CN103772713A - Graft-modified polyacrylamide and preparation method thereof - Google Patents
Graft-modified polyacrylamide and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a graft-modified polyacrylamide and a preparation method thereof, and is used for mainly solving the problems in the prior art that polyacrylamide has poor temperature resistance, poor salt resistance, poor aging resistance and poor displacement efficiency. The graft-modified polyacrylamide has the chemical formula of HPAM-g-R, wherein HPAM is an ultra-high molecular weight polyacrylamide, R is selected from one of PEO-b-PNAM, PPO-b-PNAM, P(EO-r-PO)-b-PNAM, PEO-b-PPO-b-PNAM or PPO-b-PEO-b-PNAM, EO represents epoxy ethane, PO represents propylene oxide, PEO represents polyethylene oxide, PPO represents polypropylene oxide, and PNAM represents poly(N-substituted acrylamide); the viscosity average molecular weight of the graft-modified polyacrylamide is not less than 27000000; the preparation method is provided. Through adopting the above technical schemes, the problems are relatively well solved, and the graft-modified polyacrylamide can be used in industrial production of a polymer oil-displacing agent and in oil displacement of a high-temperature high-salinity oil reservoir.
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 polymers: 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 ℃) improve tar productivity under comparatively high temps in anaerobic, without divalent ion environment, when conventional water-soluble polymers 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 ℃, 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; Soltion 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 investigator has carried out a large amount of research to polyacrylamide polymers for oil displacement macromole 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-displacing agent, adopt graft copolymerization method that heat-resistance type function monomer is introduced on xanthan gum macromolecular chain, improved viscoelasticity and the biologically stable of biomacromolecule.Document (B ü y ü kya c A, Tuzcu G, Aras L. Synthesis of copolymers of methoxy polyethylene glycol acrylate and 2-acrylamido-2-methyl-1-propanesulfonic acid:Its characterization and application as superplasticizer in concrete. Cement and Concrete Research, 2009, 39 (7): 629-635.) reported the synthetic and application as the polyacrylamide graft copolymer of polymeric surface active agent, the large monomer adopting is mainly the Soxylat A 25-7 esters of acrylic acid of facile hydrolysis under acid or alkaline condition.And the above-mentioned polymkeric substance 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 antisalt ageing resistance and the tertiary oil recovery displacement research etc. of molecular weight equimolecular textural 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 efficiency of displacement, 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 efficiency of displacement 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 oxyethane;
PO is propylene oxide;
PEO is polyethylene oxide;
PPO is poly(propylene oxide);
PNAM is poly-N-substituted acrylamide;
Viscosity-average molecular weight >=2,700 ten thousand of this graft modification polypropylene acid amides.
In technique scheme, R is the controlled block type multipolymer of molecular weight that adopts active free radical polymerization method to make, in its molecular formula
bexpression multipolymer is block type,
rexpression multipolymer 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) take at least one epoxy alkane in oxyethane or propylene oxide as raw material, with 2,2,6,6-tetramethyl--4-halogen-1-oxygen phenylpiperidines sodium is initiator, be under 1:1～200,20～120 ℃ of temperature of reaction, the condition in 2～15 hours reaction times in the mol ratio of initiator and epoxy alkane, reaction obtains respectively
x-PEO,
x-PPO,
x-P (EO-
r-PO),
x-PEO-
b-PPO or
x-PPO-
bthe polymkeric substance of-PEO,
xit is 2,2,6,6-tetramethyl--4-halogen-1-oxygen phenylpiperidines base;
B) respectively to
x-PEO,
x-PPO,
x-P (EO-
r-PO),
x-PEO-
b-PPO or
x-PPO-
bin the polymkeric substance of-PEO, add the oxynitride 2,2,6 with epoxide group, 6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical, at 50～125 ℃, continue reaction 1～8 hour, reaction obtains respectively the polyalkylene oxide of associated end band nitrogen oxygen activity group NO
x-PEO-NO,
x-PPO-NO,
x-P (EO-
r-PO)-NO,
x-PEO-
b-PPO-NO or
x-PPO-
bthe polymkeric substance of-PEO-NO;
C) respectively take 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 ℃ of temperature of reaction, the condition in 1～16 hour reaction times 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 multipolymer
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 multipolymer 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 type
g-(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 polymkeric substance 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 Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organo-peroxide preferred version is selected from least one in isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, the peroxidation trimethylacetic 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 multipolymer, 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 bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide 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 diethylformamide 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 99.5 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 oxynitride with epoxide group and makes telogen, thus prepare series hydrophilic-hydrophobic block type multipolymer, regraft on the macromolecular chain of super high molecular weight polyacrylamide.Oxynitride with epoxide group of the present invention is 2,2,6,6-tetramethyl--4-epoxypropyl 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 alkaline condition, to add successively 4-butyl ammonium hydrogen sulfate catalyzer, epoxy chloropropane, 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-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical.Wherein, the feed intake mol ratio of middle epoxy chloropropane 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 multipolymer, 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 oxynitride with epoxide group is telogen to the inventive method, in gained segmented 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 resistance, the viscosity retention ratio under 85 ℃ 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 molecular chain special association, increase three-dimensional space network structure, under shearing action, be difficult for occurring curling, efficiency of displacement 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.
