CN103772713B - Graft modification polypropylene acid amides and preparation method thereof - Google Patents
Graft modification polypropylene acid amides and preparation method thereof Download PDFInfo
- Publication number
- CN103772713B CN103772713B CN201210393357.1A CN201210393357A CN103772713B CN 103772713 B CN103772713 B CN 103772713B CN 201210393357 A CN201210393357 A CN 201210393357A CN 103772713 B CN103772713 B CN 103772713B
- Authority
- CN
- China
- Prior art keywords
- acrylamide
- peo
- ppo
- pnam
- acid amides
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of graft modification polypropylene acid amides and preparation method thereof, mainly solve polyacrylamide heatproof in prior art, anti-salt, ageing-resistant performance and the poor problem of displacement efficiency. The present invention is by adopting a kind of graft modification polypropylene acid amides, and chemical general formula is: HPAM-<i>g</i>-R, wherein, HPAM is super high molecular weight polyacrylamide, R is for being selected from PEO-<i>b</i>-PNAM, PPO-<i>b</i>-PNAM, P (EO-<i>r</i>-PO)-<i>b</i>-PNAM, PEO-<i>b</i>-PPO-<i>b</i>-PNAM or PPO-<i>b</i>-PEO-<i>b</i>One in-PNAM, EO is oxirane, PO is expoxy propane, PEO is PEO, PPO is PPOX, PNAM is poly-N-substituted acrylamide, and the technical scheme of viscosity average molecular weigh>=2,700 ten thousand of this graft modification polypropylene acid amides and preparation method thereof has solved this problem preferably, can be used in the industrial production and the high temperature and high salt oil deposit displacement of reservoir oil of polymer oil-displacing agent.
Description
Technical field
The present invention relates to tertiary oil recovery field, be specifically related to a kind of graft modification super high molecular weight polyacrylamide and preparation method thereof.
Background technology
Exploitation of oil-gas field requires to mainly contain by the universal performance of water-soluble polymer: water-soluble, tackifying, suspension, shear thinning behavior and thixotropy, stability and seepage characteristic meet the requirement of oil-gas mining engineering etc. Although super high molecular weight polyacrylamide still can (as 120 DEG C) improve tar productivity under higher temperature in anaerobic, without divalent ion environment, when conventional water-soluble polymer is used for the displacement of reservoir oil in tertiary oil recovery at present, also there are many problems. As serious in hydrolysis of polyacrylamide in the time that temperature is higher; Formation temperature exceedes after 75 DEG C, and along with formation temperature raises, super high molecular weight polyacrylamide precipitation forms to be accelerated; High temperature and high salt easily causes super high molecular weight polyacrylamide to be precipitated out from the aqueous solution, and the higher this phenomenon of degree of hydrolysis is more remarkable; Solution viscosity is very responsive to temperature and salinity, and in high temperature and high salt environment, the reservation viscosity of solution is very low. Therefore, both at home and abroad researcher has carried out a large amount of research to the large molecule of polyacrylamide polymers for oil displacement so that its special reservoir condition while meeting field use.
Patent CN102051165A discloses a kind of method for making and application of the xanthan gum graft copolymer as oil displacement agent, adopt graft copolymerization method that heat-resistance type function monomer is introduced on xanthans macromolecular chain, improved viscoelasticity and the biological stability of large biological molecule. document (B ü y ü kya c A, TuzcuG, ArasL.Synthesisofcopolymersofmethoxypolyethyleneglycolac rylateand2-acrylamido-2-methyl-1-propanesulfonicacid:Its characterizationandapplicationassuperplasticizerinconcre te.CementandConcreteResearch, 2009, 39 (7): 629-635.) reported the synthetic and application as the polyacrylamide graft copolymer of high molecular surfactant, the large monomer adopting is mainly the APEO esters of acrylic acid of facile hydrolysis under acid or alkali condition. and the above-mentioned polymer side chain being grafted on macromolecular chain, chain length differs and is uncontrollable, and this brings difficulty for further Study Polymer Melts grafted chain length and rheological property, temperature-resistant anti-salt ageing resistace and the tertiary oil recovery displacement research etc. of molecular weight equimolecular structural factor to graft copolymer.
