CN101492515B - Acrylic amide modified graft copolymer, preparation method and application thereof - Google Patents
Acrylic amide modified graft copolymer, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an acrylamide modified graft copolymer and a preparation method and usage thereof. The invention is characterized in that 20 parts of acrylamide, 1-20 parts of anionic monomer and/or cationic monomer, 0.1-15 parts of macromonomer, 0.05-10 parts of ionic lyophobic monomer and 50-1000 parts of deionized water are added into a three-necked reaction bottle, the pH value is adjusted to be 3-9, N2 is introduced for 30min, then 0.002-0.5 parts of initiator persulfate is added at 30-75 DEG C, the copolymer PAB is obtained by reacting for 8-36h, and finally water is used for dilution to obtain strong PAB solution. The PAB has higher apparent viscosity in high saline solution than in fresh water. The PAB is prepared into a water solution with mass concentration of 0.2-3.0g/L and surfactant concentration of 0.01-2 mmol/L, then the water solution is added into a mixing vessel with a stirring device, and then a polymer oil-displacing agent is obtained through uniform mixing at a room temperature. The copolymer PABE is prepared into water solution which has mass concentration of 0.05-7%, and obtains the macromolecule surfactant and is applicable to an emulsifier, an emulsion splitter, a solubilizer and a wetting agent.
Description
One, technical field
The present invention relates to a kind of acrylic amide modified graft copolymer and its production and use, belong to macromolecular material and improve the oil recovery field.
Two, technical background
In order to improve oil recovery, the polymkeric substance of using in polymer displacement of reservoir oil tech at present mainly is partially hydrolyzed polyacrylamide (HPAM).HPAM is the molecular structure of line style, and its tackify mainly depends on ultra-high molecular weight, and molecular weight is up to 1.6 * 10
7～3.0 * 10
7, degree of hydrolysis is generally 10～30%.The thread-like molecule structure of HPAM and high degree of hydrolysis make its salt resistance in the high salinity oil reservoir and heatproof, solution property such as anti-shearing and anti-aging relatively poor, and therefore, HPAM can only be used for low temperature low mineralization oil reservoir.For the salt resistance that improves HPAM solution and other solution property, the investigator has carried out modification by following approach to polyacrylamide both at home and abroad: 1. with have the unitary function monomer copolymerization of temperature resistant antisalt performance structure, preparation line style temperature resistant antisalt multipolymer; 2. in HPAM solution, add small molecules organic or inorganic linking agent, crosslinked a little less than HPAM is carried out, obtain flowable weak gel; 3. utilize hydrogen bond and statcoulomb power between macro-radical, carry out the macromole self-assembly, as amphoteric ion polymer and polymer composite body system; 4. with the hydrophobic monomer copolymerization that has hydrophobic grouping, obtain the line style hydrophobic associated copolymer; 5. with big monomer copolymerization, obtain comb copolymer.Above-mentioned all kinds of acrylic amide modified polymer respectively has its outstanding characteristics, but also exist significantly not enough, the crosslinked weak gel of HPAM is strong because of the molecule chain rigidity, its heatproof and anti-salt property are better, but because its hydrodynamic radius is big, easily stop up the fine porosity of petroleum reservoir, particularly in, the pore throat of low permeability reservoir, only be applicable to high infiltration oil reservoir.For the temperature resistant antisalt multipolymer of line style, because of the effect of salt pair ionic electrostatic shielding, the adding of salt makes the linear macromolecule chain curl inevitably; For line style hydrophobic association ionic multipolymer, the effect of salt pair ionic electrostatic shielding causes intermolecular association to be had a strong impact on; For comb type ionic multipolymer with rigid conformation, though changed the traditional thread-like molecule structure of displacement of reservoir oil polymkeric substance, strengthened the salt resistance of polymkeric substance, there is salt effect too in copolymer solution.Therefore, the adding of different concns salt all makes the solution viscosity of above-mentioned three kinds of