CN103539946A - Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof - Google Patents
Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof Download PDFInfo
- Publication number
- CN103539946A CN103539946A CN201210239960.4A CN201210239960A CN103539946A CN 103539946 A CN103539946 A CN 103539946A CN 201210239960 A CN201210239960 A CN 201210239960A CN 103539946 A CN103539946 A CN 103539946A
- Authority
- CN
- China
- Prior art keywords
- acrylamide
- polymer
- hydrophobic
- hydrophobic polymer
- graft modification
- 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.)
- Granted
Links
Abstract
The invention provides a hydrophobic polymer graft modified acrylamide polymer and a preparation method thereof, mainly for solving the problem in the prior art that general acrylamide polymers have poor temperature resistance, poor resistance to salinity, poor ageing-resistance performance and poor displacement effect. The chemical general formula of the hydrophobic polymer graft modified acrylamide polymer is P-g-X, wherein P is polyacrylamide or acrylamide polymer, X is hydrophobic polymer the molecular chain structure of which is in a form of homopolymerisation, random copolymerization or block copolymerization, and the viscosity average molecular weight of the graft compound is more than or equal to seventeen million. The adoption of the hydrophobic polymer graft modified acrylamide polymer and the preparation method thereof well solves the problem in the prior, and the technical scheme can be used in industrial production and displacement of reservoir oil.
Description
Technical field
The present invention relates to tertiary oil recovery field, be specifically related to a kind of hydrophobic polymer graft modification acrylamide polymer 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 when temperature is higher; After formation temperature surpasses 75 ℃, 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 the displacement of reservoir oil with acrylic amide macromole so that its special reservoir condition while meeting field use.Although appropriate heatproof, anti-salt monomer and acrylamide are carried out to copolymerization, can improve to a certain extent the temperature resistant antisalt performance of polymkeric substance, but still cannot meet the requirement of current height or ultra-high water-containing, high salinity reservoirs was.
Graft copolymer is because it shows good rheological property and stability compared with large molecular chain structure.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.Also has investigator according to polymer molecule principle of design; lengthen the side group of novel monomeric; obtain the larger comb shaped antisalt polymer of hydraulic radius of curling more difficult, the molecular chain rotation of molecular chain, and in tertiary oil production in oil field and the application of deep transfer drive, obtained the good effect that increases oil, falls cost and protection of the environment.And the above-mentioned molecular weight distribution that is grafted to the polymkeric substance side chain on macromolecular chain is all wider, chain length differs and is uncontrollable, and this brings difficulty to the temperature resistant antisalt ageing resistance of graft copolymer and tertiary oil recovery displacement research etc. for further Study Polymer Melts grafted chain length and molecular weight equimolecular textural factor.
Summary of the invention
One of technical problem to be solved by this invention be in prior art general acrylamide polymer when adopting field for three, there is the problem of temperature resistant antisalt ageing-resistant performance and displacement weak effect, a kind of new hydrophobic polymer graft modification acrylamide polymer is provided.This hydrophobic polymer graft modification acrylamide polymer has advantages of that temperature resistant antisalt ageing-resistant performance is good and displacement effect is high.Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with the hydrophobic polymer graft modification acrylamide polymer 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 hydrophobic polymer graft modification acrylamide polymer, has following chemical general formula:
P-
g-X
Wherein, P is polyacrylamide or acrylamide based copolymer;
X is the hydrophobic polymer that molecular chain structure is homopolymerization type, random copolymerization type or block copolymerization type;
Viscosity-average molecular weight >=1,700 ten thousand of this hydrophobic polymer graft modification acrylamide polymer.
In technique scheme, X adopts oxynitride to telomerize the controlled hydrophobic polymer of activity that free radical polymerisation process makes.Monomeric repeating unit number in X is selected from the arbitrary integer in 1～200.
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 hydrophobic polymer graft modification acrylamide polymer, comprises the following steps:
A) take hydrophobic monomer as raw material, functionalized 3-(1-the phenyl ethoxy)-3-aza-hexane derivative of take is telogen, mol ratio at telogen, radical initiator and hydrophobic monomer is under 1:0.1～10:1～500,30～130 ℃ of temperature of reaction, the condition in 2～20 hours reaction times, cause hydrophobic monomer and telomerize radical polymerization, obtain the hydrophobic polymer X that molecular chain is homopolymerization type, random copolymerization type or block copolymerization type structure;
B) above-mentioned gained hydrophobic polymer is mixed with acrylamide polymer, under medium and backflow effect, graft copolymerization occurs, obtain the graft modification acrylamide polymer P-that side chain is hydrophobic type
g-X, wherein,
gexpression product is graft type.