Embodiment
[embodiment 1]
In dry reaction bottle, inject 0.14mol 2,2,6,6-tetramethyl--4-bromo-1-oxygen phenylpiperidines sodium and 2.5mol oxyethane, at 47 ℃, react after 7 hours, add 0.14mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 6 hours at 78 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 760 polyoxyethylene
x-PEO-NO.With functionalized polymer 0.07mol and the 0.6mol N of above-mentioned preparation, N-DMAA (NDMAM), 0.08mol benzoyl peroxide, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 98 ℃, react 5 hours, obtain hydrophobic section molecular weight and be 800 block type multipolymer
x-PEO-
b-PNDMAM.It is 3,050 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.05g and 2.0g viscosity-average molecular weight, 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 polymkeric substance 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 mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the product BROOKFIELD of Brookfield company of U.S. III type viscometer test 1500mg/L concentration at 85 ℃, 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 ℃ of oxygen free conditions.
Structural Performance Analysis result to above-mentioned gained graft copolymer is as follows: the viscosity-average molecular weight of gained graft copolymer is 3,100 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 18.7mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 0.15mol 2,2,6,6-tetramethyl--4-chloro-1-oxygen phenylpiperidines sodium and 2.0mol oxyethane, at 55 ℃, react after 6 hours, add 0.15mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 80 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 550 polyoxyethylene
x-PEO-NO.With functionalized polymer 0.06mol and the 0.3mol N of above-mentioned preparation, N-dibutyl acrylamide (NDBAM), the 0.07mol peroxidation 2 ethyl hexanoic acid tert-butyl ester, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 102 ℃, react 7 hours, obtain hydrophobic section molecular weight and be 900 block type multipolymer
x-PEO-
b-PNDBAM.It is 2,800 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.06g and 1.8g viscosity-average molecular weight, 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 weight of gained graft copolymer is 2,840 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 19.1mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 0.13mol 2,2,6,6-tetramethyl--4-chloro-1-oxygen phenylpiperidines sodium and 1.8mol propylene oxide, at 52 ℃, react after 6 hours, add 0.14mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 4 hours at 88 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 800 polyoxytrimethylene
x-PPO-NO.With functionalized polymer 0.05mol and the 0.2mol N 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 ℃, react 6 hours, obtain hydrophobic section molecular weight and be 900 block type multipolymer
x-PPO-
b-PNDOAM.It is 3,200 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.05g and 1.2g viscosity-average molecular weight, under strong stirring effect, be scattered in 102g sodium hydroxide 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 weight of gained graft copolymer is 3,210 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 20.1mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 0.11mol 2,2,6,6-tetramethyl--4-bromo-1-oxygen phenylpiperidines sodium and 1.3mol propylene oxide, at 60 ℃, react after 5 hours, add 0.12mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 87 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be 650 polyoxytrimethylene
x-PPO-NO.With functionalized polymer 0.08mol and the 0.18mol N of above-mentioned preparation, N-bis-dodecyl acrylamides (NDDAM), 0.10mol Diisopropyl azodicarboxylate, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 82 ℃, react 8 hours, obtain hydrophobic section molecular weight and be 680 block type multipolymer
x-PPO-
b-PNDDAM.It is 3,200 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.08g and 0.98g viscosity-average molecular weight, under strong stirring effect, be scattered in 95g aqueous sodium hydroxide solution (pH=10.6), under backflow effect, there is graft copolymerization, obtain the graft copolymer HPAM-of polyacrylamide
g-(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 weight of gained graft copolymer is 3,220 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 21.5mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 0.18mol 2,2,6,6-tetramethyl--4-bromo-1-oxygen phenylpiperidines sodium, 1.0mol oxyethane and 1.2mol propylene oxide, at 68 ℃, react after 6 hours, add 0.19mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 5 hours at 89 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be poly-(ethylene oxide-propylene oxide) random copolymers of 600
x-P (EO-
r-PO)-NO.With the functionalized polymer 0.05mol of above-mentioned preparation and 0.2mol N-cyclohexyl acrylamide (NCHAM), 0.06mol dicumyl peroxide, add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 78 ℃, react 8 hours, obtain hydrophobic section molecular weight and be 500 block type multipolymer
x-P (EO-
r-PO)-
b-PNCHAM.It is 2,700 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.03g and 1.0g viscosity-average molecular weight, 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 weight of gained graft copolymer is 2,720 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 17.9mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 0.13mol 2,2,6,6-tetramethyl--4-chloro-1-oxygen phenylpiperidines sodium and 1.0mol propylene oxide, at 60 ℃, react after 6 hours, 0.5mol oxyethane reinjects, at 60 ℃, continue reaction after 4 hours, add 0.13mol 2,2,6,6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical continues reaction 6 hours at 70 ℃, adds Virahol termination reaction, with after ether sedimentation, obtain hydrophilic section molecular weight and be poly-(propylene oxide-ethylene oxide) segmented copolymer of 600
x-PPO-
b-PEO-NO.With the functionalized polymer 0.02mol of above-mentioned preparation and 0.15mol N phenyl acrylamide (NBAM), 0.025mol 2,2'-Azobis(2,4-dimethylvaleronitrile), add in reactor, letting nitrogen in and deoxidizing, be uniformly mixed, at 71 ℃, react 7 hours, obtain hydrophobic section molecular weight and be 900 block type multipolymer
x-PPO-
b-PEO-
b-PNBAM.It is 3,000 ten thousand super high molecular weight polyacrylamide by gained multipolymer 0.08g and 1.08g viscosity-average molecular weight, 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 weight of gained graft copolymer is 3,020 ten thousand, the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 19.2mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 multipolymer
x-PEO-
b-PNDBAM mixes with super high molecular weight polyacrylamide, tests its temperature resistant antisalt, 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 salt brine solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the polymeric blends of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 14.8mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 multipolymer
x-PPO-
b-PDDAM mixes with super high molecular weight polyacrylamide, tests its temperature resistant antisalt, 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 salt brine solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of the polymeric blends of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 13.0mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 antisalt of standard testing, ageing-resistant performance and simulation displacement test.
Interpretation of result is as follows: the polymer salt aqueous solution (total mineralization 32868mg/L, calcium ions and magnesium ions concentration 874mg/L) of 1500mg/L concentration is at 85 ℃, 7.34s
-1under apparent viscosity be 10.1mPas, the viscosity retention ratio under 85 ℃ 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 rate of permeation is 1.5 microns
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then carry out saturated with Shengli Oil Field block dewatered oil, under 85 ℃ 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 (8)
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-PNAM or PPO-
b-PEO-
bone in-PNAM;
EO is oxyethane;
PO is propylene oxide;
PEO is polyethylene oxide;
PPO is poly(propylene oxide);
PNAM is poly-N-substituted acrylamide;
Viscosity-average molecular weight >=2,700 ten thousand of this graft modification polypropylene acid amides.
2. graft modification polypropylene acid amides claimed in claim 1, is characterized in that R is the controlled block type multipolymer of molecular weight that adopts active free radical polymerization method to make, in its molecular formula
bexpression multipolymer is block type,
rexpression multipolymer is random.
3. graft modification polypropylene acid amides claimed in claim 1, is characterized in that the number of repeat unit of monomer in PEO, PPO, PNAM is all selected from the arbitrary integer in 1～100.
4. the preparation method of graft modification polypropylene acid amides claimed in claim 1, comprises the following steps:
A) take at least one epoxy alkane in oxyethane or propylene oxide as raw material, with 2,2,6,6-tetramethyl--4-halogen-1-oxygen phenylpiperidines sodium is initiator, be under 1:1～200,20～120 ℃ of temperature of reaction, the condition in 2～15 hours reaction times in the mol ratio of initiator and epoxy alkane, reaction obtains respectively
x-PEO,
x-PPO,
x-P (EO-
r-PO),
x-PEO-
b-PPO or
x-PPO-
bthe polymkeric substance of-PEO,
xit is 2,2,6,6-tetramethyl--4-halogen-1-oxygen phenylpiperidines base;
B) respectively to
x-PEO,
x-PPO,
x-P (EO-
r-PO),
x-PEO-
b-PPO or
x-PPO-
bin the polymkeric substance of-PEO, add the oxynitride 2,2,6 with epoxide group, 6-tetramethyl--4-epoxypropyl oxygen phenylpiperidines-1-oxygen base free radical, at 50～125 ℃, continue reaction 1～8 hour, reaction obtains respectively the polyalkylene oxide of associated end band nitrogen oxygen activity group NO
x-PEO-NO,
x-PPO-NO,
x-P (EO-
r-PO)-NO,
x-PEO-
b-PPO-NO or
x-PPO-
bthe polymkeric substance of-PEO-NO;
C) respectively take 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 ℃ of temperature of reaction, the condition in 1～16 hour reaction times 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 multipolymer
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 multipolymer 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 type
g-(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 polymkeric substance is graft type.
5. the preparation method of graft modification polypropylene acid amides according to claim 4, is characterized in that described in step c) that radical initiator is selected from least one in azo-initiator or organic peroxide evocating agent; Described azo-initiator is selected from least one in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile); Described organo-peroxide is selected from least one in isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, the peroxidation trimethylacetic acid tert-butyl ester or peroxy dicarbonate diisobutyl ester.
6. the preparation method of graft modification polypropylene acid amides according to claim 4, it is characterized in that described in step c) that hydrophobic type monomer N-substituted acrylamide is 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.
7. the preparation method of graft modification polypropylene acid amides according to claim 4, it is characterized in that steps d) described in the ratio range of hydrophilic-hydrophobic block type multipolymer, super high molecular weight polyacrylamide and medium, by weight percentage, be 0.05～5.0:0.05～5.0:90.0～99.9.
8. the preparation method of graft modification polypropylene acid amides according to claim 4, is characterized in that described medium is selected from least one in the aqueous solution of sodium bicarbonate, saleratus, sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide.
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Cited By (1)
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|---|---|---|---|---|
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