CN1528796A - Silicone modified polyacrylamide and preparing method thereof - Google Patents
Silicone modified polyacrylamide and preparing method thereof Download PDFInfo
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- CN1528796A CN1528796A CNA031390765A CN03139076A CN1528796A CN 1528796 A CN1528796 A CN 1528796A CN A031390765 A CNA031390765 A CN A031390765A CN 03139076 A CN03139076 A CN 03139076A CN 1528796 A CN1528796 A CN 1528796A
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Abstract
The invention relates to an organosilicon monomer modified polyacrylamide and its preparing method. The C-C double bond containing organosilicon is used as modifying monomer, under the initiation of low-temperature redox initiating system, emulsified in water, and then copolymerizes with acrylamide free group to hydrolyze and obtain ternary copolymer, or makes free group co- polymerization together with acrylamide and crylic acid to directly obtain ternary copolymer. The organosilicon monomer has better temperature resistance and stronger association, so the obtained copolymer has excellent temperature-resistant performance and better salt resistance, able to be widely applied in fields such as tertiary oil recovery, drilling fluid, paint, etc.
Description
Technical field: the present invention relates to monomer modified polyacrylamide of a kind of novel organosilicon and preparation method thereof, i.e. terpolymer of acrylamide, vinylformic acid and organosilane monomer and preparation method thereof.
Background technology: in the application of tertiary oil recovery technology, polymer flooding is a kind of well stimulation with fastest developing speed and quite potential at present.And partially hydrolyzed polyacrylamide has obtained widespread use as a kind of water-soluble polymers oil-displacing agent of excellent property in improving oil recovery.But, limited giving full play to of its displacement of reservoir oil usefulness because polyacrylamide is not suitable for the high temperature and high salt oil reservoir.For can be under China's high temperature and high salt reservoir condition the using polymer technology of reservoir sweep, must carry out modification to polymkeric substance.The polymer property of seeking modification comprises the thermostability of polymkeric substance, shear stability, oxidative stability and to the adaptability of hypersaline environment and different salinities, improves recovery ratio to greatest extent.
The approach of synthetic heat-resistant salt-resistant polymkeric substance has following several usually: 1. introduce big side group or rigidity side group to improve the thermostability of polymkeric substance; 2. in molecule, introduce to improve high molecular salt tolerance to the insensitive sulfonic group of salt; 3. the hydrolysis of amide group is the major cause that causes polymkeric substance temperature resistant antisalt performance to reduce on the common molecular chain, and the monomer that introducing can suppress the amide group hydrolysis can make the temperature resistant antisalt performance of polymkeric substance improve; 4. introduce hydrophobic grouping, the hydrophobic association by hydrophobic grouping is used for improving the polymkeric substance temperature resistant antisalt.
In recent ten years, water-soluble hydrophobic associated type polymkeric substance is because its unique solution behavior and rheological property more and more cause people's attention.Hydrophobic associated polymer has been proved to be a kind of effective way that improves the heat-resistant salt-resistant ability of polymkeric substance, becomes a hot research direction.The hydrophobic association monomeric species that is adopted is more, but from existing report, can be divided into two big classes, and a class is to be hydrophobic grouping with the hydrocarbon group, another kind of a spot of research with the carbon fluorin radical as hydrophobic grouping.Domestic oilfield chemistry institute of Shi Ke institute, Southwest Petroleum Institute, Chinese Academy of Sciences Changchun should change institute, Chinese Academy of Sciences Shanghai organic etc. all obtained some positive progress.
Chang Zhiying etc. select for use oxidation/reduction initiating system to carry out the low temperature copolymerization of AMPS/AM, have obtained high molecular (10
6～10
7) and the AMPS/AM copolymer product of high linear regularity, show that after measured this multipolymer has outstanding viscosifying action and to the stability of high temperature and high salt effect, this respect has had the report of industrial application.Employing free radical copolymerizations such as Ye Lin have prepared water soluble propene's acid amides (AM)/2-acrylamido-2-methyl propane sulfonic acid sodium (NaAMPS)/2-methylacryoyloxyethyl-hydrophobic ampholyte copolymer of dimethyl dodecyl bromination ammonium (DMDA), show after tested, owing to introduced hydrophobic structure and zwitter-ion structure in same polymkeric substance, the hydrophobic amphiphilic polymers of this class shows preferably performances such as temperature resistant antisalt.Li Ji etc. have studied acrylamide, 2-acrylamido-2-methyl propane sulfonic acid and a kind of terpolymer ZYS that had not only contained sulfonic group but also contained the amphipathic surface active monomer of hydrophobicity chain alkyl, this multipolymer has higher salt tolerance, short-term and long-term temperature tolerance, injection and shear resistant in solution after tested.
