, U.S.Pat.No.3,247,171 once attempted improving temperature resistance and anti-shearing by crosslinked polymer, but the result is not ideal.U.S.Pat.No.3,984,333 have reported with a kind of block polymer that contains hydrophobic segment and hydrophilic segment simultaneously to have anti-shear performance preferably as tackifier, but this block polymer is difficult for preparation.U.S.Pat.No.4,463,152 have reported the multipolymer of acrylamide and the big monomer acrylic acid alkyl acid of non-ionic surface active polyoxyethylene ester, the relative polyacrylamide of this multipolymer has tackifying preferably, and the viscosity that reaches a certain threshold concentration post polymerization thing solution when concentration presents significantly increase.And its polymers soln shows salt thickening characteristic preferably, this patent ascribes these performances of polymkeric substance to and has introduced a spot of hydrophobic grouping on the polymer chain, hydrophobic grouping can associate together mutually in polymers soln, form intermolecular or the intramolecularly association, thereby cause tackifying preferably.Report (methyl) alkyl acrylate (U.S.Pat.NO.4 is arranged subsequently in succession, 814,096), (methyl) acrylic acid alkyl polyoxyethylene ester (U.S.Pat.NO.4,075,411), N-alkyl acrylamide (U.S.Pat.NO.4,395,524) with acrylamide copolymerization hydrophobic associated polymer.The most frequently used method of present synthetizing hydrophobic associated polymkeric substance is free micell polymerization method, need add a large amount of tensio-active agent (as SDS) when adopting the polymerization of this kind method and make the hydrophobic monomer solubilising in micella.But in polymerization process, add a large amount of tensio-active agents the association behavior of polymkeric substance is had remarkable influence (Chang Y, McCormick C L, Synthesis and SolutionCharaterization of Cationic Hydrophobically-modified AcrylamideCopolymers.Polym.Prepr., 1992,33 (2): 202～203), and remove the complicacy that these tensio-active agents also can increase last handling processes such as separation and purifying.In order to simplify last handling process and to strengthen the solvability of polymkeric substance, can employing itself just have surface-active hydrophobic monomer.Synthesized 2-acrylamido-2-alkyl ethyl sulfonic acid (U.S.Pat.NO.4 at present; 894; 422), (the rare acyl group of 2-methyl-prop) oxygen ethyl dimethyl dodecyl bromination ammonium (oilfield chemistry; 1999; 261～264), acrylamido propyl-dimethyl dodecyl bromination ammonium (Ezzell 15 (3):; S.A.; McCormick; C.L.; Macromolecules 1992,25 (7), 1881～1886), dimethyl-allyl alkyl ammomium chloride (Zheng Yan; the Southwest Petroleum Institute Ph D dissertation, 1999.6).This class monomer contains hydrophobic grouping and hydrophilic radical simultaneously, does not need to add in addition tensio-active agent when copolymerization, can directly adopt traditional free yl solution polymerization, and can make that the hydrophobic monomer height is unordered irregularly to be introduced in the multipolymer.But by discovering, the critical association concentration of the multipolymer of this class ionic hydrophobic monomer in the aqueous solution is (Ezzell, the S.A. more than 2 times of the identical hydrophobic chain length of micella multipolymer, McCormick, C.L., Macromolecules 1992,25 (7), 1881～1886).This is totally unfavorable in industrial application to hydrophobic associated polymer.
Summary of the invention
The object of the present invention is to provide AM/NaAA/AHAC ternary hydrophobic associated polymer, be acrylamide/sodium acrylate/allyl group hexadecylamine (AM/NaAA/AHAC) ternary hydrophobic associated polymer and synthetic method thereof, this polymkeric substance has tackifying and salt resistance preferably, this simple synthetic method is feasible, mild condition, the yield height, and be easy to purify, separate.This polymkeric substance can be used as tackifier and is used in industries such as oil production, coating, medicine.
A kind of novel water-soluble hydrophobic associated polymer A M/NaAA/AHAC ternary hydrophobic associated polymer comprises acrylamide, sodium acrylate, three kinds of structural units of allyl group hexadecylamine, and its structural formula is as follows:
Wherein x is a molar percentage 0.6%, and y is a molar percentage 0～34.1%.