Summary of the invention
One of technical problem to be solved by this invention is, when super high molecular weight polyacrylamide is for tertiary oil recovery field in prior art, to have heatproof, anti-salt, ageing-resistant performance and the poor problem of displacement efficiency, and a kind of new graft modification polypropylene acid amides is provided. This graft modification polypropylene acid amides has advantages of heatproof, anti-salt, ageing-resistant performance is good and displacement efficiency is high. Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with the graft modification polypropylene acid amides of one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of graft modification polypropylene acid amides, has following chemical general formula:
HPAM-g-R
Wherein, HPAM is super high molecular weight polyacrylamide;
R is for being selected from PEO-b-PNAM、PPO-b-PNAM、P(EO-r-PO)-b-PNAM、PEO-b-PPO-b-PNAM or PPO-b-PEO-bOne in-PNAM;
EO is oxirane;
PO is expoxy propane;
PEO is PEO;
PPO is PPOX;
PNAM is poly-N-substituted acrylamide;
Viscosity average molecular weigh >=2,700 ten thousand of this graft modification polypropylene acid amides.
In technique scheme, R is the controlled block type copolymer of molecular weight that adopts active free radical polymerization method to make, in its molecular formulabExpression copolymer is block type,rExpression copolymer is random. In PEO, PPO, PNAM, the number of repeat unit of monomer is all selected from the arbitrary integer in 1～100.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of graft modification polypropylene acid amides, comprises the following steps:
A) taking at least one epoxyalkane in oxirane or expoxy propane as raw material, with 2,2,6,6-tetramethyl-4-halogen-1-oxygen phenylpiperidines sodium is initator, be under 1:1～200,20～120 DEG C of reaction temperatures, the condition in 2～15 hours reaction time in the mol ratio of initator and epoxyalkane, reaction obtains respectivelyX-PEO、X-PPO、X-P(EO-r-PO)、X-PEO-b-PPO orX-PPO-bThe polymer of-PEO,XIt is 2,2,6,6-tetramethyl-4-halogen-1-oxygen phenylpiperidines base;
B) respectively toX-PEO、X-PPO、X-P(EO-r-PO)、X-PEO-b-PPO orX-PPO-bIn the polymer of-PEO, add the nitrogen oxide 2,2,6 with epoxide group, 6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical, at 50～125 DEG C, continue reaction 1～8 hour, reaction obtains respectively the polyalkylene oxide of associated end band nitrogen oxygen activity group NOX-PEO-NO·、X-PPO-NO·、X-P(EO-r-PO)-NO·、X-PEO-b-PPO-NO orX-PPO-bThe polymer of-PEO-NO;
C) respectively taking the polyalkylene oxide of above-mentioned end band nitrogen oxygen activity group NO as free radical scavenger, under radical initiator effect, be under 1:0.5～10,40～125 DEG C of reaction temperatures, the condition in 1～16 hour reaction time in the mol ratio of free radical scavenger and radical initiator, cause the polymerization of hydrophobic type monomer N-substituted acrylamide, reaction obtain respectively corresponding hydrophilic-hydrophobic block type copolymerX-PEO-b-PNAM、X-PPO-b-PNAM、X-P(EO-r-PO)-b-PNAM、X-PEO-b-PPO-b-PNAM orX-PPO-b-PEO-b-PNAM；
D) respectively by above-mentioned hydrophilic-hydrophobic block type copolymer and super high molecular weight polyacrylamide be dissolved in the medium of pH value 7.5～13.5, there is graft copolymerization, obtain respectively the graft modification super high molecular weight polyacrylamide HPAM-that corresponding side chain is hydrophilic-hydrophobic block typeg-(PEO-b-PNAM)、HPAM-g-(PPO-b-PNAM)、HPAM-g-(P(EO-r-PO)-b-PNAM)、HPAM-g-(PEO-b-PPO-b-PNAM) or HPAM-g-(PPO-b-PEO-b-PNAM), wherein,gExpression polymer is graft type.