People such as Zhang Yunxiang adopt carbon fluorine chain as the hydrophobic association group first, carry out copolymerization with acrylamide and derivative thereof, have obtained the new type water-solubility hydrophobic associated polymer.Because carbon fluorine chain has littler cohesive energy density(CED) and surface energy, therefore stronger hydrophobicity is arranged, intermolecular easy formation comprises the hydrophobic association structure of many macromolecular chains, hydrodynamic volume sharply increases, make contain the fluorocarbon group copolymer solution than synthetic hydrocarbon chain multipolymer under the same terms want thickness many.
From existing research, no matter be with hydrocarbon group or with the carbon fluorin radical as hydrophobic grouping, association temperature influence between the polymer hydrophobic base is bigger, especially when high temperature (greater than 80 ℃), because the aggravation of the weakening of aquation group hydration, molecular thermalmotion, viscosity degradation is very fast.The existence of these characteristics just requires polymkeric substance that higher low temperature viscosity must be arranged, and higher viscosity residual value is arranged in the time of could guaranteeing high temperature, and higher low temperature viscosity can to the scene annotate poly-bring unfavorable.
Though hydrophobic associated polymer has good heat-resistant salt-resistant performance, its synthesis technique more complicated.This is owing to be difficult to oil-soluble monomer and water-soluble monomer thorough mixing in building-up process.Generally there are two kinds of methods that hydrophobic part is connected on the water-soluble polymers chain, a kind of method that is direct with hydrophobic monomer and water-soluble monomer copolymerization; Another kind is that functionalized macromolecular reaction method is carried out in first copolymerization again.Copolymerization synthetic primary product is the multipolymer of acrylic amide.The macromolecular reaction method is mainly used in derivatived cellulose, polyethyleneglycol derivative and polyacrylic hydrophobically modified etc.
The copolymerization of oil-soluble monomer and water-soluble monomer has three kinds of methods, promptly heterogeneous copolymerization, homogeneous phase copolymerization, micella copolymerization.People such as Hill are with N-(4-ethyl) Phenyl Acrylamide (E Φ AM) and acrylamide copolymerization in water.Make E Φ AM with fine Powdered being dispersed in the acrylamide solution by mechanical stirring in polymerization process, with the increase of system transformation efficiency, fines shape particle dissolves gradually.The reaction product that adopts this method to obtain depends on the composition that feeds intake.In the lower copolymerization of hydrophobic monomer content, reaction system finally becomes homogeneous phase.But under hydrophobic monomer content condition with higher, the transformation efficiency of hydrophobic monomer is lower.
Replacing water with single solvent or mixed solvent is to overcome the not codissolved short-cut method of hydrophobic monomer and water-soluble monomer, people such as people such as Ezzell and Dowling studies show that, this method can solve hydrophobic monomer and the miscible problem of water-soluble monomer, system can reach the dispersion of molecular level, but the polymkeric substance that often occurs generating is insoluble to the phenomenon of reaction solvent, fell compound and precipitate before obtaining to produce the required sufficiently high molecular weight of effective hydrophobic association.The selectable overwhelming majority can be miscible with water solvent (as alcohol, ether, ketone etc.) all owing to the free radical chain transferance makes the copolymerization product molecular weight on the low side.What obtain by this homogeneous phase copolymerization is random copolymers, and the hydrophobic association effect is not obvious in the aqueous solution.
Preparation hydrophobic associated water-soluble polymer copolymerization process commonly used is the micella copolymerization, comes the solubilizing hydrophobic monomer by add suitable tensio-active agent in water, carries out copolymerization with water-soluble monomer.This copolymerization comes down to a kind of microcosmic heterogeneous process.The micella copolymerization is the efficient ways of the good hydrophobic associated water-soluble polymer of preparation tackifying.
Summary of the invention: purpose of the present invention will provide a kind of organic-silicon-modified polyacrylamide and preparation method thereof exactly.
The object of the present invention is achieved like this, and this polymkeric substance is the terpolymer of acrylamide, vinylformic acid and organosilane monomer, and molecular weight is 8,000,000～2,500 ten thousand, has following general structure:
Wherein, R
SiBe organosilicon radical.