The synthetic method of AM/NaAA/AHAC ternary hydrophobic associated polymer may further comprise the steps successively:
(1) with ethanol as reaction solvent, be raw material with chlorallylene and hexadecylamine, temperature of reaction is between 40～70 ℃, the reaction times is 20～30h, synthetic amine salt type surface-active macromonomers allyl group hexadecyl amine hydrochlorate (AHAC);
(2) in the AHAC aqueous solution, add acrylamide (AM), add again initiator potassium persulfate solution and N-(N ', N '-dimethylaminomethylene) acrylamide (DMAMAM) solution, total monomer is 10～20%, and concentration of initiating system is 40～120mg/L, and polymeric reaction temperature is at 40～60 ℃, reaction times is at 2～8h, inflated with nitrogen deoxygenation 30～60min seals in the rearmounted water bath with thermostatic control and reacts, preparation acrylamide/allyl group hexadecylamine (AM/AHAC) copolymer;
(3) add appropriate amount of NaOH solution as hydrolytic reagent, polymer concentration is 1～4%, hydrolysis temperature is 50～90 ℃, be uniformly dispersed and be placed on the reaction that is hydrolyzed in the water bath with thermostatic control, under different hydrolytic reagent consumptions and hydrolysis time, obtain degree of hydrolysis at 0～34.1% AM/NaAA/AHAC ter-polymers.
In the present invention, at first prepare surface-active macromonomers, because chlorallylene and hexadecylamine all are dissolved in ethanol, so adopt ethanol as reaction solvent, temperature of reaction can be between 40～70 ℃, and 50 ℃ of yields are the highest; Reaction times is 20～30h, and the 30h yield is the highest; Because amine is easy to oxidation in air, entire reaction is preferably under the nitrogen protection carries out; Reaction stops afterreaction liquid and is cooled to the white solid of separating out after the room temperature and is AHAC.
The AM/AHAC copolymer is to adopt free micell polymerization method to make in the aqueous solution.Take by weighing the AHAC of aequum earlier, and add the distilled water of aequum, place 40 ℃ water bath with thermostatic control to treat that AHAC dissolves fully then after.The AM that adds aequum again, inflated with nitrogen deoxygenation 30～60min adds the initiator solution prepare then, and sealing is placed on reacts certain hour in the temperature required water bath with thermostatic control down and gets final product.Initiator can adopt Potassium Persulphate, Diisopropyl azodicarboxylate, Potassium Persulphate/sodium bisulfite, Potassium Persulphate/tertiary amine etc.Because document (Pan Songhan etc., polymer journal 1994,1:99～102) reported once that Potassium Persulphate/N-(N ', N '-dimethylaminomethylene) acrylamide was polymerizing acrylamide triggered, not only can obtain the high-molecular weight polyacrylamide, and the synthetic polymkeric substance has certain degree of branching.Because the used hydrophobic monomer of the present invention---allyl group hexadecyl amine hydrochlorate from inhibition, make to be difficult to preparation high-molecular weight multipolymer.Therefore, in order to improve the molecular weight of multipolymer, adopt this initiator system, N-(N ', N '-dimethylaminomethylene) acrylamide (DMAMAM) synthetic sees embodiment 2, and concentration of initiating system is at 40～120mg/L, polymeric reaction temperature between 40～60 ℃ better, total monomer is better, especially all better in the polymer water dissolubility and the tackifying of 20% time preparation at 10～20%.Polymerization reaction time is no less than 2h, but after surpassing 8h, polyreaction stops substantially.The polymericular weight of preparation is between 400～6,000,000.
The hydrolysis of polymkeric substance not only increases the water-soluble of polymkeric substance in order to introduce ionic group, and the repulsion between ionic group more stretches polymer chain, helps intermolecular association, further improves the tackifying of polymkeric substance.Both can directly get and go on foot the polymeric colloid that has reacted, the also available polymkeric substance that had carried out separation and purified.Add an amount of hydrolytic reagent solution (45%NaOH), being uniformly dispersed is placed on the reaction that is hydrolyzed in the water bath with thermostatic control.Polymer concentration is about 1～4% during hydrolysis, and concentration is too big, and hydrolysis reaction is inhomogeneous.Hydrolysis temperature is 50～90 ℃, for fear of polymer degradation, selects 50 ℃ better.The degree of hydrolysis of polymkeric substance is controlled by the amount of hydrolytic reagent and hydrolysis time, obtains degree of hydrolysis at last at 0～34.1% AM/NaAA/AHAC ter-polymers.Reaction formula is as follows:
Polymkeric substance separates and purification has two kinds of methods: a kind of is by adding polar organic matter matter (as: methyl alcohol, ethanol, acetone etc.) precipitated outlet water dissolubility hydrophobic associated polymer to polymerization reaction system, collecting the back drying under reduced pressure and get final product; Another kind of separation and method of purification are used the film dialysis exactly, decompression oven dry then.
Compared with prior art, the present invention has following beneficial effect:
(1) first step of this synthetic method has been synthesized a kind of surface-active macromonomers that belongs to the amine salt type, does not need to add extraly tensio-active agent when polymerization;
(2) the synthetic polymkeric substance is transformed into amine and becomes the non-ionic hydrophobic association polymer along with amine salt in the posthydrolysis process, thereby reduces its critical association concentration;
(3) adopt the method for copolymerization posthydrolysis to introduce carboxylic acid sodium, make polymkeric substance have better water solubility;
(4) this polymkeric substance shows good tackifying in deionized water; In salts solution, especially under the inorganic salt concentration condition with higher, show certain salt thickening property.
Description of drawings
Fig. 1 is the γ-lgC curve (25 ℃) of amine salt type surface-active macromonomers of the present invention
Fig. 2 is the relation of polymers soln relative viscosity of the present invention and concentration
Fig. 3 is polymers soln relative viscosity of the present invention and the relation that adds inorganic salt concentration
Fig. 4 is the infrared spectrum of amine salt type surface-active macromonomers allyl group hexadecyl amine hydrochlorate (AHAC)
Embodiment
Synthesizing of embodiment 1 amine salt type surface-active macromonomers (AHAC)
In being housed, the flask of reflux condensing tube (100mL) adds hexadecylamine 4.829g (0.02mol), dehydrated alcohol 40mL, propenyl chloride 1.531g (0.02mol), react 30h down at 50 ℃, be cooled to room temperature and separate out solid, behind the suction filtration, filter residue obtains white crystal 3.657g (yield is about 57.5%) and is product with dehydrated alcohol recrystallization twice.
Embodiment 2N-(N ', N '-dimethylaminomethylene) acrylamide (DMAMAM) synthetic
In the 500mL three-necked flask of agitator, thermometer, reflux condensing tube is housed, add 35.53g (0.5mol) AM and 100mL distilled water, after the stirring and dissolving, add the saturated Na of 37.9mL
2CO
3Transfer to neutral formaldehyde solution, add the dimethylamine agueous solution 77.96mL of aequum again, reaction 1h under 60 ~ 70 ℃, adds the underpressure distillation of 200mg Resorcinol and collects 132-133 ℃/20mmHg cut except that after anhydrating with Rotary Evaporators.
Synthesizing of embodiment 3 binary hydrophobic associated polymers
Take by weighing the wide-necked bottle that hydrophobic monomer AHAC and distilled water place 100mL by the proportioning of table 1, put into after 40 ℃ water bath with thermostatic control dissolves it fully, take by weighing acrylamide again and add solution, treat its dissolving fully, logical N
2After half an hour, add the persulfate aqueous solution (4mg/mL), the DMAMAM aqueous solution (4mg/mL) that prepare in advance, after continuing logical nitrogen 10min, be placed in the water bath with thermostatic control (45 ℃) 8 hours with emulsion tube sealing, precipitate with dehydrated alcohol, with scissors throw out is cut into small pieces, uses soaked in absolute ethyl alcohol 3 days, 45 ℃ of following vacuum-dryings promptly get polymkeric substance.
The prescription of the synthetic copolymer of table 1
Medicine dosage (g)
AHAC 0.135
Distilled water 24.5
AM 5.0
K
2S
2O8 1.96×10
-3
DMAMAM 1.47×10
-3
Synthesizing of the hydrolysis of embodiment 4 copolymers or ternary hydrophobic associated polymer
In the wide-necked bottle of 250mL, routine synthetic copolymer 0.5g and 100ml distilled water in the adding, treat that polymkeric substance dissolves fully after, press Tab.2 and add hydrolytic reagent NaOH, react 4h down at 50 ℃, go out polymkeric substance, dry in the vacuum drying oven under 45 ℃ then with acetone precipitation.Can make the hydrophobic associated polymer of different degree of hydrolysis, specifically see Table 2.
The degree of hydrolysis of table 2 terpolymer
Sample number into spectrum NaOH (g) degree of hydrolysis (%)
16-0.6-6.8 0.039 6.8
16-0.6-14.5 0.118 14.5
16-0.6-23.9 0.232 23.9
16-0.6-29.5 0.328 29.5
16-0.6-34.1 0.47 34.1
The surfactivity of embodiment 5 big monomer A HAC
See Fig. 1, cmc=5.42 * 10 of this amine salt type surface-active macromonomers
-4Mol/L, γ cmc=38.9mN/m has the similar surfactivity of quaternary surface-active macromonomers, thereby does not need to add extra tensio-active agent during polymerization.
The rheological of embodiment 6AM/NaAA/AHAC ternary hydrophobic associated polymer
See Fig. 2, the sample number into spectrum of polymkeric substance is 16-0.6-14.5, and when polymer concentration was lower than 0.001g/mL, the relative viscosity of this polymers soln slowly rose with the increase of polymer concentration; When polymer concentration surpassed 0.001g/mL, the relative viscosity of solution increased and sharply rising with the concentration of polymkeric substance.Show the thickening property different with partially hydrolyzed polyacrylamide.Show that this polymkeric substance has tackifying preferably in the aqueous solution.
The salt resistance of embodiment 7AM/NaAA/AHAC ternary hydrophobic associated polymer
See Fig. 3, the sample number into spectrum of polymkeric substance is 16-0.6-14.5, and the viscosity of this polymers soln can sharply descend along with the adding of inorganic salt, and this point is similar with the situation of partially hydrolyzed polyacrylamide, salt concn be about 5% drop to minimum.The trend that then presents slow rising along with the further increase of salt concn.This point is that partially hydrolyzed polyacrylamide is not available.Thereby show that this polymkeric substance has certain salt resistance.
The structural characterization of embodiment 8 amine salt type surface-active macromonomers allyl group hexadecyl amine hydrochlorates
The infrared spectrum of the amine salt type surface-active macromonomers AHAC that makes by embodiment 1 is seen Fig. 4, learns that from figure the stretching vibration peak of C=C is at 1643cm
-1The place, C-H (CH
3), C-H (CH
2-) stretching vibration peak respectively at 2927cm
-1, 2850cm
-1The place, C-N (CH
2-NH-), (stretching vibration peak NH-) is respectively at 1145cm for N-H
-1, 3428cm
-1The place.
Claims (2)
1AM/NaAA/AHAC ternary hydrophobic associated polymer, promptly acrylamide/sodium acrylate/allyl group hexadecylamine ternary hydrophobic associated polymer comprises acrylamide, sodium acrylate, three kinds of structural units of allyl group hexadecylamine, and its structural formula is as follows:
Wherein x is a molar percentage 0.6%, and y is a molar percentage 0～34.1%.
The synthetic method of 2 ternary hydrophobic associated polymers as claimed in claim 1 may further comprise the steps successively:
(1) with ethanol as reaction solvent, be raw material with chlorallylene and hexadecylamine, temperature of reaction is between 40～70 ℃, the reaction times is 20～30h, synthetic amine salt type surface-active macromonomers allyl group hexadecyl amine hydrochlorate AHAC;
(2) in the AHAC aqueous solution, add acrylamide AM, add again initiator potassium persulfate solution and N-(N ', N '-dimethylaminomethylene) acrylamide DMAMAM solution, total monomer is 10～20%, and concentration of initiating system is 40～120mg/L, and polymeric reaction temperature is at 40～60 ℃, reaction times is at 2～8h, inflated with nitrogen deoxygenation 30～60min seals in the rearmounted water bath with thermostatic control and reacts, and preparation acrylamide/allyl group hexadecylamine is the AM/AHAC copolymer;
(3) add appropriate amount of NaOH solution as hydrolytic reagent, polymer concentration is 1～4%, hydrolysis temperature is 50～90 ℃, be uniformly dispersed and be placed on the reaction that is hydrolyzed in the water bath with thermostatic control, under different hydrolytic reagent consumptions and hydrolysis time, obtain degree of hydrolysis at acrylamide/sodium acrylate/allyl group hexadecylamine AM/NaAA/AHAC ter-polymers of 0～34.1%.
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| CN102520117A (en) * | 2011-10-23 | 2012-06-27 | 四川光亚聚合物化工有限公司 | Method for testing hydrolysis degree of hydrophobically associating polymer in oil reservoir sewage |
| CN103435750B (en) * | 2013-08-27 | 2015-10-21 | 中国海洋大学 | Hydrophobic associated polymer containing capsaicine activity monomer and preparation method thereof |
| CN105646773B (en) * | 2015-12-29 | 2018-11-13 | 四川光亚聚合物化工有限公司 | A kind of hydrophobic associated polymer and preparation method thereof |
| CN105646771A (en) * | 2015-12-29 | 2016-06-08 | 四川光亚聚合物化工有限公司 | Hydrophobic associated polymer and preparation method thereof |
| CN113348187A (en) * | 2018-07-17 | 2021-09-03 | 聚合分析公司 | Synthesis method for preparing rheology modified polymer and application thereof |
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