In technique scheme, functionalized 3-(1-the phenyl ethoxy)-3-aza-hexane derivative preferred version of step described in a) is selected from 1-function base-2, 2, 4, 4-tetramethyl--3-(1-phenyl ethoxy)-3-aza-pentane, 1-function base-2, 5-dimethyl-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 1-function base-2, 2, 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 1-function base-2, 5, 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane or 1-function base-2, 2, 5, at least one in 5-tetramethyl--3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane.The functional group preferred version of functionalized 3-(1-phenyl ethoxy)-3-aza-hexane derivative is selected from a kind of in hydroxyl, alkoxyl group, halogen, alkoxy carbonyl, carboxyl, aldehyde radical or amido.The radical initiator preferred version of step described in a) is 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 organic peroxide evocating agent preferred version is selected from least one in hydrogen peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxy dicarbonate diisobutyl ester or 1,1-di-t-butyl peroxy hexanaphthene.The hydrophobic monomer preferred version of step described in a) is selected from N tert butyl acrylamide, N-normal-butyl acrylamide, N-n-hexyl acrylamide, N-n-octyl acrylamide, N-dodecyl acrylamide, N-n-hexadecyl acrylamide, N phenyl acrylamide, N, N-DMAA, N, N-dibutyl acrylamide, N, at least one in N-dioctyl acrylamide, butyl acrylate, butyl methacrylate, vinylbenzene, 4-t-butyl styrene, 4-Vinyl phenol, NEM or N-phenylmaleimide.By weight percentage, the ratio preferable range of the hydrophobic polymer step b), acrylamide polymer and medium is: 0.01～5.0:0.01～5.0:90.0～99.98, more preferably scope is 0.1～3.5:0.1～3.5:93.0～99.8.Described medium is selected from least one in the aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, sodium carbonate or salt of wormwood that pH value preferable range is 7.2～13.8.
The key of the inventive method has been to add the appropriate oxynitride with functional group and has made telogen, prepares the controlled hydrophobic associated polymer of Series Molecules chain, regrafts on the macromolecular chain of acrylamide polymer.
The functionalized 3-adopting in the present invention (1-phenyl ethoxy)-3-aza-hexane derivative is reference literature (Benoit D, Chaplinski V, Braslau R, Hawker C J. Development of a universal alkoxyamine for " living " free radical polymerizations. Journal of the American Chemical Society, 1999, 121:3904-3920.) in method, by to 5mL 1-trimethylsiloxy group-2, 2, in the methanol solution of 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane (0.241mol), add 50mg citric acid, in room temperature, stir lower reaction after 5 minutes, solution is after vacuum filtration, with hexane/ethyl acetate mixed solvent (volume ratio 30:1), thick product wash-out is carried out to rapid column chromatography, 1-hydroxyl-2 of the colorless oil obtaining, 2, 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane.
The inventive method is telogen by introducing functionalized 3-(1-phenyl ethoxy)-3-aza-hexane derivative, in the controlled hydrophobic polymer of gained chain, the length of micro-block can design arbitrarily, it is controlled that molecular structure reaches, adopt the hydrophobic polymer graft modification acrylamide polymer in the present invention, can further improve significantly temperature resistant antisalt, ageing resistance and the displacement effect of acrylamide polymer, the viscosity retention ratio under 85 ℃ of oxygen free conditions aging 3 months time is up to 93.4%.The existence of hydrophobic type grafted chain has increased the space structure of acrylamide polymer, and give its special three-dimensional space network structure, under shearing action, be also difficult for generation curling, efficiency of displacement can further improve oil recovery factor and reaches 10.8% on water drive basis, has obtained good result.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
In dry reaction bottle, inject 0.10mol 1-hydroxyl-2,2,5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 0.12mol dicumyl peroxide and 0.8mol N, N-DMAA, at 87 ℃, react after 6 hours, add Virahol termination reaction, with after ether sedimentation, the molecular weight obtaining is 770 the poly-N,N-DMAA homopolymer of hydrophobic association type.It by resulting polymers 0.08g and 2.2g viscosity-average molecular weight, is 2,850 ten thousand polyacrylamide, under strong stirring effect, be scattered in 97g wet chemical (pH=8.0), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly acrylamide-
g-poly-N,N-DMAA.
Adopt following method or standard testing gained to dredge structure and the performance of polymer graft modification polyacrylamide: press GB/T12005.10-92 Molecular Weight for Polyacrylamide and measure the intrinsic viscosity that (viscosimetry) measures polymkeric substance, 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 U.S. Brookfield company 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; Displacement test: with salinity 32868mg/L, (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 by rock core
2) saturated, the volume of voids (PV) of measuring rock core is 48.8%, then with Shengli Oil Field block dewatered oil, carry out saturated, 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 hydrophobic polymer graft modification acrylamide polymer of metaideophone 0.15PV (rock pore volume) synthesized, water drive, to moisture 99.0%, records the recovery ratio that can improve again crude oil on water drive basis.
Result to above-mentioned analysis is as shown in table 1.
[embodiment 2]
In dry reaction bottle, inject 0.13mol 1-chloro-2,5-dimethyl-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 0.15mol benzoyl peroxide and 0.25mol N-dodecyl acrylamide, at 75 ℃, react after 7 hours, add Virahol termination reaction, with after ether sedimentation, obtain molecular weight and be 500 the poly-N-dodecyl methacrylamide homopolymer of hydrophobic association type.By gained multipolymer 0.06g and 1.98g viscosity-average molecular weight be 2,670 ten thousand poly-(acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium) (degree of hydrolysis 18.2%), under strong stirring effect, be scattered in 98g potassium bicarbonate aqueous solution (pH=10.0), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly (acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium)-
g-poly-N-dodecyl acrylamide.
Adopt the method described in embodiment 1 or structure and the performance of standard testing gained hydrophobic polymer graft modification acrylamide polymer, analytical results is as shown in table 1.
[embodiment 3]
In dry reaction bottle, inject 0.11mol 1-amido-2,5,5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 0.125mol isopropyl benzene hydroperoxide, 0.2mol N tert butyl acrylamide and 0.1mol N phenyl acrylamide, at 92 ℃, react after 7 hours, add Virahol termination reaction, with after ether sedimentation, obtain molecular weight and be 350 hydrophobic association type poly-(N tert butyl acrylamide-
r-N phenyl acrylamide) random copolymers.It by gained multipolymer 0.05g and 1.7g viscosity-average molecular weight, is 1,720 ten thousand super high molecular weight polyacrylamide, under strong stirring effect, be scattered in 99g potassium hydroxide aqueous solution (pH=9.8), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly acrylamide-
g-poly-(N tert butyl acrylamide-
r-N phenyl acrylamide).
Adopt the method described in embodiment 1 or structure and the performance of standard testing gained hydrophobic polymer graft modification polypropylene acid amides, analytical results is as shown in table 1.
[embodiment 4]
In dry reaction bottle, inject 0.16mol 1-carboxyl-2,2,4,4-tetramethyl--3-(1-phenyl ethoxy)-3-aza-pentane, 0.18mol Diisopropyl azodicarboxylate, 0.5mol butyl methacrylate are reacted after 5 hours at 66 ℃, then add 0.2mol 4-t-butyl styrene, at 89 ℃, continue reaction 4 hours, add Virahol termination reaction, with after ether sedimentation, obtain molecular weight and be 500 hydrophobic association type poly-(butyl methacrylate-
b-4-t-butyl styrene) segmented copolymer.By gained multipolymer 0.09g and 0.9g viscosity-average molecular weight be 2,060 ten thousand poly-(acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium) (degree of hydrolysis 16.9%), under strong stirring effect, be scattered in 99g aqueous sodium hydroxide solution (pH=10.9), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly (acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium)-
g-poly-(butyl methacrylate-
b-4-t-butyl styrene).
Adopt the method described in embodiment 1 or structure and the performance of standard testing gained hydrophobic polymer graft modification acrylamide polymer, analytical results is as shown in table 1.
[embodiment 5]
In dry reaction bottle, inject 0.17mol 1-aldehyde radical-2,2,5,5-tetramethyl--3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 0.19mol benzoyl peroxide, 0.3mol N tert butyl acrylamide and 0.1mol N, N-dioctyl acrylamide, at 78 ℃, react after 6 hours, add again 0.2mol vinylbenzene, at 89 ℃, continue reaction 4 hours, add Virahol termination reaction, with after ether sedimentation, obtain molecular weight and be 500 hydrophobic association type poly-(N tert butyl acrylamide-
r-N, N-dioctyl acrylamide)-
b-polystyrene block copolymer.By gained multipolymer 0.04g and 1.4g viscosity-average molecular weight be 2,320 ten thousand poly-(acrylamide-
b-2-acrylamide-2-methylpro panesulfonic acid sodium) (degree of hydrolysis 22.5%), under strong stirring effect, be scattered in 98g aqueous sodium carbonate (pH=11.2), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly (acrylamide-
b-2-acrylamide-2-methylpro panesulfonic acid sodium)-
g-(poly-(N tert butyl acrylamide-
r-N, N-dioctyl acrylamide)-
b-polystyrene).
Adopt the method described in embodiment 1 or structure and the performance of standard testing gained hydrophobic polymer graft modification acrylamide polymer, analytical results is as shown in table 1.
[embodiment 6]
In dry reaction bottle, inject 0.13mol 1-bromo-2,2,5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, the 0.14mol peroxidation trimethylacetic acid tert-butyl ester and 0.3mol N-n-hexyl acrylamide, at 100 ℃, react after 6 hours, 0.2mol vinylbenzene and 0.2mol 4-Vinyl phenol reinject, at 103 ℃, continue reaction after 5 hours, add Virahol termination reaction, with after ether sedimentation, obtain molecular weight and be 660 the poly-N-n-hexyl acrylamide of hydrophobic association type-
b-poly-(vinylbenzene-
r-4-Vinyl phenol) segmented copolymer.By gained multipolymer 0.08g and 1.8g viscosity-average molecular weight be 2,500 ten thousand poly-(acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium) (degree of hydrolysis 24.8%), under strong stirring effect, be scattered in 97g sodium bicarbonate aqueous solution (pH=7.5), under backflow effect, there is graft copolymerization, obtain graft modification polymer poly (acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium)-
g-(poly-N-n-hexyl acrylamide-
b-poly-(vinylbenzene-
r-4-Vinyl phenol)).
Adopt the method described in embodiment 1 or structure and the performance of standard testing gained hydrophobic polymer graft modification acrylamide polymer, analytical results is as shown in table 1.
[comparative example 1]
With [embodiment 2], just do not implement graft copolymerization, only by the hydrophobic poly-N-dodecyl methacrylamide homopolymer of gained with gather (acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium) (degree of hydrolysis 18.2%) mixes, and adopts temperature resistant antisalt, ageing-resistant performance and the imitation oil displacement experiment test of the method described in embodiment 1 or standard testing gained mixture, and analytical results is as shown in table 1.
[comparative example 2]
Do not implement controllable free-radical polymerisation and graft copolymerization, only in [embodiment 6] used poly-(acrylamide-
r-2-acrylamide-2-methylpro panesulfonic acid sodium) performance of (degree of hydrolysis 24.8%) is analyzed, and adopts the method described in embodiment 1 or its temperature resistant antisalt of standard testing, ageing-resistant performance and imitation oil displacement experiment test, and analytical results is as shown in table 1.
The structure of table 1 polymkeric substance and performance
Claims (10)
1. a hydrophobic polymer graft modification acrylamide polymer, has following chemical general formula:
P-
g-X
Wherein, P is polyacrylamide or acrylamide based copolymer;
X is the hydrophobic polymer that molecular chain structure is homopolymerization type, random copolymerization type or block copolymerization type;
Viscosity-average molecular weight >=1,700 ten thousand of this hydrophobic polymer graft modification acrylamide polymer.
2. hydrophobic polymer graft modification acrylamide polymer claimed in claim 1, is characterized in that X adopts oxynitride to telomerize the controlled hydrophobic polymer of activity that free radical polymerisation process makes.
3. hydrophobic polymer graft modification acrylamide polymer claimed in claim 1, is characterized in that the monomeric repeating unit number in X is selected from the arbitrary integer in 1～200.
4. the preparation method of hydrophobic polymer graft modification acrylamide polymer claimed in claim 1, comprises the following steps:
A) take hydrophobic monomer as raw material, functionalized 3-(1-the phenyl ethoxy)-3-aza-hexane derivative of take is telogen, mol ratio at telogen, radical initiator and hydrophobic monomer is under 1:0.1～10:1～500,30～130 ℃ of temperature of reaction, the condition in 2～20 hours reaction times, cause hydrophobic monomer and telomerize radical polymerization, obtain the hydrophobic polymer X that molecular chain is homopolymerization type, random copolymerization type or block copolymerization type structure;
B) above-mentioned gained hydrophobic polymer is mixed with acrylamide polymer, under medium and backflow effect, graft copolymerization occurs, obtain the graft modification acrylamide polymer P-that side chain is hydrophobic type
g-X, wherein,
gexpression product is graft type.
5. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, it is characterized in that the functionalized 3-described in step a) (1-phenyl ethoxy)-3-aza-hexane derivative is selected from 1-function base-2, 2, 4, 4-tetramethyl--3-(1-phenyl ethoxy)-3-aza-pentane, 1-function base-2, 5-dimethyl-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 1-function base-2, 2, 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane, 1-function base-2, 5, 5-trimethylammonium-3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane or 1-function base-2, 2, 5, at least one in 5-tetramethyl--3-(1-phenyl ethoxy)-4-phenyl-3-aza-hexane.
6. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, the functional group that it is characterized in that functionalized 3-(1-phenyl ethoxy)-3-aza-hexane derivative is selected from a kind of in hydroxyl, alkoxyl group, halogen, alkoxy carbonyl, carboxyl, aldehyde radical or amido.
7. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, is characterized in that the radical initiator described in step a) 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 organic peroxide evocating agent is selected from least one in hydrogen peroxide, isopropyl benzene hydroperoxide, dicumyl peroxide, benzoyl peroxide, the peroxidation 2 ethyl hexanoic acid tert-butyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxy dicarbonate diisobutyl ester or 1,1-di-t-butyl peroxy hexanaphthene.
8. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, it is characterized in that the hydrophobic monomer described in step a) is selected from N tert butyl acrylamide, N-normal-butyl acrylamide, N-n-hexyl acrylamide, N-n-octyl acrylamide, N-dodecyl acrylamide, N-n-hexadecyl acrylamide, N phenyl acrylamide, N, N-DMAA, N, N-dibutyl acrylamide, N, N-dioctyl acrylamide, butyl acrylate, butyl methacrylate, vinylbenzene, 4-t-butyl styrene, 4-Vinyl phenol, at least one in NEM or N-phenylmaleimide.
9. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, it is characterized in that by weight percentage step b) described in the ratio range of hydrophobic polymer, acrylamide polymer and medium be: 0.01～5.0:0.01～5.0:90.0～99.98.
10. the preparation method of hydrophobic polymer graft modification acrylamide polymer according to claim 4, is characterized in that described medium is selected from least one in the aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, sodium carbonate or salt of wormwood that pH value scope is 7.2～13.8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210239960.4A CN103539946B (en) | 2012-07-12 | 2012-07-12 | Hydrophobic polymer graft modification acrylamide polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210239960.4A CN103539946B (en) | 2012-07-12 | 2012-07-12 | Hydrophobic polymer graft modification acrylamide polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103539946A true CN103539946A (en) | 2014-01-29 |
| CN103539946B CN103539946B (en) | 2016-06-08 |
Family
ID=49963839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210239960.4A Active CN103539946B (en) | 2012-07-12 | 2012-07-12 | Hydrophobic polymer graft modification acrylamide polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539946B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273129A (en) * | 2015-11-06 | 2016-01-27 | 东营市诺尔化工有限责任公司 | Preparation method of anionic polyacrylamide with ultrahigh viscosity |
| CN106589232A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparing method |
| CN107629771A (en) * | 2017-09-29 | 2018-01-26 | 中国石油天然气集团公司 | The low preparation method for gluing high cut type oil-well cement suspension stabilizer of big temperature difference well cementation |
| CN107746447A (en) * | 2017-10-25 | 2018-03-02 | 中国石油化工股份有限公司 | Profile control delay Tackified polymeric and preparation method thereof |
| CN108431170A (en) * | 2016-01-13 | 2018-08-21 | 巴斯夫欧洲公司 | By Hydrophobic association property polymer tertiary recovery mineral oil method |
| CN111286315A (en) * | 2020-03-26 | 2020-06-16 | 东野升富 | Compound oil-displacing agent for increasing recovery ratio of low-permeability reservoir and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532052A (en) * | 1978-09-28 | 1985-07-30 | Halliburton Company | Polymeric well treating method |
| US20040262000A1 (en) * | 2003-06-27 | 2004-12-30 | Morgan Rickey L. | Cement compositions with improved fluid loss characteristics and methods of cementing in surface and subterranean applications |
| CN101314711A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Elastic particle oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
| CN101314710A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
| 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 |
-
2012
- 2012-07-12 CN CN201210239960.4A patent/CN103539946B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532052A (en) * | 1978-09-28 | 1985-07-30 | Halliburton Company | Polymeric well treating method |
| US20040262000A1 (en) * | 2003-06-27 | 2004-12-30 | Morgan Rickey L. | Cement compositions with improved fluid loss characteristics and methods of cementing in surface and subterranean applications |
| CN101314711A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Elastic particle oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
| CN101314710A (en) * | 2008-07-18 | 2008-12-03 | 中国石油大学(华东) | Oil displacement profile control agent, displacement of reservoir oil system and displacement of reservoir oil method |
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589232A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparing method |
| CN106589232B (en) * | 2015-10-20 | 2020-08-07 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer and preparation method thereof |
| CN105273129A (en) * | 2015-11-06 | 2016-01-27 | 东营市诺尔化工有限责任公司 | Preparation method of anionic polyacrylamide with ultrahigh viscosity |
| CN108431170A (en) * | 2016-01-13 | 2018-08-21 | 巴斯夫欧洲公司 | By Hydrophobic association property polymer tertiary recovery mineral oil method |
| CN107629771A (en) * | 2017-09-29 | 2018-01-26 | 中国石油天然气集团公司 | The low preparation method for gluing high cut type oil-well cement suspension stabilizer of big temperature difference well cementation |
| CN107629771B (en) * | 2017-09-29 | 2020-08-11 | 中国石油天然气集团公司 | Preparation method of low-viscosity high-shear oil well cement suspension stabilizer for large-temperature-difference well cementation |
| CN107746447A (en) * | 2017-10-25 | 2018-03-02 | 中国石油化工股份有限公司 | Profile control delay Tackified polymeric and preparation method thereof |
| CN107746447B (en) * | 2017-10-25 | 2020-04-07 | 中国石油化工股份有限公司 | Delayed tackifying polymer for profile control and preparation method thereof |
| CN111286315A (en) * | 2020-03-26 | 2020-06-16 | 东野升富 | Compound oil-displacing agent for increasing recovery ratio of low-permeability reservoir and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103539946B (en) | 2016-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539946A (en) | Hydrophobic polymer graft modified acrylamide polymer and preparation method thereof | |
| CN109705834B (en) | Composition, temperature-resistant salt-resistant fracturing fluid thickening agent prepared from composition and preparation method of thickening agent | |
| CN106866878B (en) | Polymer-type profile control agent and preparation method thereof suitable for high temperature and high salt harshness oil reservoir | |
| CN104449636B (en) | Oil displacement agent of recovery ratio and preparation method thereof is improved suitable for high temperature and high salt harshness oil reservoir | |
| CN111499793B (en) | Nano composite polymer and temperature-resistant and salt-resistant profile control agent containing same | |
| CN104388063B (en) | Micro-crosslinked polymer fluid loss additive for drilling fluid and preparation method thereof | |
| CN102181010B (en) | Preparation method of high-temperature-resistant high-salt polymer oil-replacement agent | |
| CN104448128A (en) | Polymer mobility control agent suitable for high-temperature and high-salinity harsh reservoir and preparation method of polymer mobility control agent | |
| CN105567208B (en) | Improved displacement of reservoir oil composition of injection and its preparation method and application | |
| CN102050926A (en) | Heat-resistant salt-tolerate graft polyacrylamide and preparation method thereof | |
| CN108299592B (en) | 3-methacrylamide dopamine and acrylamide mixed polymer and preparation method and application thereof | |
| CN106589227B (en) | High-temperature high-salinity oil reservoir polyacrylamide oil displacement agent and preparation method thereof | |
| CN104628944B (en) | Acrylamide copolymer, as well as preparation method and application thereof | |
| CN103666433A (en) | Oil-displacing agent composition used for improving recovery ratio of high-temperature reservoir and preparation method of composition | |
| CN103897115B (en) | Terpolymer as concrete workability improver | |
| CN102746441B (en) | Acrylamide terpolymer and polymer and preparation method and application thereof | |
| CN102029124B (en) | Polyacrylamide surfactant and preparation method thereof | |
| CN102464782B (en) | Thermo-thickening water-soluble tricopolymer, its preparation method and application | |
| CN102746456B (en) | Terpolymer and polymer and preparation method and application thereof | |
| JP2021524872A (en) | High melt index thermoplastic elastomer and its manufacturing method | |
| CN102453254B (en) | Acrylic acid ester compound and polymer, preparation method and application thereof | |
| CN102746455B (en) | Acrylamide terpolymer and polymer and preparation method and application thereof | |
| CN110790859B (en) | Acrylamide copolymer and preparation method and application thereof | |
| CN106589232B (en) | Hydrophobic association acrylamide copolymer and preparation method thereof | |
| CN110790862B (en) | Acrylamide copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |