CN103833898A - Synthesis technology of twin-tailed hydrophobic association polymer based on reaction temperature control - Google Patents
Synthesis technology of twin-tailed hydrophobic association polymer based on reaction temperature control Download PDFInfo
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- CN103833898A CN103833898A CN201210471562.5A CN201210471562A CN103833898A CN 103833898 A CN103833898 A CN 103833898A CN 201210471562 A CN201210471562 A CN 201210471562A CN 103833898 A CN103833898 A CN 103833898A
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Abstract
The invention discloses a synthesis technology of a twin-tailed hydrophobic association polymer based on reaction temperature control. The technology comprises the following steps: preparing a twin-tailed hydrophobic monomer; weighing the twin-tailed hydrophobic monomer and sodium dodecyl sulfate, placing the twin-tailed hydrophobic monomer and sodium dodecyl sulfate in a reaction container; adding a solvent, and stirring; adding AM, acrylic acid, EDTA and urea under an ice bath condition, and stirring for dissolving; adjusting the pH value, and adding sodium bicarbonate; stirring, and adding an initiator; letting in an inert gas under a water bath condition, and carrying out a constant temperature reaction at 15-25DEG C to obtain a polymer colloid; adding water for swelling and dissolving, dumping into acetone to obtain a precipitate, and washing the precipitate; removing residual water; and carrying out vacuum drying crushing, and putting the obtained powder in a dryer for later use. The twin-tailed hydrophobic association polymer can be successfully synthesized through the technology, and the synthesized twin-tailed hydrophobic association polymer has the advantages of excellent performances, simple synthesis steps and substantially reduced synthesis cost; and the reaction temperature in the synthesis process is controlled to improve the intrinsic viscosity of the target product.
Description
Technical field
The present invention relates to a kind of synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction.
Background technology
Hydrophobic associated water-soluble polymer, refers to the water-soluble polymers with a small amount of hydrophobic grouping on polymer hydrophilicity macromolecular chain.On water-soluble macromolecule chain, introducing a small amount of hydrophobic grouping makes its aqueous solution show unique rheological property.On certain polymer concentration, hydrophobic part associates and forms dynamic three-dimensional net structure, thereby forms very large supramolecule chain aggregation body, increases the hydrodynamic volume of polymkeric substance, improves significantly the viscosity of solution.The electrolytical polarity that can increase solvent that adds of small molecules, strengthens hydrophobic association effect, produces obvious salt resistance.Under high shear forces, the dynamic physical cross-linked network structure that hydrophobic association forms is destroyed, soltion viscosity declines, shearing action reduction or the physical crosslinking of eliminating between rear macromolecular chain form again, viscosity will be recovered again, the irreversible machinery degraded of the polymkeric substance that general high molecular do not occur under high shear rate.Just because of its unique SOLUTION PROPERTIES, it may be applied in a lot of fields, as tertiary oil recovery, pharmacy, solar energy converting, makeup, coating, water treatment and flow improver etc.Its correlative study in recent years receives much attention.
Hydrophobic close ester phenomenon is very general, below critical association concentration, mainly forms in molecule and associates, and consequently makes a ball of string shrink, and hydrodynamic volume reduces; More than CAC, main formation taking Interpolymer Association as main supramolecular structure has good tackifying.By Interpolymer Association, on the macro property of solution, show the feature that tackifying is strong, have certain temperature resistance, anti-salt and anti-shear ability.These special performances of hydrophobic associated polymer make it in many industrial technologies, all show huge application potential, and have great importance for the solution behavior that imitates the amphiphilic class material in life entity, thereby the exploration of hydrophobic associated water-soluble polymer is become to recent two decades carry out one of problem the most interesting in water-soluble polymers research field, and become the focus that industry and academia are studied.
Should trace back to the fifties initial stage to the research of amphiphilic base polymer, Strauss and assistant thereof have synthesized the solution behavior of a series of polysoaps in order to mimic protein for this reason, first Kauzmann has proposed the concept of " hydrophobic interaction ", and describes biological polymer as a series of phenomenons relevant to life science such as the formation of film in the constraint to enzyme of the conformation transition of protein, matrix, organism with it.In the later stage in the sixties, Strauss group has synthesized again a series of hydrophobic super coil polymkeric substance that have.Contemporaneity, hydrophobically modified urea alkane (HEUR) comes out and is very fast for improving the rheological of water-based latex coating.Until today, researchist, still in effort, attempts that HEUR is made further improvements or find novel material and replaces HEUR.
Last century the eighties, the SOLUTION PROPERTIES of hydrophobic associated polymer uniqueness and huge application potential thereof have attracted a large amount of researchists.Landoll is considered to study the real beginning of hydrophobic associated water-soluble polymer about the research of Natvosol (HEC) hydrophobically modified.The people such as Emmons have delivered the patent with chain alkyl N-substituted acrylamide (CnAM) copolymerization cooperation water-based paint with acrylamide (AM).Before and after 1984, the researchist of Exxon research and engineering corporation starts to inquire into hydrophobic associated polymer the feasibility for oil-gas mining, and this is carried out to lasting and deep research, develop various hydrophobic monomer, and invent the novel polymeric method that solves hydrophilic monomer and the inconsistent problem of hydrophobic monomer in hydrophobic associated polymer polymerization process, it is micellar free radical copolymerization method, be called for short micellar copolymerization, the method is still the best approach in all polymerization processs of hydrophobic associated polymer up to now.
At home, petroleum exploration and development research institute oiling the research that first started hydrophobic associated water-soluble polymer in 1995 of researchist, found that this base polymer has good temperature resistance, anti-salt and anti-shear ability, but while using, need to add stablizer in salt solution.After this, the yellow high honour of Sichuan University has been carried out desk study with vinylformic acid n-octyl as hydrophobic monomer, obtained hydrophobic associated water-soluble polymer with cationic surfactivity hydrophobic monomer 2-methylacryoyloxyethyl-dimethyl dodecyl bromination amine and AM copolymerization that oneself synthesizes again afterwards, but the viscosity of the water-soluble polymers obtaining is very low, and critical association is dense.
Hydrophobic associated water-soluble polymer is by the atom difference that forms main chain, can be divided into carbochain and heteroatoms molecular backbone chain polymkeric substance, the former is mainly the multipolymer being obtained by the alkene monomer polymer of hydrophilic radical and hydrophobic grouping, what hydrophilic monomer was conventional mainly contains acrylamide and vinylformic acid etc., and hydrophobic monomer mainly contains acrylamide derivative, long-chain acrylate etc.; The latter mainly passes through water-soluble high-molecular compound modification through macromolecular reaction, introduces hydrophobic functional group.Macromolecular reaction method advantage is directly to make starting raw material with commercial polymer, and the product relative molecular mass obtaining is high, and its shortcoming is that reaction is carried out in full-bodied polymers soln, and reactant is not easy to mix.Natvosol (HEC) can be reacted with the hydrophobic compound with active group in this way, these hydrophobic compounds can be with the epoxy compounds of chain alkyl, halohydrocarbon, carboxylic acid halides, isocyanic ester etc., also can be at polyoxyethylene glycol (PEG) two termination hydrophobic groupings, but the amount of the general hydrophobic grouping of introducing is all little, because the high solvability that can significantly reduce water-soluble polymer of content of hydrophobic monomers, and heteroatoms trunk polymer is compared with carbon chain polymer, thermostability is poor.Because when the carbon atom in macromolecular chain is replaced by heteroatomss such as oxygen, sulphur, nitrogen, the bond energy of C-O, C-S, C-N key is lower than C-C key, and polymer thermostable reduces.Therefore be, mainly the multipolymer being obtained by the vinyl monomer polymerization of hydrophilic radical and hydrophobic grouping for the hydrophobic associated water-soluble polymer of tertiary oil production in oil field at present.The conventional hydrophilic monomer of hydrophobic associated polymer that utilizes process for copolymerization to prepare is acrylamide (AM), because acrylamide is suitable for preparing the water-soluble polymers of high molecular, reasonable price.In addition, in order to increase the solvability of multipolymer, the anionic monomer that also can add other as vinylformic acid (methacrylic acid), vinylsulfonate, 2-methyl-2-acrylamido propanesulfonic acid (AMPS) etc. with cationic monomer as β-dimethyl-aminoethylmethacrylate base trimethyl ammonium chloride, 2-acrylimide base-2-trimethoxysilyl propyl methacrylate ammonium chloride (AMPTAC), diallyldimethylammonium chloride etc.
Acrylamide hydrophobic associated copolymer is divided into three major types by the hydrophobic monomer of introducing: N-alkyl acrylamide hydrophobically modified multipolymer, acrylate hydrophobically modified multipolymer, Styrene and its derivatives hydrophobically modified multipolymer.
Because the intrinsic viscosity of polymkeric substance directly has influence on use properties, the also molecular size range of reactive polymeric thing of while, so weigh the quality of reaction conditions with the intrinsic viscosity of polymkeric substance.In the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction, temperature of reaction will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable temperature of reaction, the synthesis technique of twin tail hydrophobic associated polymer is seemed to particularly important.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction is provided, this synthesis technique can successfully synthesize twin tail hydrophobic associated polymer, and the excellent property of the twin tail hydrophobic associated polymer synthesizing, synthesis step is simple, greatly reduces synthetic cost; And by controlling the temperature of reaction in building-up process, thereby improve the intrinsic viscosity of target product.
Object of the present invention is achieved through the following technical solutions: a kind of synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction, comprises the following steps:
(a) first, prepare twin tail hydrophobic monomer;
(b) then, take a certain amount of twin tail hydrophobic monomer and sodium lauryl sulphate and be placed in reaction vessel;
(c) add solvent and be stirred to solution transparent;
(d) under condition of ice bath, add a certain amount of AM, vinylformic acid, EDTA, urea, and stirring is dissolved it completely;
(e) regulate temperature of reaction, add a certain amount of sodium bicarbonate;
(f) logical stirring of inert gas, adds initiator;
(g) under water bath condition, continue logical rare gas element, 15 DEG C～25 DEG C reactions of constant temperature, obtain polymeric colloid;
(h) polymeric colloid is shredded, add water swelling, dissolve after, pour in acetone and precipitate, and by methanol wash;
(i) polymkeric substance precipitation being obtained with dehydrated alcohol extraction to remove residual moisture;
(j) last, vacuum-drying is pulverized, and puts into moisture eliminator for subsequent use.
The detailed process of described step (a) is as follows:
(a1) first, acrylate chloride is dissolved in dichloromethane solution;
(a2) then, acrylate chloride and methylene dichloride mixing solutions, Di-n-Butyl Amine, the NaOH aqueous solution are added in reaction vessel, fully shake up;
(a3) then, reaction vessel is placed in to water-bath;
(a4) stir and pass into rare gas element;
(a5) separate organic layer washing;
(a6) dry, steam solvent, obtain light yellow oily liquid;
(a7) add stopper, underpressure distillation at certain vacuum degree and temperature, obtains colourless oil liquid and is twin tail hydrophobic monomer.
Described solvent is distilled water.
In described step (e), by NaOH solution regulator solution temperature of reaction.
Described rare gas element is nitrogen.
In described step (g), temperature of reaction is 18 DEG C.
In described step (g), temperature of reaction is 20 DEG C.
In described step (g), temperature of reaction is 22 DEG C.
In sum, the invention has the beneficial effects as follows: can successfully synthesize twin tail hydrophobic associated polymer, and the excellent property of the twin tail hydrophobic associated polymer synthesizing, synthesis step is simple, greatly reduces synthetic cost; And by controlling the temperature of reaction in building-up process, thereby improve the intrinsic viscosity of target product.
Brief description of the drawings
?fig. 1 is the schematic diagram of differential responses temperature on the impact of product performance viscosity number.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited only to this.
Embodiment:
The synthesis technique of a kind of twin tail hydrophobic associated polymer based on control temperature of reaction the present invention relates to, comprises the following steps:
(a) first, prepare twin tail hydrophobic monomer;
(b) then, take a certain amount of twin tail hydrophobic monomer and sodium lauryl sulphate and be placed in reaction vessel;
(c) add solvent and be stirred to solution transparent;
(d) under condition of ice bath, add a certain amount of AM, vinylformic acid, EDTA, urea, and stirring is dissolved it completely;
(e) regulate temperature of reaction, add a certain amount of sodium bicarbonate;
(f) logical stirring of inert gas, adds initiator;
(g) under water bath condition, continue logical rare gas element, 15 DEG C～25 DEG C reactions of constant temperature, obtain polymeric colloid;
(h) polymeric colloid is shredded, add water swelling, dissolve after, pour in acetone and precipitate, and by methanol wash;
(i) polymkeric substance precipitation being obtained with dehydrated alcohol extraction to remove residual moisture;
(j) last, vacuum-drying is pulverized, and puts into moisture eliminator for subsequent use.
The detailed process of described step (a) is as follows:
(a1) first, acrylate chloride is dissolved in dichloromethane solution;
(a2) then, acrylate chloride and methylene dichloride mixing solutions, Di-n-Butyl Amine, the NaOH aqueous solution are added in reaction vessel, fully shake up;
(a3) then, reaction vessel is placed in to water-bath;
(a4) stir and pass into rare gas element;
(a5) separate organic layer washing;
(a6) dry, steam solvent, obtain light yellow oily liquid;
(a7) add stopper, underpressure distillation at certain vacuum degree and temperature, obtains colourless oil liquid and is twin tail hydrophobic monomer.
Described solvent is distilled water.
In described step (e), by NaOH solution regulator solution temperature of reaction.
Described rare gas element is nitrogen.
Because the intrinsic viscosity of polymkeric substance directly has influence on use properties, the also molecular size range of reactive polymeric thing of while, so weigh the quality of reaction conditions with the intrinsic viscosity of polymkeric substance.In the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction, temperature of reaction will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable temperature of reaction, the synthesis technique of the twin tail hydrophobic associated polymer based on controlling temperature of reaction is seemed to particularly important.In order to obtain best temperature of reaction, the present invention has done the impact experiment of differential responses temperature on product performance viscosity number, and as shown in Figure 1, result is known as shown in Figure 1 for experimental result: the intrinsic viscosity of polymkeric substance reduces a little with the increase of temperature.From reaction kinetics, in the ordinary course of things, temperature of reaction is more low better, but too low-grade polymer product relative molecular mass is not high for temperature, and temperature of reaction is when too high, and the relative mass of product significantly reduces, and is prone to implode.Temperature is less on the impact of polyreaction.Increase temperature profile viscosity number and decrease, but impact is little.Consider, this polyreaction is selected 20 DEG C as reaction conditions.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction, every foundation technical spirit of the present invention, and any simple modification, equivalent variations that above embodiment is done, within all falling into protection scope of the present invention.
Claims (8)
1. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction, is characterized in that, comprises the following steps:
(a) first, prepare twin tail hydrophobic monomer;
(b) then, take a certain amount of twin tail hydrophobic monomer and sodium lauryl sulphate and be placed in reaction vessel;
(c) add solvent and be stirred to solution transparent;
(d) under condition of ice bath, add a certain amount of AM, vinylformic acid, EDTA, urea, and stirring is dissolved it completely;
(e) regulate temperature of reaction, add a certain amount of sodium bicarbonate;
(f) logical stirring of inert gas, adds initiator;
(g) under water bath condition, continue logical rare gas element, 15 DEG C～25 DEG C reactions of constant temperature, obtain polymeric colloid;
(h) polymeric colloid is shredded, add water swelling, dissolve after, pour in acetone and precipitate, and by methanol wash;
(i) polymkeric substance precipitation being obtained with dehydrated alcohol extraction to remove residual moisture;
(j) last, vacuum-drying is pulverized, and puts into moisture eliminator for subsequent use.
2. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, the detailed process of described step (a) is as follows:
(a1) first, acrylate chloride is dissolved in dichloromethane solution;
(a2) then, acrylate chloride and methylene dichloride mixing solutions, Di-n-Butyl Amine, the NaOH aqueous solution are added in reaction vessel, fully shake up;
(a3) then, reaction vessel is placed in to water-bath;
(a4) stir and pass into rare gas element;
(a5) separate organic layer washing;
(a6) dry, steam solvent, obtain light yellow oily liquid;
(a7) add stopper, underpressure distillation at certain vacuum degree and temperature, obtains colourless oil liquid and is twin tail hydrophobic monomer.
3. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, described solvent is distilled water.
4. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, in described step (e), by NaOH solution regulator solution temperature of reaction.
5. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, described rare gas element is nitrogen.
6. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, in described step (g), temperature of reaction is 18 DEG C.
7. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, in described step (g), temperature of reaction is 20 DEG C.
8. the synthesis technique of the twin tail hydrophobic associated polymer based on control temperature of reaction according to claim 1, is characterized in that, in described step (g), temperature of reaction is 22 DEG C.
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| CN104744631A (en) * | 2015-03-30 | 2015-07-01 | 长江大学 | Oil-phase-free high-efficiency instant low-friction-resistance slick-water fracturing fluid drag reducer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104744631A (en) * | 2015-03-30 | 2015-07-01 | 长江大学 | Oil-phase-free high-efficiency instant low-friction-resistance slick-water fracturing fluid drag reducer |
| CN104744631B (en) * | 2015-03-30 | 2017-07-07 | 长江大学 | Slippery water fracturing fluid system drag reducer without the low frictional resistance of oil phase efficient instant |
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Application publication date: 20140604 |