In technique scheme, step c) described in radical initiator preferred version be selected from least one in azo-initiator or organic peroxide evocating agent, described azo-initiator preferred version is selected from least one in azodiisobutyronitrile, AMBN, ABVN, described organic peroxide preferred version is selected from least one in isopropyl benzene hydroperoxide, cumyl peroxide, benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, the peroxidating pivalic acid tert-butyl ester or peroxy dicarbonate diisobutyl ester. step c) described in hydrophobic type monomer N-substituted acrylamide preferred version be selected from N methacrylamide, N-ethyl acrylamide, N-normal-butyl acrylamide, N tert butyl acrylamide, N-n-hexyl acrylamide, N-cyclohexyl acrylamide, N-n-octyl acrylamide, N-dodecyl acrylamide, N-n-hexadecyl acrylamide, N phenyl acrylamide, N-p-methylphenyl acrylamide, N-is to hydroxyphenyl acrylamide, N, N-DMAA, N, N-diethyl acrylamide, N, N-dibutyl acrylamide, N, N-dihexyl acrylamide, N, N-dioctyl acrylamide, N, N-bis-dodecyl acrylamide or N, at least one in N-bis-n-hexadecyl acrylamides. steps d) described in the ratio preferable range of hydrophilic-hydrophobic block type copolymer, super high molecular weight polyacrylamide and medium, by weight percentage, be 0.05～5.0:0.05～5.0:90.0～99.9. described medium preferred version is selected from least one in the aqueous solution of sodium acid carbonate, saleratus, sodium carbonate, potash, NaOH or potassium hydroxide.
In technique scheme, adopt 2,2,6,6-tetramethyl-4-chloro-1-oxygen phenylpiperidines sodium is that first with reference to CA1252783A method, to adopt mol ratio be 1:1 2,2,6,6-tetramethyl-4-hydroxy piperidine-1-oxygen base free radical and chlorination dimethyl chloride are for imonium salt compound, in DEF solution, under room temperature, react after 4～8 hours, in frozen water, leach crystallization, then obtain 2,2 through washing, being dried, 6,6-tetramethyl-4-chloro piperidines-1-oxygen base free radical; It refluxes 4～8 hours with the sodium metal of a molar equivalent in tetrahydrofuran solution again, the white powder solid 2,2,6 obtaining by filtration drying, 6-tetramethyl-4-chloro-1-oxygen phenylpiperidines sodium.
Key of the present invention is also to have added the appropriate nitrogen oxide with epoxide group and makes telogen, thus prepare series hydrophilic-hydrophobic block type copolymer, regraft on the macromolecular chain of super high molecular weight polyacrylamide. Nitrogen oxide with epoxide group of the present invention is 2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical, it is by 2,2 by classical phase transfer method, 6,6-tetramethyl-4-hydroxy piperidine-1-oxygen base free radical reacts with epoxyhalopropane and makes. Concrete operation method is under alkali condition, to add successively 4-butyl ammonium hydrogen sulfate catalyst, epoxychloropropane, after mixing, in 1～5 hour, dropwise add 2,2,6,6-tetramethyl-4-hydroxy piperidine-1-oxygen base free radical, react 15～30 hours, by extraction, recrystallization, obtain 2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical. Wherein, the feed intake mol ratio of middle epoxychloropropane and 2,2,6,6-tetramethyl-4-hydroxy piperidine-1-oxygen base free radical is 1:0.5～10.
In technique scheme, described hydrophilic-ratio range of hydrophobic block type copolymer, super high molecular weight polyacrylamide and medium, by weight percentage, for: 0.05～5.0:0.05～5.0:90.0～99.9, preferable range is 0.1～3.0:0.2～5.0:92.0～99.7.
By introducing, the nitrogen oxide with epoxide group is telogen to the inventive method, in gained block copolymer, the length of polyethers section, poly-N-substituted acrylamide section can design arbitrarily, it is controlled that molecular structure reaches, adopt the graft modification super high molecular weight polyacrylamide in the present invention to be used for the displacement of reservoir oil, can improve significantly heatproof, anti-salt and ageing resistace, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is up to 89.0%. The existence of hydrophilic-hydrophobic block type grafted chain, give super high molecular weight polyacrylamide strand special association, increase three-dimensional space network structure, under shear action, be difficult for occurring curling, displacement efficiency also can further improve oil recovery factor and reaches 12.4% on water drive basis, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
In dry reaction bottle, inject 0.14mol2,2,6,6-tetramethyl-4-bromo-1-oxygen phenylpiperidines sodium and 2.5mol oxirane, at 47 DEG C, react after 7 hours, add 0.14mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 6 hours at 78 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 760 polyethylene glycol oxideX-PEO-NO. With functionalized polymer 0.07mol and the 0.6molN of above-mentioned preparation, N-DMAA (NDMAM), 0.08mol benzoyl peroxide, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 98 DEG C, react 5 hours, obtain hydrophobic section molecular weight and be 800 block type copolymerX-PEO-b-PNDMAM. It is 3,050 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.05g and 2.0g viscosity average molecular weigh, under strong stirring effect, be scattered in 98g sodium bicarbonate aqueous solution (pH=7.9), under backflow effect, there is graft copolymerization, obtain graft copolymer HPAM-g-(PEO-b-PNDMAM)。
Adopt with the following method or structure and the performance of standard testing gained graft modification super high molecular weight polyacrylamide: measure (viscosimetry) and measure the intrinsic viscosity of polymer by GB/T12005.10-92 Molecular Weight for Polyacrylamide, and by [η]=3.73×10-4 M w 0.66Calculate relative molecular mass; Adopt the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the product BROOKFIELD of Brookfield company of U.S. III type viscosimeter test 1500mg/L concentration at 85 DEG C, 7.34s-1Under apparent viscosity; The polymer salt aqueous solution of pressing Q/SH1020 test 1500mg/L concentration is the thermal stability aging 3 months time under 85 DEG C of oxygen free conditions.
Structural Performance Analysis result to above-mentioned gained graft copolymer is as follows: the viscosity average molecular weigh of gained graft copolymer is 3,100 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 18.7mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 85.5%.
With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 7.1% again.
[embodiment 2]
In dry reaction bottle, inject 0.15mol2,2,6,6-tetramethyl-4-chloro-1-oxygen phenylpiperidines sodium and 2.0mol oxirane, at 55 DEG C, react after 6 hours, add 0.15mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 80 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 550 polyethylene glycol oxideX-PEO-NO. With functionalized polymer 0.06mol and the 0.3molN of above-mentioned preparation, N-dibutyl acrylamide (NDBAM), the 0.07mol peroxidating 2 ethyl hexanoic acid tert-butyl ester, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 102 DEG C, react 7 hours, obtain hydrophobic section molecular weight and be 900 block type copolymerX-PEO-b-PNDBAM. It is 2,800 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.06g and 1.8g viscosity average molecular weigh, under strong stirring effect, be scattered in 98g sodium bicarbonate aqueous solution (pH=9.0), under backflow effect, there is graft copolymerization, obtain graft copolymer HPAM-g-(PEO-b-PNDBAM)。
Adopt structure and the performance of method described in embodiment 1 or standard testing gained graft modification super high molecular weight polyacrylamide, interpretation of result is as follows: the viscosity average molecular weigh of gained graft copolymer is 2,840 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 19.1mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 82.8%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 6.1% again.
[embodiment 3]
In dry reaction bottle, inject 0.13mol2,2,6,6-tetramethyl-4-chloro-1-oxygen phenylpiperidines sodium and 1.8mol expoxy propane, at 52 DEG C, react after 6 hours, add 0.14mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 4 hours at 88 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 800 PPOXX-PPO-NO. With functionalized polymer 0.05mol and the 0.2molN of above-mentioned preparation, N-dioctyl acrylamide (NDOAM), 0.06mol benzoyl peroxide, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 100 DEG C, react 6 hours, obtain hydrophobic section molecular weight and be 900 block type copolymerX-PPO-b-PNDOAM. It is 3,200 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.05g and 1.2g viscosity average molecular weigh, under strong stirring effect, be scattered in 102g NaOH sodium water solution (pH=8.8), under backflow effect, there is graft copolymerization, obtain graft copolymer HPAM-g-(PPO-b-PNDOAM)。
Adopt structure and the performance of method described in embodiment 1 or standard testing gained graft modification super high molecular weight polyacrylamide, interpretation of result is as follows: the viscosity average molecular weigh of gained graft copolymer is 3,210 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 20.1mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 87.2%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 9.5% again.
[embodiment 4]
In dry reaction bottle, inject 0.11mol2,2,6,6-tetramethyl-4-bromo-1-oxygen phenylpiperidines sodium and 1.3mol expoxy propane, at 60 DEG C, react after 5 hours, add 0.12mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 87 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 650 PPOXX-PPO-NO. With functionalized polymer 0.08mol and the 0.18molN of above-mentioned preparation, N-bis-dodecyl acrylamides (NDDAM), 0.10mol azodiisobutyronitrile, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 82 DEG C, react 8 hours, obtain hydrophobic section molecular weight and be 680 block type copolymerX-PPO-b-PNDDAM. It is 3,200 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.08g and 0.98g viscosity average molecular weigh, under strong stirring effect, be scattered in 95g sodium hydrate aqueous solution (pH=10.6), under backflow effect, there is graft copolymerization, obtain the graft copolymer HPAM-of polyacrylamideg-(PPO-b-PNDDAM)。
Adopt structure and the performance of method described in embodiment 1 or standard testing gained graft modification super high molecular weight polyacrylamide, interpretation of result is as follows: the viscosity average molecular weigh of gained graft copolymer is 3,220 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 21.5mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 89.0%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 8.6% again.
