CN1056856C - 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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- CN1056856C CN1056856C CN94100644A CN94100644A CN1056856C CN 1056856 C CN1056856 C CN 1056856C CN 94100644 A CN94100644 A CN 94100644A CN 94100644 A CN94100644 A CN 94100644A CN 1056856 C CN1056856 C CN 1056856C
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Abstract
The present invention relates to a photo polymerization method for synthesizing binary, ternary and polynary water soluble copolymers with high molecular weight. Compared with a thermal polymerization method, the photo polymerization method has the characteristics of convenience, rapidness, energy saving, easy technology control, etc. The photo polymerization method is used for preparing polymers with high viscosity, shear resistance, and high temperature and heavy salt resistance. The polymers can be used as thickening agents, emulsion dispersing agents and chemical oil displacement agents for tertiary oil recovery.
Description
The invention belongs to the technical field of photopolymers.
At present, the hot research on polymers for oil displacement in various countries around the world mainly focuses on copolymers mainly comprising acrylamide and derivatives thereof, the synthesis method generally adopts a free radical thermal polymerization mode, wherein the copolymers are produced by a gamma-ray polymerization mode, and the radiation polymerization of ultrasonic waves and electron beams is still in an exploration stage. In China, partial hydrolyzed polyacrylamide is mainly used for polymer oil displacement at present, a production process basically adopts a free radical solution polymerization method for intermittent production, the scale is small, the product quality is not stable enough, polymer products with excellent performance are difficult to provide, and the conventional oil displacement agent such as polyacrylamide has no effect at all when being used for oil fields with complex geological conditions, high oil layer temperature and high salinity of formation water. Therefore, it is necessary to develop a novel temperature-resistant and salt-resistant polymer for oil displacement to prepare such products, and the conventional radical thermal polymerization method is mainly used at present, so that the synthesis process is complex, the reaction time is long or the molecular weight is low, and the expected result is difficult to achieve. Photopolymerization is a new method for initiating polymerization by photolysis of a photoinitiator with ultraviolet light or visible light as an energy source to generate active free radicals. The reaction is carried out at room temperature, the speed is high, the method is simple and convenient, the control is easy, the product is relatively pure, and the photopolymerization is an effective method particularly in the aspect of synthesizing high-viscosity water-soluble polymers. When the polymer for oil displacement is prepared, a series of binary, ternary and multicomponent water-soluble high molecular compounds are synthesized by using a free radical photopolymerization mode, the polymer has excellent performances of high viscosity, shear resistance, temperature resistance, salt resistance and the like, and is suitable to be used as a chemical oil displacement agent for tertiary oil recovery, and the photochemical method for synthesizing the polymer for oil fields belongs to the first time in China.
The temperature-resistant salt-resistant polymer prepared by the invention can be composed of four types of monomers, wherein the type (1) is acrylamide, N-alkylacrylamide, N-hydroxyalkyl acrylamide, N-dialkyl acrylamide; the (2) type monomers are acrylic acid and acrylic acid esters such as acrylic acid, methacrylic acid, alkyl acrylate, hydroxyalkyl acrylate, alkyl methacrylate, hydroxyalkyl methacrylate; the monomer of the (3) type is a vinyl cyclic ketone compound, such as N-vinyl pyrrolidone; the monomer of the (4) group is aliphatic sulfonate containing vinyl group, such as alkylene sulfonate, acrylamide methyl propane sulfonate. The total concentration of the above monomers during polymerization is controlled at 10-45 wt%, wherein the content of the (4) type monomer is not less than 30 wt% of the total content of the monomers
The contents of the monomers are respectively as follows:
(1) acrylamide compounds, such as acrylamide, in an amount of 33.98 to 56.22% by weight of the total monomers;
(2) acrylic acid and acrylic ester compounds, such as β -hydroxypropyl acrylate, in an amount of 0-3.86% by weight of the total monomers;
(3) vinyl cyclic ketones, such as N-vinyl pyrrolidone, in an amount of 0-18.53% by weight of the total monomers
(4) Vinyl aliphatic sulfonate compounds, such as 2-acrylamido-2-methylpropanesulfonic acid, account for 36.95 to 60% by weight of the total monomers;
the invention uses water as solvent, oralcohol-water mixed solvent, the alcohol-water ratio is 1: 13-1: 24, the PH value should be adjusted to 5.0-8.5 before polymerization, the PH value of the reaction system has great influence on the photopolymerization speed, and the optimal PH value is 7.0.
The photoinitiator adopts a photocracking type or hydrogen extraction reaction type initiator, and comprises benzophenone, benzoin ether and various benzophenone derivatives, and the photoinitiator can generate photolysis reaction with the following formula under the action of light to generate active free radicals R and initiate the polymerization of monomers. Photolytic decomposition
Initiation of M: monomer chain extension Chain termination
The initiator concentration is generally 1X 10-4-1×10-3mol/l, 4.0-5.5ml of ethanol solution per 100ml of solution, carrying out photopolymerization under the protection of nitrogen, introducing nitrogen into the prepared solution for 20 minutes (common nitrogen or high-purity nitrogen can be used), controlling the photopolymerization temperature to be 15-30 ℃, optimally controlling the temperature to be 18 ℃, and carrying out illumination for 45-80 minutes, optimally controlling the time to be 60 minutes. Light source: a straight-tube type high-pressure mercury lamp,the power is 1000W. The polymer solution has the property of 1, the viscosity of 12-15mPa.SConditions are as follows: polymer concentration 2000ppm
Degree of mineralization 8-10 ppm (Ca)2+800ppm Mg2+200ppm) temperature: NDJ-1 type viscometer at 25 ℃, 6 rpm/min 2 shear resistance
As shown in FIG.1, curve 1 is a copolymer prepared by the process of the present invention, and curve 2 is a polyacrylamide homopolymer under the same experimental conditions (shear rate 850S)-1Time 1 hour), curve 1 is much superior to curve 2 in shear resistance. 3. Salt resistance
The polymer was formulated into a 2000ppm solution with a degree of mineralization of 10 ppm (Ca)2+800ppmMg2+200ppm) and the Brookfield viscosity is 8-14 mPa.S after 6-month test, which shows that the copolymer product has good salt resistance.
EXAMPLE 1 acrylamide 4.0g (40% by weight of total monomers) 2-acrylamido-2-methylpropanesulfonic acid 6.0g (60% by weight of total monomers) Benzoinum bismethyl Ethanol EtOH solution 4.7ml (3X 10 concentration)-3mol/l) distilled water to 100ml step:
(1) the monomers used were dissolved with a small amount of distilled water, the pH was adjusted to 7.0, then transferred to a 100ml volumetric flask, the photoinitiator was added and finally the scale was brought up with distilled water.
(2) Placing the prepared solution in a glass test tube or a flat-plate container, introducing nitrogen for 20 minutes (common nitrogen or high-purity nitrogen can be used), and then placing the solution under a high-pressure mercury lamp at 18 ℃ for illumination for 60 minutes to obtain a colorless transparent polymer product. Example 2
Acrylamide 13.25g (53% of total monomer weight)
N-vinylpyrrolidone 1.75g (7.0% by weight of the total monomer)
2-acrylamido-2-methylpropanesulfonic acid (10.0 g, based on 40% by weight of the total monomers)
Benzoin dimethyl ether ethanol solution 5.0ml
(concentration 3X 10)-3mol/l)
Distilled water was supplemented to 100ml the same procedure as in example 1, example 3
Acrylamide 8.8g (33.98% of total monomer weight)
β -hydroxypropyl acrylate 1.0g (3.86% by weight of total monomers)
N-vinylpyrrolidone 4.8g (18.53% by weight based on the total monomer)
2-acrylamido-2-methylpropanesulfonic acid (11.3 g, 43.63% by weight based on the total monomers)
Benzoin dimethyl ether ethanol solution 5.0ml
(concentration 3X 10)-3mol/l)
Distilled water was supplemented to 100ml the same procedure as in example 1, example 4
Acrylamide 14.0g (56.22% of total monomer weight)
N-vinylpyrrolidone 1.70g (6.83% by weight of the total monomer)
2-acrylamido-2-methylpropanesulfonic acid 9.2g (36.95% by weight of the total monomers)
4.5ml of benzoin isopropyl ether ethanol solution
(concentration 6X 10)-3mol/l)
The procedure of example 1, example 5, was followed with distilled water to make up to 100 ml:
photopolymerization was carried out in the same proportion and operation method using a photoinitiator benzoin ethylene diether (the structure of which is shown in the following figure) instead of benzoin isopropyl ether of example 2.
Description of the drawings:
FIG. 1 is a viscosity-time curve for a photopolymer of the present invention and a polyacrylamide homopolymer, curve 1 for the photopolymer and curve 2 for the polyacrylamide. Conditions are as follows: polymer concentration: 1mg/ml (H)2O) temperature: NDJ-79 viscometer at 30 deg.C, 750 rpm, shear reduction speed 850S-1
Claims (8)
1. A photopolymer is characterized in that the viscosity is 12-15mPa.S under the conditions of 25 ℃, the concentration is 2000ppm and the mineralization degree is 8-10 ppm, and the photopolymer is composed of four types of monomers, namely (1) monomer acrylamide accounting for 33.98-56.22% of the total monomer weight, (2) monomer acrylic acid β -hydroxypropyl ester accounting for 0-3.86% of the total monomer weight, (3) monomer N-vinyl pyrrolidone accounting for 0-18.53% of the total monomer weight, and (4) monomer 2-acrylamide-2-methyl propanesulfonic acid accounting for 36.95-60% of the total monomer weight;
the monomer is subjected to photopolymerization reaction in aqueous solution or ethanol-water mixed solution under the action of ultraviolet light or visible light and photo-cracking or hydrogen extraction reaction type photopolymerization initiator, the pH value of the reaction system is 5.0-8.5, the illumination time is controlled to be 45-80 minutes, the photopolymerization temperature is controlled to be 15-30 ℃, and the concentration of the photopolymerization initiator is 1 x 10-4-1×10-3mol/l。
2. Photopolymer according to claim 1, characterized in that the photoinitiators are benzophenone, benzoin ethers and acetophenone derivatives.
3. The preparation method of photopolymer is characterized by that firstly, monomer acrylamide accounting for 33.98% -56.22% of total monomer weight, monomer acrylic acid β -hydroxypropyl ester accounting for 0% -3.86% of total monomer weight, monomer N-vinyl pyrrolidone accounting for 0% -18.53% of total monomer weight, monomer 2-vinyl pyrrolidone accounting for 36.95% -60% of total monomer weightDissolving acrylamido-2-methylpropanesulfonic acid in distilled water, regulating pH to 5.0-8.5, transferring into volumetric flask, adding ethanol solution of photo-cracking or hydrogen-extracting photopolymerization initiator with concentration of 1 × 10-4-1×10-3And (3) adding distilled water to the scale, introducing nitrogen into the prepared solution for 20 minutes, and controlling the light polymerization temperature to be 15-30 ℃ to obtain the temperature-resistant salt-resistant water-soluble photopolymer, wherein the light irradiation time is 45-80 minutes.
4. The method of producing a photopolymer according to claim 3, wherein the pH is 7.0.
5. The method for producing a photopolymer according to claim 3, wherein the photopolymerization temperature is controlled to 18 ℃.
6. The method of preparing a photopolymer according to claim 3, wherein the light irradiation time is 60 minutes.
7. The method for producing a photopolymer according to claim 3, wherein the photopolymerization is carried out in water or an ethanol-water mixed solution, and the ethanol-water ratio is 1: 13 to 1: 24.
8. Use of a photopolymer according to claim 1 as a chemical oil displacement agent, emulsion dispersant or thickener for enhanced oil recovery.
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| 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 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN94100644A CN1056856C (en) | 1994-01-20 | 1994-01-20 | High-temp. resistance and antisalt water-soluble optical polymer |
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| CN1105675A CN1105675A (en) | 1995-07-26 |
| CN1056856C true CN1056856C (en) | 2000-09-27 |
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| CN94100644A Expired - Fee Related CN1056856C (en) | 1994-01-20 | 1994-01-20 | High-temp. resistance and antisalt water-soluble optical polymer |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| GB2476976A (en) * | 2010-01-18 | 2011-07-20 | Lintfield Ltd | Protected aryl ketones and their use as photoinitiators |
| 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 |
| CN103665259B (en) * | 2013-12-13 | 2015-12-09 | 山东大学 | One is high temperature resistant and shear-stable water-soluble branched polymer 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 |
Citations (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 |
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Patent Citations (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 |
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