CN1105675A - High-temp. resistance and antisalt water-soluble optical polymer - Google Patents
High-temp. resistance and antisalt water-soluble optical polymer Download PDFInfo
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- CN1105675A CN1105675A CN 94100644 CN94100644A CN1105675A CN 1105675 A CN1105675 A CN 1105675A CN 94100644 CN94100644 CN 94100644 CN 94100644 A CN94100644 A CN 94100644A CN 1105675 A CN1105675 A CN 1105675A
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- photopolymerization
- photopolymer
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Abstract
The present invention uses a photopolymerization method to synthesize binary, ternary and polynary high-molecular water-soluble copolymers. As compared with thermal polymerization method, the invented photopolymerization method features that its process is simple, convenient, quick, energy-saving and easy to control. The invented polymerization method is ued for preparing the polymer with high viscosity, resistance to shear and resistance to high-temp. and heavy salt. Said polymer can be used as thickening agent, emulsion dispersing agent and chemical oil displacement agent for tertiary recovery.
Description
The technical field of the invention is a photopolymer.
At present, countries in the world are to the focus of the displacement of reservoir oil with polymkeric substance research, mainly concentrating on acrylamide and derivative thereof is main multipolymer, the general free radical thermopolymerization forms that adopt of synthetic method more, wherein also useful r-ray polymerization mode is produced, and ultrasonicly involves the electron beam irradiation polymerization and also be in the exploratory stage.In China, polymer flooding mainly uses partially hydrolyzed polyacrylamide at present, and production technique adopts free radical solution polymerization method batch production basically, and scale is less, and quality product is stable inadequately, the also still difficult polymeric articles that superior performance is provided.Particularly for some geologic condition more complicated, the reservoir temperature height, the oil field that the local water saltness is high uses the so conventional oil-displacing agent of polyacrylamide then not have effect fully.Therefore, be necessary to carry out the novel temperature resistant antisalt displacement of reservoir oil polymkeric substance of development.Prepare this series products, at present still based on traditional free radical thermopolymerization method, like this, synthesis technique is more complicated often, and the reaction times is long or molecular weight is low, is difficult to reach the result of the phase of giving.Photopolymerization is to be the energy with UV-light or visible light, by the light trigger photodissociation, produces a kind of novel method of living radical initiated polymerization, be reflected at room temperature and carry out, speed is fast, and is easy, be easy to control, product is also purer, and especially aspect synthetic high viscosity water soluble polymer, photopolymerization is a kind of highly effective method, when the present invention uses polymkeric substance in the preparation displacement of reservoir oil, utilization radical photopolymerization mode, synthetic a series of binary, ternary and polywater solubleness high molecular compound.This polymkeric substance has high viscosity, and is anti-shearing, heatproof, and premium propertiess such as anti-salt are suitable as the used for tertiary oil recovery chemical oil displacement agent.Thisly belong to first at home with polymkeric substance with photochemical method synthetic oil field.
The temperature resistant antisalt polymkeric substance of the present invention's preparation can be made up of four types of monomers.(1) class is an acrylamide, the N-alkyl acrylamide, and N-hydroxyalkyl acrylamide, N, N-dialkyl group acrylamide, (2) class monomer is vinylformic acid and acrylate.As vinylformic acid, methacrylic acid, alkyl acrylate, hydroxy alkyl ester, alkyl methacrylate, hydroxy alkyl ester.(3) class monomer is the vinyl cyclopropyl ketone compounds, as the N-vinyl pyrrolidone, (4) class monomer is the aliphatic sulfonate that contains vinyl, as allylic alkylation sulfonate, acrylamide group methyl propanesulfonic acid salt, the total concn of above monomer when polymerization is controlled at 10-45Wt%, and wherein the monomeric content of (4) class should be no less than the 30Wt% of monomer total content.
The present invention is solvent with water, also available alcohol-water mixed solvent, and alcohol-water ratio is 1: 13-1: 24, should adjust pH value before the polymerization is 5.0-8.5, and the size of reacting system PH value is very big to the influence of photopolymerization speed, and best pH value is 7.0.
Light trigger adopts the photodestruciton type or carries H-H reaction type initiator, comprises benzophenone, st-yrax, benzoin ether and various acetophenone derivs, light trigger under light action, can take place as shown in the formula photolysis, generate living radical R, and trigger monomer polymerization thus.
Cause R+M → MR → M: monomer
Chainpropagation MR+M → P
Chain termination P+P → polymkeric substance
Initiator concentration is generally at 1X10
-3-1X10
-4Mol/l, ethanolic soln consumption 4.0-5.5ml/100ml solution.Photopolymerization reaction carries out under nitrogen protection, and the logical nitrogen of the solution for preparing 20 minutes (general nitrogen or high purity nitrogen all can), the photopolymerization temperature be controlled at 15-30 ℃, and optimum temps is 18 ℃, and light application time 45-80 minute, Best Times was 60 minutes.
Polymers soln character
1. viscosity: 12-15mPaS
Condition: polymer concentration 2000ppm
Salinity 8-10 ten thousand ppm(are Ca wherein
800ppm Mg
200ppm)
Temperature: 25 ℃, NDJ-1 type viscometer, 6 rev/mins
2. anti-shear performance
As shown in Figure 1, curve 1 is that curve 2 is polyacrylamide homopolymer with the multipolymer of the inventive method preparation, and (shearing rate is 850S under identical experiment condition
-1, 1 hour time), curve 1 is much more superior than the anti-shear performance of curve 2.
3. salt resistant character
Polymkeric substance is made into the solution of 2000ppm concentration, and salinity is wherein Ca of 100,000 ppm(
800ppm Mg
200ppm), through test in 6 months, brookfield viscosity was 8-14mPaS.Illustrate that copolymer product has good anti-salt property.
Embodiment 1
Acrylamide 4.0g
2-acrylamido-2-methyl propane sulfonic acid 6.0g
The benzoin dimethylether ethanolic soln
(concentration 3.0X10
-3Mol/l) 4.7ml
Distilled water is supplemented to 100ml
Step: (1) adjusts pH value to 7.0 to two kinds of a small amount of dissolved in distilled water of monomer, moves into then in the 100ml volumetric flask, adds light trigger again, adds to scale with distilled water at last.
(2) solution for preparing is placed glass test tube or flat-shaped container, logical nitrogen 20 minutes (general nitrogen or high purity nitrogen all can) placed under the high voltage mercury lamp illumination 60 minutes then under 18 ℃ of temperature, promptly get water white transparency shape macromolecule product.
Light source: straight pipe type high voltage mercury lamp, power: 1000W
Embodiment 2
Acrylamide 13.25g
N-vinyl pyrrolidone 1.75g
2-acrylamido-2-methyl propane sulfonic acid 10.0g
The benzoin dimethylether ethanolic soln
(concentration 3.0X10
-3Mol/l) 5.0ml
Distilled water is supplemented to 100ml
Operation steps is with embodiment 1.
Embodiment 3
Acrylamide 8.8g
Propenoic acid beta-hydroxy propyl ester 1.0g
N-vinyl pyrrolidone 4.8g
2-acrylamido-2-methyl propane sulfonic acid 11.3g
The benzoin dimethylether ethanolic soln
(concentration 3.0X10
-3Mol/l) 5.0ml
Distilled water is supplemented to 100ml
Operation steps is with embodiment 1.
Embodiment 4
Acrylamide 14.0g
N-vinyl pyrrolidone 1.70g
2-acrylamido-2-methyl propane sulfonic acid 9.2g
The benzoin isopropyl ether ethanolic soln
(concentration 6.0X10
-3Mol/l) 4.5ml
Distilled water is supplemented to 100ml
Operation steps is with embodiment 1.
Embodiment 5
Adopt light trigger
Replace the benzoin isopropyl ether of embodiment 4, carry out photopolymerization by same prescription.
Fig. 1 is the viscosity-time curve of photopolymer of the present invention and polyacrylamide homopolymer, and curve 1 is a photopolymer, and curve 2 is a polyacrylamide.
Claims (6)
1, a kind of photopolymer is characterized in that by following monomer (1) acrylamide and derivative thereof, (2) vinylformic acid and acrylate thereof, and (3) vinyl cyclopropyl ketone compounds, (4) vinyl fat family sulfonate is formed.Under the effect of UV-light or visible light and Photoepolymerizationinitiater initiater, in the aqueous solution, carry out binary (1.4), ternary (1.3.4), and polynary (1.2.3.4) photopolymerization, the total concn of polymer monomers in water is 10-45Wt%, and wherein the content of monomer (4) should be no less than the Wt30% of monomer total amount.
2, photopolymer according to claim 1 is characterized in that polymer monomers has following chemical structure.
3, photopolymer according to claim 1 is characterized in that Photoepolymerizationinitiater initiater has following structure.
R
4, R
5: hydrogen, alkyl, cycloalkyl
R
6, R
7, R
8: hydrogen, alkyl, hydroxyl, alkoxyl group, the cycloalkyl photoinitiator concentration is generally at 1X10
-3Mol/l-1X10
-4Mol/l, ethanolic soln consumption 4.0-5.5ml/100ml solution.
4, a kind of preparation method of photopolymer, it is characterized in that earlier polymer monomers with a small amount of dissolved in distilled water, adjust pH value 5.0-8.5, optimum value is 7.0, the logical nitrogen of the solution for preparing 20 minutes (general nitrogen or high purity nitrogen all can), the photopolymerization temperature is controlled at 15-30 ℃, and optimum temps is 18 ℃, polymerization time 45-80 minute, Best Times was 60 minutes.
5, photopolymerization preparation method thereof according to claim 4 is characterized in that photopolymerization can carry out in the aqueous solution, also can carry out in ethanol-water mixed solvent, and the alcohol-water ratio is 1: 13-1: 24.
6, a kind of application of photopolymer is characterized in that this polymkeric substance can be used as thickening material, the chemical oil displacement agent of emulsion dispersion agent and tertiary oil recovery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94100644A CN1056856C (en) | 1994-01-20 | 1994-01-20 | High-temp. resistance and antisalt water-soluble optical polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94100644A CN1056856C (en) | 1994-01-20 | 1994-01-20 | High-temp. resistance and antisalt water-soluble optical polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105675A true CN1105675A (en) | 1995-07-26 |
| CN1056856C CN1056856C (en) | 2000-09-27 |
Family
ID=5029755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100644A Expired - Fee Related CN1056856C (en) | 1994-01-20 | 1994-01-20 | High-temp. resistance and antisalt water-soluble optical polymer |
Country Status (1)
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|---|---|
| CN (1) | CN1056856C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386403C (en) * | 2005-06-10 | 2008-05-07 | 中国石油天然气股份有限公司 | Braided comb-shaped thickener for salt-resistant polymer |
| CN101260171B (en) * | 2008-04-22 | 2010-08-04 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
| CN102453194A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Copolymer and preparation method thereof |
| JP2013517345A (en) * | 2010-01-18 | 2013-05-16 | リントフィールド リミテッド | Photoinitiated reaction |
| CN103665259A (en) * | 2013-12-13 | 2014-03-26 | 山东大学 | High-temperature resistant and anti-shearing water-soluble branched polymer and preparation method thereof |
| CN113817097A (en) * | 2021-09-10 | 2021-12-21 | 黑龙江吉地油田服务股份有限公司 | Salt-resistant antibacterial functional polymer for oil displacement and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5260391A (en) * | 1987-03-23 | 1993-11-09 | Michael Stephens | Tetrapolymerization product of 2-acrylamido-2-methyl propane sulfonic acid/associated salts, n-vinyl pyrrolidone, acrylamide, and acrylic acid/associated salts |
-
1994
- 1994-01-20 CN CN94100644A patent/CN1056856C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386403C (en) * | 2005-06-10 | 2008-05-07 | 中国石油天然气股份有限公司 | Braided comb-shaped thickener for salt-resistant polymer |
| CN101260171B (en) * | 2008-04-22 | 2010-08-04 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
| JP2013517345A (en) * | 2010-01-18 | 2013-05-16 | リントフィールド リミテッド | Photoinitiated reaction |
| CN102453194A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Copolymer and preparation method thereof |
| CN102453194B (en) * | 2010-10-25 | 2014-07-09 | 中国石油化工股份有限公司 | Copolymer and preparation method thereof |
| CN103665259A (en) * | 2013-12-13 | 2014-03-26 | 山东大学 | High-temperature resistant and anti-shearing water-soluble branched polymer and preparation method thereof |
| CN113817097A (en) * | 2021-09-10 | 2021-12-21 | 黑龙江吉地油田服务股份有限公司 | Salt-resistant antibacterial functional polymer for oil displacement and preparation method thereof |
| CN113817097B (en) * | 2021-09-10 | 2022-12-06 | 黑龙江吉地油田服务股份有限公司 | Salt-resistant antibacterial functional polymer for oil displacement and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1056856C (en) | 2000-09-27 |
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