[embodiment 5]
In dry reaction bottle, inject 0.18mol2,2,6,6-tetramethyl-4-bromo-1-oxygen phenylpiperidines sodium, 1.0mol oxirane and 1.2mol expoxy propane, at 68 DEG C, react after 6 hours, add 0.19mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 89 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be poly-(ethylene oxide-propylene oxide) random copolymer of 600X-P(EO-r-PO)-NO. With the functionalized polymer 0.05mol of above-mentioned preparation and 0.2molN-cyclohexyl acrylamide (NCHAM), 0.06mol cumyl peroxide, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 78 DEG C, react 8 hours, obtain hydrophobic section molecular weight and be 500 block type copolymerX-P(EO-r-PO)-b-PNCHAM. It is 2,700 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.03g and 1.0g viscosity average molecular weigh, under strong stirring effect, be scattered in 98g aqueous sodium carbonate (pH=12.4), under backflow effect, there is graft copolymerization, obtain graft copolymer HPAM-g-(P(EO-r-PO)-b-PNCHAM)。
Adopt structure and the performance of method described in embodiment 1 or standard testing gained graft modification super high molecular weight polyacrylamide, interpretation of result is as follows: the viscosity average molecular weigh of gained graft copolymer is 2,720 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 17.9mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 81.8%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 12.4% again.
[embodiment 6]
In dry reaction bottle, inject 0.13mol2,2,6,6-tetramethyl-4-chloro-1-oxygen phenylpiperidines sodium and 1.0mol expoxy propane, at 60 DEG C, react after 6 hours, 0.5mol oxirane reinjects, at 60 DEG C, continue reaction after 4 hours, add 0.13mol2,2,6,6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 6 hours at 70 DEG C, adds isopropyl alcohol cessation reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be poly-(propylene oxide-ethylene oxide) block copolymer of 600X-PPO-b-PEO-NO. With the functionalized polymer 0.02mol of above-mentioned preparation and 0.15molN-Phenyl Acrylamide (NBAM), 0.025mol ABVN, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 71 DEG C, react 7 hours, obtain hydrophobic section molecular weight and be 900 block type copolymerX-PPO-b-PEO-b-PNBAM. It is 3,000 ten thousand super high molecular weight polyacrylamide by gained copolymer 0.08g and 1.08g viscosity average molecular weigh, under strong stirring effect, be scattered in 96g potassium bicarbonate aqueous solution (pH=7.7), under backflow effect, there is graft copolymerization, obtain graft copolymer HPAM-g-(PPO-b-PEO-b-PNBAM)。
Adopt structure and the performance of method described in embodiment 1 or standard testing gained graft modification super high molecular weight polyacrylamide, interpretation of result is as follows: the viscosity average molecular weigh of gained graft copolymer is 3,020 ten thousand, the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 19.2mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 81.9%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the polyacrylamide graft copolymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 11.1% again.
[comparative example 1]
With [embodiment 2], just do not implement graft copolymerization, only by gained block type copolymerX-PEO-b-PNDBAM mixes with super high molecular weight polyacrylamide, tests its temperature-resistant anti-salt, ageing-resistant performance and imitation oil displacement experiment test.
The performance that adopts method described in embodiment 1 or standard testing gained blend, interpretation of result is as follows: the saline solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the polymeric blends of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 14.8mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 78.1%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the above-mentioned polymeric blends of metaideophone 0.15PV (rock pore volume), water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 2.3% again.
[comparative example 2]
With [embodiment 4], just do not implement graft copolymerization, only by gained block type copolymerX-PPO-b-PDDAM mixes with super high molecular weight polyacrylamide, tests its temperature-resistant anti-salt, ageing-resistant performance and imitation oil displacement experiment test.
The performance that adopts method described in embodiment 1 or standard testing gained blend, interpretation of result is as follows: the saline solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the polymeric blends of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 13.0mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 71.9%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the above-mentioned polymeric blends of metaideophone 0.15PV (rock pore volume), water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 1.8% again.
[comparative example 3]
Do not implement open loop, controllable polymerization and graft copolymerization, only the performance of super high molecular weight polyacrylamide used in [embodiment 6] is analyzed, adopted method described in embodiment 1 or its temperature-resistant anti-salt of standard testing, ageing-resistant performance and simulation displacement experiment.
Interpretation of result is as follows: the polymer salt aqueous solution (total salinity 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 DEG C, 7.34s-1Under apparent viscosity be 10.1mPas, the viscosity retention ratio under 85 DEG C of oxygen free conditions aging 3 months time is 51.1%. With salinity 32868mg/L, by rock core, (length is 30 centimetres to the injected water of calcium ions and magnesium ions concentration 874mg/L, and diameter is 2.5 centimetres, and permeability is 1.5 microns2) saturated, the pore volume (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 DEG C of constant temperature, carry out imitation oil displacement experiment test: first water drive is to moisture 92%, record water drive and improve oil recovery factor 30.8%, again after the above-mentioned polymeric blends of metaideophone 0.15PV (rock pore volume), water drive, to moisture 99.0%, record on water drive basis and can improve oil recovery factor 1.1% again.
Claims (7)
1. a graft modification polypropylene acid amides, has following chemical general formula:
HPAM-g-R
Wherein, HPAM is super high molecular weight polyacrylamide;
R is for being selected from PEO-b-PNAM, PPO-b-PNAM, P (EO-r-PO)-b-PNAM, PEO-b-PPO-b-PNAMOr one in PPO-b-PEO-b-PNAM;
EO is oxirane;
PO is expoxy propane;
PEO is PEO;
PPO is PPOX;
PNAM is poly-N-substituted acrylamide, the hydrophobic type monomer N-substituted acrylamide choosing in poly-N-substituted acrylamideJust own from N methacrylamide, N-ethyl acrylamide, N-normal-butyl acrylamide, N tert butyl acrylamide, N-Base acrylamide, N-cyclohexyl acrylamide, N-n-octyl acrylamide, N-dodecyl acrylamide, N-positive 16Alkyl acrylamide, N phenyl acrylamide, N-p-methylphenyl acrylamide, N-be to hydroxyphenyl acrylamide, N, N-bis-Methacrylamide, N, N-diethyl acrylamide, N, N-dibutyl acrylamide, N, N-dihexyl acrylamide,N, N-dioctyl acrylamide, N, N-bis-dodecyl acrylamide or N, in N-bis-n-hexadecyl acrylamidesAt least one;
Viscosity average molecular weigh >=2,700 ten thousand of this graft modification polypropylene acid amides; The repetitive of monomer in PEO, PPO, PNAMNumber is all selected from the arbitrary integer in 1～100.
2. graft modification polypropylene acid amides claimed in claim 1, is characterized in that R adopts active free radical polymerization sideThe controlled block type copolymer of molecular weight that method makes, the b in its molecular formula represents that copolymer is block type, r represents copolymerizationThing is random.
3. the preparation method of graft modification polypropylene acid amides claimed in claim 1, comprises the following steps:
A) taking at least one epoxyalkane in oxirane or expoxy propane as raw material, with 2,2,6,6-tetramethyl-4-halogenBase-1-oxygen phenylpiperidines sodium is initator, the mol ratio of initator and epoxyalkane be 1:1～200, reaction temperature 20～Under 120 DEG C, the condition in 2～15 hours reaction time, reaction obtain respectively X-PEO, X-PPO, X-P (EO-r-PO),The polymer of X-PEO-b-PPO or X-PPO-b-PEO, X is 2,2,6,6-tetramethyl-4-halogen-1-oxygen phenylpiperidines base;
B) respectively in the polymer of X-PEO, X-PPO, X-P (EO-r-PO), X-PEO-b-PPO or X-PPO-b-PEOAdd the nitrogen oxide 2,2,6 with epoxide group, 6-tetramethyl-4-glycidyl oxygen phenylpiperidines-1-oxygen base free radical, 50～At 125 DEG C, continue reaction 1～8 hour, reaction obtains respectively the polyalkylene oxide of associated end band nitrogen oxygen activity group NOX-PEO-NO, X-PPO-NO, X-P (EO-r-PO)-NO, X-PEO-b-PPO-NO or X-PPO-b-PEO-NO'sPolymer;
C) respectively taking the polyalkylene oxide of above-mentioned end band nitrogen oxygen activity group NO as free radical scavenger, cause at free radicalUnder agent effect, the mol ratio of free radical scavenger and radical initiator be 1:0.5～10,40～125 DEG C of reaction temperatures,Under the condition in 1～16 hour reaction time, cause the polymerization of hydrophobic type monomer N-substituted acrylamide, reaction obtains respectively correspondingHydrophilic-hydrophobic block type copolymer X-PEO-b-PNAM, X-PPO-b-PNAM, X-P (EO-r-PO)-b-PNAM,X-PEO-b-PPO-b-PNAM or X-PPO-b-PEO-b-PNAM;
D) respectively by above-mentioned hydrophilic-hydrophobic block type copolymer and super high molecular weight polyacrylamide be dissolved in pH value 7.5～13.5Medium in, occur graft copolymerization, obtain respectively the graft modification superelevation that corresponding side chain is hydrophilic-hydrophobic block typeMolecular weight polypropylene acid amides HPAM-g-(PEO-b-PNAM), HPAM-g-(PPO-b-PNAM),HPAM-g-(P (EO-r-PO)-b-PNAM), HPAM-g-(PEO-b-PPO-b-PNAM) orHPAM-g-(PPO-b-PEO-b-PNAM), wherein, g represents that polymer is graft type.
4. the preparation method of graft modification polypropylene acid amides according to claim 3, is characterized in that c) middle institute of stepState radical initiator and be selected from least one in azo-initiator or organic peroxide evocating agent; Described azo causesAgent is selected from least one in azodiisobutyronitrile, AMBN, ABVN; Described organic peroxide choosingFrom isopropyl benzene hydroperoxide, cumyl peroxide, benzoyl peroxide, the peroxidating 2 ethyl hexanoic acid tert-butyl ester, peroxidatingAt least one in the pivalic acid tert-butyl ester or peroxy dicarbonate diisobutyl ester.
5. the preparation method of graft modification polypropylene acid amides according to claim 3, is characterized in that c) middle institute of stepState hydrophobic type monomer N-substituted acrylamide and be selected from N methacrylamide, N-ethyl acrylamide, N-normal-butyl acryloylAmine, N tert butyl acrylamide, N-n-hexyl acrylamide, N-cyclohexyl acrylamide, N-n-octyl acrylamide,N-dodecyl acrylamide, N-n-hexadecyl acrylamide, N phenyl acrylamide, N-p-methylphenyl acrylamide,N-is to hydroxyphenyl acrylamide, N,N-DMAA, N, N-diethyl acrylamide, N, N-dibutyl thirdAlkene acid amides, N, N-dihexyl acrylamide, N, N-dioctyl acrylamide, N, N-bis-dodecyl acrylamidesOr N, at least one in N-bis-n-hexadecyl acrylamides.
6. the preparation method of graft modification polypropylene acid amides according to claim 3, is characterized in that steps d) middle instituteState the ratio range of hydrophilic-hydrophobic block type copolymer, super high molecular weight polyacrylamide and medium, by weight percentage,For: 0.05～5.0:0.05～5.0:90.0～99.9.
7. the preparation method of graft modification polypropylene acid amides according to claim 3, is characterized in that described medium choosingAt least one in the aqueous solution of sodium acid carbonate, saleratus, sodium carbonate, potash, NaOH or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210393357.1A CN103772713B (en) | 2012-10-17 | 2012-10-17 | Graft modification polypropylene acid amides and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210393357.1A CN103772713B (en) | 2012-10-17 | 2012-10-17 | Graft modification polypropylene acid amides and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772713A CN103772713A (en) | 2014-05-07 |
| CN103772713B true CN103772713B (en) | 2016-05-18 |
Family
ID=50565516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210393357.1A Active CN103772713B (en) | 2012-10-17 | 2012-10-17 | Graft modification polypropylene acid amides and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772713B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109837746B (en) * | 2019-01-24 | 2021-05-07 | 华北水利水电大学 | Hydrophobic polypropylene fiber for water treatment and preparation method thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5134215A (en) * | 1990-10-15 | 1992-07-28 | Nalco Chemical Company | Method for reducing fluid loss from oilfield cement slurries using vinyl grafted wattle tannin |
| CN101284893A (en) * | 2008-06-06 | 2008-10-15 | 成都理工大学 | Comb-typed amphiphilic water-soluble co-polymer, method for preparing same and use |
| CN101492515A (en) * | 2009-01-23 | 2009-07-29 | 成都理工大学 | Acrylic amide modified graft copolymer, preparation method and application thereof |
| CN102050913A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Temperature and salt resistant grafted polyacrylamide and preparation method thereof |
| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
| CN102051165A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Xanthan gum graft copolymer oil displacement agent as well as preparation method and application thereof |
| CN102382241A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Long-branched chain polyacrylamide copolymer and preparation method thereof |
| CN102453252A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylamide type macromonomer and comb type copolymer, and preparation method and application thereof |
| CN102464782A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Thermal thickening water-soluble terpolymer and preparation method and application thereof |
| WO2012069478A1 (en) * | 2010-11-24 | 2012-05-31 | Basf Se | Method for oil recovery using hydrophobically associating polymers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7351681B2 (en) * | 2004-02-17 | 2008-04-01 | Halliburton Energy Services, Inc. | Well bore servicing fluids comprising thermally activated viscosification compounds and methods of using the same |