Adopt the method for micella copolymerization to prepare organic-silicon-modified polyacrylamide.In adopting acrylamide and organosilane monomer binary copolymerization system, the mass ratio of acrylamide and organosilane monomer is (99.8～90): (0.2～10), better quality is than being (99.5～95.0): (0.5～5.0), and the process hydrolysis obtains the terpolymer of acrylamide, vinylformic acid and organosilane monomer; In the ternary copolymerization system that adopts acrylamide, vinylformic acid and organosilane monomer, the mass ratio of acrylamide, vinylformic acid and organosilane monomer is (50～80): (49.8～10): (0.2～10), preferable mass ratio are (50～85): (49.5～10): (0.5～5).Organosilane monomer can be that vinylformic acid contains the organosilicon oligomer that estersil or methacrylic acid contain estersil or vinyl silanes and contain carbon-carbon double bond.Used tensio-active agent is sodium lauryl sulphate or sodium laurylsulfonate or Dodecyl trimethyl ammonium chloride or dodecyl dihydroxy ethyl trimethyl-glycine or lauroyl diethanolamine or polysorbas20 or class of department 20.Emulsification method can be mechanical stirring emulsification or ultrasonic emulsification.The processing condition of polyreaction are:
Polymerisation medium PH is 5～13, and the best is 7～11;
Polymerization temperature is 0～30 ℃, and the best is 5～25 ℃;
Reaction times is 3～10 hours, and the best is 5～8 hours;
Monomer mass concentration is 10～40%, and the best is 15～35%.
The hydrolysis process parameter is:
The add-on of alkali accounts for 1～30% of total acrylamide quality, is recommended as 5～25%;
60～90 ℃ of hydrolysis temperatures are recommended as 65～85 ℃;
Hydrolysis time 2～12 hours is recommended as 3～10 hours;
Obtain degree of hydrolysis and be 20～30% anionic polymer.
Embodiment: the present invention is described in detail in detail below in conjunction with embodiment.
The polymkeric substance of indication of the present invention is the terpolymer of acrylamide, vinylformic acid and organosilane monomer, has following general structure:
Wherein, R
SiBe organosilicon radical
Adopt the method for micella copolymerization to prepare siliceous polyacrylamide copolymer, in acrylamide and organosilane monomer binary copolymerization system, the mass ratio of acrylamide and organosilane monomer is (99.8～90): (0.2～10); In the ternary copolymerization system of acrylamide, vinylformic acid and organosilane monomer, the mass ratio of acrylamide, vinylformic acid and organosilane monomer is (50～80): (49.8～10): (0.2～10).Organosilane monomer can be that vinylformic acid contains the organosilicon oligomer that estersil or methacrylic acid contain estersil or vinyl silanes and contain carbon-carbon double bond.Used tensio-active agent is sodium lauryl sulphate or sodium laurylsulfonate or Dodecyl trimethyl ammonium chloride or dodecyl dihydroxy ethyl trimethyl-glycine or lauroyl diethanolamine or polysorbas20 or class of department 20.Emulsification method can be mechanical stirring emulsification or ultrasonic emulsification.The processing condition of polyreaction are:
Polymerisation medium PH is 5～13, and the best is 7～11;
Polymerization temperature is 0～30 ℃, and the best is 5～25 ℃;
Reaction times is 3～10 hours, and the best is 5～8 hours;
Monomer mass concentration is 10～40%, and the best is 15～35%.
The hydrolysis process parameter is:
The add-on of alkali accounts for 1～30% of total acrylamide quality, is recommended as 5～25%;
60～90 ℃ of hydrolysis temperatures are recommended as 65～85;
Hydrolysis time 2～12 hours is recommended as 3～10 hours;
Obtain degree of hydrolysis and be 20～30% anionic polymer.
Following examples will help to understand the present invention, but be not limited to the present invention:
Embodiment 1, take by weighing 30 gram acrylamide solids, vinylformic acid 15 grams, 0.5 gram organosilane monomer, 0.05 gram urea, 0.1 gram EDTA-4Na, 68.5 restrain deionized waters, are added in the port grinding bottle to stir, with NaOH regulator solution PH to 11, port grinding bottle is put into 15 ℃ of water-baths, logical nitrogen drove oxygen 30 minutes, added 0.001 gram Potassium Persulphate, 0.01 gram triethylamine initiation reaction, continued logical nitrogen and stopped logical nitrogen after 5 minutes, standing and reacting 5 hours obtains transparent resilient blob of viscose.Take out blob of viscose, shred, dry, pulverize, sieve, obtain the white powder shaped polymer of 20～80 orders, limiting viscosity 17.9dl/g.
Embodiment 2, take by weighing 30 gram acrylamide solids, 0.5 gram organosilane monomer, 0.05 gram urea, 0.1 gram EDTA-4Na, 1 gram NaOH, 68.5 gram deionized waters, be added in the port grinding bottle and stir, port grinding bottle is put into 15 ℃ of water-baths, logical nitrogen drove oxygen 30 minutes, added 0.001 gram Potassium Persulphate, 0.01 gram triethylamine initiation reaction, continued logical nitrogen and stopped logical nitrogen after 5 minutes, standing and reacting 5 hours obtains transparent resilient blob of viscose.Port grinding bottle is put in 80 ℃ of water-baths hydrolysis 3 hours, takes out blob of viscose, shred, dry, pulverize, sieve, obtain the white powder shaped polymer of 20～80 orders, limiting viscosity 19.0dl/g.This polymkeric substance is made into the 5000ppm mother liquor with triumph salt solution (the about 6000ppm of total mineralization, the wherein about 500ppm of calcium ions and magnesium ions), stirred 1.5 hours, obtain 1500ppm solution with the dilution of triumph salt solution again in 700rpm oar formula.This solution is at 70 ℃, 2S
-1Shearing rate under, the apparent viscosity value 33mpa.s that records; 80 ℃, 5S
-1Shearing rate under, the apparent viscosity value 29mpa.s that records; 90 ℃, 5S
-1Shearing rate under, the apparent viscosity value 24.5mpa.s that records;
This polymkeric substance is owing to the temperature resistant capability and the hydrophobic association effect of silicon-containing group, and when high temperature (greater than 80 ℃) high salinities (greater than 20000ppm), soltion viscosity contrast ultra-high molecular weight HPAM has remarkable advantages.This has great significance for the present situation of improving polymer flooding, raising oil recovery factor.
Claims (10)
1, a kind of organic-silicon-modified polyacrylamide, the molecular weight that it is characterized in that this polymkeric substance is 8,000,000～2,500 ten thousand, general structure is:
Wherein, R
SiBe organosilicon radical.
2, a kind of organic-silicon-modified Preparation of Polyacrylamide method is characterized in that being to carry out the binary free radicals copolymerization reaction in the medium with the emulsion or being to carry out the ternary free radicals copolymerization reaction in the medium with the emulsion with acrylamide, vinylformic acid and organosilane monomer with acrylamide and the organosilicon that contains carbon-carbon double bond; In the binary polymerization system, the mass ratio of acrylamide and organosilane monomer is (99.8～90): (0.2～10), preferable mass ratio are (99.5～95): (0.5～5); In ternary copolymerization system, the mass ratio of acrylamide, vinylformic acid and organosilane monomer is (50～80): (49.8～10): (0.2～10), preferable mass ratio are (50～85): (49.5～10): (0.5～5).
3, preparation method as claimed in claim 2 is characterized in that the organosilane monomer that adopts is that vinylformic acid contains the organosilicon oligomer that estersil or methacrylic acid contain estersil or vinyl silanes or contain carbon-carbon double bond.
4, preparation method as claimed in claim 2 is characterized in that the dispersing mode of organosilane monomer in acrylamide solution is on the basis of adding tensio-active agent, behind mechanical stirring or ultrasonic emulsification, obtains stable emulsion again.
5,, it is characterized in that the tensio-active agent that emulsification is adopted is sodium lauryl sulphate or sodium laurylsulfonate or Dodecyl trimethyl ammonium chloride or dodecyl dihydroxy ethyl trimethyl-glycine or lauroyl diethanolamine or polysorbas20 or class of department 20 as claim 2 or 4 described preparation methods.
6, preparation method as claimed in claim 2, it is characterized in that binary copolymerization reaction adopts " preceding add alkali copolymerization posthydrolysis " or " back alkaline hydrolysis " technology, introduce carboxyl on polymer molecular chain, the hydrolytic reagent of employing is that sodium hydroxide or yellow soda ash or sodium bicarbonate or sodium phosphate or sodium hydroxide add boric acid.
7, preparation method as claimed in claim 2, it is characterized in that polymerization process condition is: the pH value of polymerisation medium is 5～13, and polymerization temperature is 0～30 ℃, and the reaction times is 3～10 hours, and the monomer total mass concentration is 10～40%.
8, preparation method as claimed in claim 2, it is characterized in that adopting persulphate and aliphatic amide is redox initiation system.
9,, it is characterized in that the persulphate as redox initiation system is Potassium Persulphate or Sodium Persulfate or ammonium persulphate as claim 2 or 8 described preparation methods; Aliphatic amide is diethylamine or propylamine or triethylamine or aniline or tetramethyl-ethanamide or N-methylmorpholine or N, the N xylidene(s).
10, preparation method as claimed in claim 2 is characterized in that the add-on of alkali accounts for 1～30% of total acrylamide quality in the hydrolysis process, 60～90 ℃ of hydrolysis temperatures, hydrolysis time 2～12 hours.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649832A (en) * | 2012-05-17 | 2012-08-29 | 陕西科技大学 | Preparation method for nonionic hydrophobic association polyacrylamide |
| CN102649830A (en) * | 2012-05-17 | 2012-08-29 | 陕西科技大学 | Preparation method for cation organic silicon modified polyacrylamide |
| CN102675533A (en) * | 2012-05-17 | 2012-09-19 | 陕西科技大学 | Ultrasound auxiliary preparation method of hydrophobic association polyacrylamide (HAPAM) |
| CN103525298A (en) * | 2013-09-24 | 2014-01-22 | 江苏荣昌新材料科技有限公司 | Superhigh-temperature-resisting and anti-corrosion coating as well as preparation method thereof |
| CN105693925A (en) * | 2016-04-13 | 2016-06-22 | 中国石油大学(华东) | Sand prevention multi-branched polymer for oil-water well and preparation method of sand prevention multi-branched polymer |
| CN105694837A (en) * | 2016-04-13 | 2016-06-22 | 中国石油大学(华东) | Polymer sand consolidating agent and preparation method thereof |
| CN106543377A (en) * | 2016-07-13 | 2017-03-29 | 成都菲尔特技术开发有限公司 | A kind of copolymer fluid loss agent and preparation method thereof |
| CN111138589A (en) * | 2020-01-07 | 2020-05-12 | 武汉奥克化学有限公司 | Concrete viscosity regulator and preparation method and application thereof |
| CN115109204A (en) * | 2022-08-09 | 2022-09-27 | 山东大明精细化工有限公司 | Organic silicon surface polymerization agent and application thereof in thickened oil recovery |
-
2003
- 2003-09-28 CN CNA031390765A patent/CN1528796A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649832A (en) * | 2012-05-17 | 2012-08-29 | 陕西科技大学 | Preparation method for nonionic hydrophobic association polyacrylamide |
| CN102649830A (en) * | 2012-05-17 | 2012-08-29 | 陕西科技大学 | Preparation method for cation organic silicon modified polyacrylamide |
| CN102675533A (en) * | 2012-05-17 | 2012-09-19 | 陕西科技大学 | Ultrasound auxiliary preparation method of hydrophobic association polyacrylamide (HAPAM) |
| CN102649832B (en) * | 2012-05-17 | 2013-10-23 | 陕西科技大学 | Preparation method for nonionic hydrophobic association polyacrylamide |
| CN102649830B (en) * | 2012-05-17 | 2013-11-27 | 陕西科技大学 | Preparation method of cation organic silicon modified polyacrylamide |
| CN103525298B (en) * | 2013-09-24 | 2016-01-20 | 江苏荣昌新材料科技有限公司 | Thermostable anticorrosive coating and preparation method |
| CN103525298A (en) * | 2013-09-24 | 2014-01-22 | 江苏荣昌新材料科技有限公司 | Superhigh-temperature-resisting and anti-corrosion coating as well as preparation method thereof |
| CN105693925A (en) * | 2016-04-13 | 2016-06-22 | 中国石油大学(华东) | Sand prevention multi-branched polymer for oil-water well and preparation method of sand prevention multi-branched polymer |
| CN105694837A (en) * | 2016-04-13 | 2016-06-22 | 中国石油大学(华东) | Polymer sand consolidating agent and preparation method thereof |
| CN105694837B (en) * | 2016-04-13 | 2018-08-24 | 中国石油大学(华东) | A kind of polymer sand-fixating agent and preparation method thereof |
| CN106543377A (en) * | 2016-07-13 | 2017-03-29 | 成都菲尔特技术开发有限公司 | A kind of copolymer fluid loss agent and preparation method thereof |
| CN106543377B (en) * | 2016-07-13 | 2018-12-18 | 成都菲尔特技术开发有限公司 | A kind of copolymer fluid loss agent and preparation method thereof |
| CN111138589A (en) * | 2020-01-07 | 2020-05-12 | 武汉奥克化学有限公司 | Concrete viscosity regulator and preparation method and application thereof |
| CN115109204A (en) * | 2022-08-09 | 2022-09-27 | 山东大明精细化工有限公司 | Organic silicon surface polymerization agent and application thereof in thickened oil recovery |
| CN115109204B (en) * | 2022-08-09 | 2023-10-13 | 山东大明精细化工有限公司 | Organosilicon surface-accumulating agent and application thereof in thickened oil exploitation |
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