multipolymers descend significantly.Therefore, under the solution lower concentration, have good solubility, high tackify, anti-salt, heatproof, anti-shearing and aging-resistant solution property simultaneously, the displacement of reservoir oil water-soluble polymers that can be used for different permeability oil reservoir remains the goal in research of displacement of reservoir oil polymer technology.Liu Kun, oilfield chemistry, 2007,24 (4): 340-343, studied the weak gel of chromium cross linker Water-Cut684 and two kinds of polymkeric substance MO-400 and permanent poly-polymer formation, found that weak gel drives the ability that improves recovery ratio and drives apparently higher than simple linear polymer, but the fill out sand tube that is used to test all is high permeabilities, is respectively 5.0 μ m
2With 1.5 μ m
2Liao Li etc., the Tianjin chemical industry, 2006,20 (4): 29-35, studied the synthetic of temperature resistant antisalt ternary displacement of reservoir oil acrylamide copolymer/3-acrylamido-3 Methylbutanoic acid sodium/2-acrylamido-2-methyl propane sulfonic acid, find that this multipolymer is at 40 ℃, 6.8s
-1When being 2.5g/L with concentration, it is that apparent viscosity in 9% the NaCl salt brine solution is all not high in the aqueous solution and mass concentration, is respectively 90mPa.s and 50mPa.s.Lv Jinglan etc., petrochemical complex, 2005,34 (6): 72-77, synthesized the methylpropene sodium sulfonate-N,N-DMAA-acrylamide temperature resistant antisalt multipolymer of line style, found that, the adding of salt makes soltion viscosity obviously descend, when this copolymer concentration is 1.5g/L, and the 60mPa.s the when apparent viscosity of solution is dropped to salinity and is 5g/L by the 260mPa.s in the fresh water.The Geng confederates etc., fine chemistry industry 2006,23 (8): 747-751 has synthesized poly-(acrylamide/sodium acrylate/N, the N-diallyl tetradecy lamine) (P (AM/NaAA/DiAC of ternary hydrophobic associated water-soluble polymer
14), discover that mass concentration is that this multipolymer of 4g/L is at 85 ℃ and 7.34s
-1The time aqueous solution apparent viscosity be 80mPa.s, the adding of salt reduces the viscosity number of solution.Luo Jianhui etc., petroleum journal, 2004,25 (2): 67-73, synthesized AM/AHPE comb-shaped copolymer (KYPAM), the molecular weight of this base polymer is up to 2.514 * 10
7Thickening capabilities in salt solution improves more than 50% than the thickening capabilities of present domestic super high molecular weight polyacrylamide in salt solution, but its apparent viscosity in salt solution also is lower than in the fresh water, and the hydrodynamic radius of comb shaped polymer is big, only be applicable to high permeable reservoir strata, in easily stopping up, the pore throat of low permeability reservoir.
Three, summary of the invention
The objective of the invention is according to present HPAM and polymer-modified present Research and deficiency thereof, fundamentally change the molecular structure of displacement of reservoir oil polymkeric substance, in conjunction with the advantage of above-mentioned temperature resistant antisalt multipolymer, hydrophobic associated copolymer, comb copolymer and amphoteric ion polymer, provide a kind of acrylic amide modified graft copolymer than apparent viscosity higher in the fresh water and strong intermolecular self-assembly ability and its production and use that in high level salt solution, has.Except that the macromole side chain that contains many chaotic distribution, also contain the Intermolecular Forces that can provide strong in the molecular side chain of this graft copolymer, make multipolymer have the hydrophobic functional group of intermolecular associative ability.Be characterized in acrylamide (AM) as main hydrophilic monomer, with 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a big monomer be comonomer, with C
1-20Alkyl dimethyl chlorallylene (bromine) is changed ammonium, C
1-20Alkyl dimethyl (4-vinyl benzyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl (2-acrylamido ethyl) chlorine (bromine) is changed ammonium, C
1-20At least a ionic hydrophobic monomer that alkyl dimethyl (2-methylacryoyloxyethyl) chlorine (bromine) is changed in the ammonium is the association function monomer, or/and cationic monomer is the solubilising hydrophilic monomer, adopt the aqueous free radical process for copolymerization to synthesize acrylic amide modified graft copolymer PAB with a spot of anionic monomer.
The present inventor finds that the mol ratio, ionic hydrophilic monomer concentration, temperature of reaction of various reaction conditionss in the polyreaction such as big monomer concentration, ionic hydrophobic monomer concentration, big monomer and ionic hydrophobic monomer etc. has a significant impact gained copolymer structure and solution behavior.Because the ionic hydrophobic monomer can be water-soluble fully, therefore, when synthetic copolymer PAB, do not need to use tensio-active agent, cause that copolymerization is easier to carry out, under the condition that the molecular dimension that satisfies multipolymer and pore throat in reservoirs diameter are complementary, can prepare the higher multipolymer of molecular weight, multipolymer also just can produce stronger intermolecular association under lower concentration like this.For general line style ionic copolymer, because the effect of salt pair ionic electrostatic shielding is curled molecular chain, therefore, under all concentration of salt, the apparent viscosity of salt brine solution all is starkly lower than the apparent viscosity in the fresh water.But for graft copolymer PAB, because suitable big monomer concentration and ionic hydrophobic monomer concentration can greatly improve multipolymer non-linearity molecule chain rigidity and intermolecular self-assembly ability, these two kinds monomeric suitable mole specific energys are brought into play the conformation and the intermolecular associating collaborative tackify saline-alkaline tolerance of molecular chain best, make copolymer p AB show unique solution property, in haline water solution, has high apparent viscosity, soltion viscosity not only not because of the adding of salt descends, also is significantly higher than the apparent viscosity in the fresh water on the contrary.Add an amount of ionic hydrophilic monomer and can increase substantially the solvability of multipolymer, and molecular chain is more stretched, help the formation of intermolecular associative structure.Suitable initiator concentration, total reaction monomer concentration, temperature of reaction and pH value in reaction can obtain to have the copolymer p AB of excellent solution property.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the prescription of acrylic amide modified graft copolymer PAB
The recipe ingredient of acrylic amide modified graft copolymer PAB is:
20 parts of acrylamides
1～20 part of hydrophilic ion monomer
0.1～15 part of big monomer
0.05～10 part of ionic hydrophobic monomer
50～1000 parts of deionized waters
Wherein anionic monomer is that vinylformic acid, methacrylic acid, 3-acrylimide base-3 Methylbutanoic acid, methylene-succinic acid, vinylbenzenesulfonic acid are or/and 2-acrylamido-2-C
1-18Alkyl C
2-18At least a in the alkylsulphonic acid; Cationic monomer is dimethyl diallyl ammonium chloride, trimethylammonium allyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride or/and at least a in trimethylammonium (2-methylacryoyloxyethyl) ammonium chloride; Big monomer is 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a; The ionic hydrophobic monomer is C
1-20Alkyl dimethyl chlorallylene (bromine) is changed ammonium, C
1-20Alkyl dimethyl (4-vinyl benzyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl (2-acrylamido ethyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl (2-methylacryoyloxyethyl) chlorine (bromine) is changed at least a in the ammonium.
2. the preparation of acrylic amide modified graft copolymer PAB
With 20 parts of acrylamides, anionic monomer is or/and 1～20 part of cationic monomer, 0.1～15 part of big monomer, and 0.05～10 part of ionic hydrophobic monomer, deionized water adds in the three neck reaction flasks for 50～1000 parts, regulator solution pH=3～9, logical N
2Behind the 30min, add 0.002～0.5 part of initiator persulphate down for 30～75 ℃ in temperature, reacted 8～36 hours, make PAB, dilute with water obtains the PAB strong solution again.
Wherein anionic monomer is that vinylformic acid, methacrylic acid, 3-acrylimide base-3 Methylbutanoic acid, methylene-succinic acid, vinylbenzenesulfonic acid are or/and 2-acrylamido-2-C
1-18Alkyl C
2-18At least a in the alkylsulphonic acid; Cationic monomer is dimethyl diallyl ammonium chloride, trimethylammonium allyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride or/and at least a in trimethylammonium (2-methylacryoyloxyethyl) ammonium chloride; Big monomer is 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a; The ionic hydrophobic monomer is C
1-20Alkyl dimethyl chlorallylene (bromine) is changed ammonium, C
1-20Alkyl dimethyl (4-vinyl benzyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl (2-acrylamido ethyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl (2-methylacryoyloxyethyl) chlorine (bromine) is changed at least a in the ammonium.
3. the performance of acrylic amide modified graft copolymer PAB
Remove specified otherwise, all do not add tensio-active agent in the following copolymer p AB solution.
(1) intrinsic viscosity of PAB sample is as shown in table 1.The intrinsic viscosity of ultra-high molecular weight HPAM generally all is higher than 20dL/g.The result shows that HPAM compares with ultra-high molecular weight, PAB be in, low-molecular weight copolymer, can be used for, low-permeability oil pool.The tackify of PAB mainly depends on the extended conformation and the intermolecular associating synergistic effect of non-linearity molecular chain.
(2) relation of the fresh water solution apparent viscosity of PAB and concentration is as shown in table 2.The result shows that PAB has good tackifying ability.
(3) relation of the salt brine solution apparent viscosity of PAB and concentration is as shown in table 3.The result shows that the polymers soln of high salt concentration (80000mg/LNaCl) has the viscosity number higher than fresh water, and this is the desired solution anti-salt property of displacement of reservoir oil polymkeric substance just.
(4) sodium chloride concentration is as shown in table 4 to the influence of 2.0g/L PAB solution apparent viscosity.The result shows that PAB has excellent anti-salt property, and in the salt concn scope of broad, polymers soln all has the viscosity number higher than fresh water.
(5) PAB concentration is as shown in table 5 to the capillary influence of polymers soln.The result shows that the surface tension of PAB solution is low, introduces the surface tension that can reduce polymers soln effectively in the time of big monomer and ionic hydrophobic monomer.
(6) relation of temperature and PAB solution viscosity is as shown in table 6.The result shows that PAB solution still has higher viscosity under higher temperature, illustrates that polymkeric substance has good heat resistance.
(7) shearing action is as shown in table 7 to the influence of the soltion viscosity of PAB.As seen from the table, this special anti-shear performance makes PAB can be used for tertiary oil recovery.When PAB passed through the pore throat of petroleum reservoir, molecular chain was subjected to shearing action, and its associative structure is destroyed, and soltion viscosity descends; Behind pore throat, shearing action weakens, and intermolecular association forms again, and soltion viscosity recovers again gradually.Result in the table has also illustrated multipolymer when being subjected to shearing, and chemical structure is not damaged, and molecular chain more stretches, and intermolecular association also has been reinforced.
4. the purposes of acrylic amide modified graft copolymer PAB
Copolymer p AB can be used as used for tertiary oil recovery oil-displacing agent and polymeric surface active agent.
(1) copolymer p AB being made into mass concentration is 0.2～3.0g/L, surfactant concentration is the aqueous solution of 0.01～2mmol/L, adding has in the mixing vessel of whipping appts, at room temperature stirs, and promptly obtains high tackify, salt tolerant, shear-stable polymer oil-displacing agent.
Wherein tensio-active agent contains: anion surfactant C
8-16Sodium alkyl benzene sulfonate or C
8-16Sodium alkyl sulfate; Cats product C
8-16Alkyl trimethyl bromine (chlorine) is changed at least a in the ammonium.
(2) copolymer p AB being made into mass concentration is 0.05～7% the aqueous solution, obtains to have excellent surface-active polymeric surface active agent, as emulsifying agent, emulsion splitter, solubilizing agent and wetting agent.
5. the advantage of acrylic amide modified graft copolymer PAB
Acrylic amide modified graft copolymer PAB of the present invention has following advantage:
The present invention is with 4-vinyl benzyl alkylphenol polyoxyethylene (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), 4-vinyl benzyl alkyl polyoxyethylene ether (CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), allyl group alkylphenol polyoxyethylene (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), allyl group alkyl polyoxyethylene ether (CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkylphenol polyoxyethylene methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20), alkyl polyoxyethylene ether acrylate (CH
2=CH-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) or/and alkyl polyoxyethylene ether methacrylic ester (CH
2=C (CH
3)-CO (OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20) at least a big monomer be comonomer, be used to improve the copolymer molecule chain rigidity.With C
1-20Alkyl dimethyl chlorallylene (bromine) is changed ammonium, C
1-20Alkyl dimethyl (4-vinyl benzyl) chlorine (bromine) is changed ammonium, C
1-20Alkyl dimethyl chlorine (2-acrylamido ethyl) (bromine) is changed ammonium, C
1-20At least a ionic hydrophobic monomer in alkyl dimethyl (2-methylacryoyloxyethyl) brometo de amonio is the association function monomer, and employing aqueous free radical process for copolymerization has synthesized anti-salt, had the copolymer p AB of low surface tension.Compare with comb type acrylamide ionic terpolymer with line style hydrophobic association acrylamide ionic terpolymer, PAB not only has the molecular structure and the solution property of these two kinds of multipolymers simultaneously, also because big monomer is distributed in the molecular chain disorderly, these molecule side chains have not only increased whole macromole chain rigidity, the conformation of macromolecular chain is stretched, the tackify and the anti-salt that help copolymer p AB, also make hydrophobic functional group in the macromolecular chain because the separation of these macromole side chains also is difficult to take place intramolecularly in salt brine solution associate, thereby significantly strengthened intermolecular association, and the mole specific energy of suitable big monomer and ionic hydrophobic monomer farthest brings into play the collaborative tackify and the saline-alkaline tolerance of molecule chain rigidity and intermolecular association, makes copolymer p AB present the solution property with above-mentioned two kinds of diverse excellences of ionic terpolymer.In addition, can adjust the mol ratio of big monomer and ionic hydrophobic monomer and the molecular weight of multipolymer according to salinity in the oil reservoir and rate of permeation, so that PAB is issued to the highest solution apparent viscosity at applied environment.Molecule side chain that these steric hindrances are bigger and hydrophobic function group can also suppress the oxidative degradation of main chain and the hydrolysis of main chain amide group, improve heatproof and the ageing resistance of copolymer p AB.Big monomer and ionic hydrophobic monomer all have surfactivity, after they are introduced at the same time molecular chain, make copolymer p AB solution have low surface tension, therefore, PAB has the dual-use function of tackifier and polymeric surface active agent, adds the low-molecular-weight surfactant of denier in PAB solution, just can significantly improve the apparent viscosity of solution, reduce the surface tension and the oil water interfacial tension of solution, help improving the recovery ratio of crude oil.
Four, embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the researchist in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
Acrylamide 20.000 grams, 2-acrylamido-2-methyl propane sulfonic acid 2.600 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 20) 6.510 grams, octadecyl dimethyl-allyl ammonium chloride 8.200 grams are dissolved in 320 ml distilled waters, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=4,65 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 8.20mL, reaction 32h, and the polymkeric substance dilute with water makes the PAB strong solution.
Embodiment 2
Acrylamide 20.000 grams, 2-acrylamido-2-tetradecyl ethyl sulfonic acid 17.310 grams, allyl group polyoxyethylene octylphenol ether (the affixture EO of Soxylat A 25-7 is 40) 11.400 grams, dodecyl dimethyl allyl ammonium chloride 5.720 grams are dissolved in 680 ml distilled waters, add in three mouthfuls of reaction flasks, with NaOH regulator solution pH=7,75 ℃ of reaction temperature, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 14.00mL, reaction 36h, and the polymkeric substance dilute with water makes the PAB strong solution.
Embodiment 3
Acrylamide 20.000 grams, vinylbenzenesulfonic acid 5.120 grams, 4-vinyl benzyl polyoxyethylene nonylphenol ether (EO is 10) 4.360 grams, dodecyl dimethyl (4-vinyl benzyl) ammonium chloride 2.380 grams are dissolved in 290 ml deionized water, regulate pH=3.5 with NaOH, 55 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L ammonium persulfate initiator solution 3.08mL, reaction 12h.The polymkeric substance water dissolution makes the PAB strong solution.
Embodiment 4
Acrylamide 20.000 grams, vinylformic acid 8.160 grams, 4-vinyl benzyl polyoxyethylene nonylphenol ether (EO is 50) 18.200 grams, eight alkyl dimethyls (4-vinyl benzyl) ammonium chloride, 4.750 grams are dissolved in 170 ml deionized water, regulate pH=6 with NaOH, 60 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 22.00mL, reaction 36h.The polymkeric substance water dissolution makes the PAB strong solution.
Embodiment 5
Acrylamide 20.000 grams, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride 16.010 grams, polyoxyethylene nonylphenol ether acrylate (EO is 40) 1.720 grams, hexadecyldimethyl benzyl ammonium (2-acrylamido ethyl) ammonium chloride 3.920 grams are dissolved in 940 ml deionized water, regulate pH=9 with NaOH, 70 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Sodium Persulfate initiator solution 16.20mL, reaction 32h, and the polymkeric substance water dissolution makes the PAB strong solution.
Embodiment 6
Acrylamide 20.000 grams, vinylformic acid 7.500 grams, octadecyl phenol polyethenoxy ether acrylate (EO is 60) 9.300 grams, tetradecyl dimethyl (2-methylacryoyloxyethyl) ammonium chloride 0.890 gram are dissolved in 445 ml deionized water, regulate pH=7 with NaOH, 35 ℃ of temperature of reaction, logical N
230min adds 0.05mol/L Potassium Persulphate initiator solution 9.00mL, reaction 16h, and the polymkeric substance water dissolution makes the PAB strong solution.
Application example 1
Get a certain amount of PAB multipolymer preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Polymer concentration is 0.5g/L, and Sodium dodecylbenzene sulfonate 0.4mmol/L adds in the mixing tank of band stirring, stirs under room temperature, obtains can be used for the polymer oil-displacing agent of tertiary oil recovery.
Application example 2
Get a certain amount of PAB multipolymer preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Polymer concentration is 0.8g/L, and trimethylammonium hexadecyl brometo de amonio 0.02mmol/L adds in the mixing tank of band stirring, stirs under room temperature, obtains to be used for the polymer oil-displacing agent of tertiary oil recovery.
Application example 3
Get a certain amount of PAB multipolymer preparation oil-displacing agent aqueous sample, sample is the water white transparency shape.Polymer concentration is 1.5g/L, and sodium lauryl sulphate 1.5mmol/L adds in the mixing tank of band stirring, stirs under room temperature, obtains to be used for the polymer oil-displacing agent of tertiary oil recovery.
Application example 4
It is 0.5% the aqueous solution that copolymer p AB is made into mass concentration, obtains to have excellent surface-active emulsifying agent.
Application example 5
It is 4% the aqueous solution that copolymer p AB is made into mass concentration, obtains to have excellent surface-active emulsion splitter.
Five, subordinate list explanation
The intrinsic viscosity of table 1 copolymer p AB sample
The relation of table 2 copolymer concentration and aqueous solution apparent viscosity
The relation of table 3 copolymer concentration and salt brine solution apparent viscosity
Annotate: NaCl concentration 80000m/L
Table 4NaCl concentration is to the influence of solution apparent viscosity
Annotate: copolymer solution concentration 2.0g/L
The relation of table 5 copolymer concentration and solution surface tension
Table 6 temperature is to the influence of solution apparent viscosity
Annotate: copolymer solution concentration 2.0g/L, NaCl concentration 80000mg/L
Table 7 shearing rate is to the influence of solution apparent viscosity
Annotate: copolymer solution concentration 2.0g/L, NaCl concentration 80000mg/L
More than the apparent viscosity in the table is except that specifying, test condition is 45 ℃, 7.34s
-1.
Claims (1)
1. the preparation method of acrylic amide modified graft copolymer is characterized in that:
Each component by weight, with 20 parts of acrylamides, anionic monomer is or/and 1～20 part of cationic monomer, 0.1～15 part of surface-active macromonomers, 0.05～10 part of ionic hydrophobic monomer, deionized water adds in the three neck reaction flasks for 50～1000 parts, regulator solution pH=3～9, logical N
2Behind the 30min, add 0.002～0.5 part of initiator persulphate down for 30～75 ℃, reacted 8～36 hours, make acrylic amide modified graft copolymer in temperature;
Wherein surface-active macromonomers is 4-vinyl benzyl alkylphenol polyoxyethylene CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20,4-vinyl benzyl alkyl polyoxyethylene ether CH
2=CH-C
6H
4-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, m=1～20, allyl group alkylphenol polyoxyethylene CH
2=CH-CH
2(OCH
2CH
2) n-O-C
6H
4-C
mH
2m+1, n=1～60, m=1～20 and allyl group alkyl polyoxyethylene ether CH
2=CH-CH
2(OCH
2CH
2) n-O-C
mH
2m+1, n=1～60, at least a in m=1～20; The ionic hydrophobic monomer is C
1 -20Alkyl dimethyl allyl ammonium chloride, C
1-20Alkyl dimethyl (4-vinyl benzyl) ammonium chloride, C
1-20Alkyl dimethyl (2-acrylamido ethyl) ammonium chloride and C
1-20At least a in alkyl dimethyl (2-methylacryoyloxyethyl) ammonium chloride; Anionic monomer is vinylformic acid, methacrylic acid, 3-acrylimide base-3 Methylbutanoic acid, methylene-succinic acid, vinylbenzenesulfonic acid and 2-acrylamido-2-C
1-18Alkyl C
2-18At least a in the alkylsulphonic acid; Cationic monomer is at least a in dimethyl diallyl ammonium chloride, trimethylammonium allyl ammonium chloride, Jia Jibingxisuanyizhi base trimethyl ammonium chloride, ethyl propenoate base trimethyl ammonium chloride, 2-acrylamido-2-trimethoxysilyl propyl methacrylate ammonium chloride and trimethylammonium (2-methylacryoyloxyethyl) ammonium chloride.
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