-
2012
- 2012-10-17 CN CN201210393357.1A patent/CN103772713B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5134215A (en) * | 1990-10-15 | 1992-07-28 | Nalco Chemical Company | Method for reducing fluid loss from oilfield cement slurries using vinyl grafted wattle tannin |
| CN101284893A (en) * | 2008-06-06 | 2008-10-15 | 成都理工大学 | Comb-typed amphiphilic water-soluble co-polymer, method for preparing same and use |
| CN101492515A (en) * | 2009-01-23 | 2009-07-29 | 成都理工大学 | Acrylic amide modified graft copolymer, preparation method and application thereof |
| CN102051165A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Xanthan gum graft copolymer oil displacement agent as well as preparation method and application thereof |
| CN102050913A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Temperature and salt resistant grafted polyacrylamide and preparation method thereof |
| CN102050926A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof |
| CN102382241A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Long-branched chain polyacrylamide copolymer and preparation method thereof |
| CN102453252A (en) * | 2010-10-20 | 2012-05-16 | 中国石油化工股份有限公司 | Acrylamide type macromonomer and comb type copolymer, and preparation method and application thereof |
| CN102464782A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Thermal thickening water-soluble terpolymer and preparation method and application thereof |
| WO2012069478A1 (en) * | 2010-11-24 | 2012-05-31 | Basf Se | Method for oil recovery using hydrophobically associating polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772713A (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448125B (en) | Amphoteric hydrophobically-associating polymer and preparation method thereof | |
| CN104448127B (en) | Polymer mobility control agent suitable for special high salinity reservoirs and preparation method thereof | |
| CN104448128B (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN104449636B (en) | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir | |
| CN102433108B (en) | Temperature-resistance salt-resistance filtrate reducer for drilling fluid and preparation method thereof | |
| CN104388063B (en) | Micro-crosslinked polymer fluid loss additive for drilling fluid and preparation method thereof | |
| CN103666433A (en) | Oil-displacing agent composition used for improving recovery ratio of high-temperature reservoir and preparation method of composition | |
| CN103539946A (en) | Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof | |
| CN105566516A (en) | Structure-oriented composite initiator system, acrylamide polymer and preparation method and application of acrylamide polymer | |
| CN103897115B (en) | Terpolymer as concrete workability improver | |
| CN101157741A (en) | Synthesis technology of high molecular weight temperature-tolerant anti-salt polyacrylamide | |
| CN105566560A (en) | Structure-oriented composite initiator system and acrylamide polymer and preparation method and application thereof | |
| CN103788295B (en) | A kind of two-step method prepares the method for acrylamide based copolymer | |
| CN103772713B (en) | Graft modification polypropylene acid amides and preparation method thereof | |
| CN102464797B (en) | Enether monomer, water-soluble thermothickening copolymer, preparation method, application thereof | |
| CN104628943B (en) | A kind of acrylamide based copolymer and its preparation method and application | |
| CN102453254B (en) | Acrylic acid ester compound and polymer, preparation method and application thereof | |
| CN103539947B (en) | Graft modification super high molecular weight polyacrylamide and preparation method thereof | |
| CN102559156B (en) | High temperature high salinity fluid loss agent for drilling fluid and preparation method thereof | |
| CN104152130A (en) | AM /NaAA/NIDA hydrophobic association polymer oil displacement agent and synthetic method thereof | |
| CN102464783B (en) | Water-soluble thermo-thickening copolymer, and preparation method and application thereof | |
| CN107226886B (en) | A kind of polymer and its preparation method and application with surface active function | |
| CN107226887B (en) | A kind of polymer and its preparation method and application with surface active function | |
| CN108503748A (en) | A kind of temperature-resistant anti-salt functional form polymer and preparation method thereof | |
| CN106588754A (en) | Styrene compound and acrylamide copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |