CN103833896A - Synthesis technology of twin-tailed hydrophobic association polymer based on monomer concentration control - Google Patents
Synthesis technology of twin-tailed hydrophobic association polymer based on monomer concentration control Download PDFInfo
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- CN103833896A CN103833896A CN201210471548.5A CN201210471548A CN103833896A CN 103833896 A CN103833896 A CN 103833896A CN 201210471548 A CN201210471548 A CN 201210471548A CN 103833896 A CN103833896 A CN 103833896A
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Abstract
The invention discloses a synthesis technology of a twin-tailed hydrophobic association polymer based on monomer concentration control. The technology comprises the following steps: preparing twin-tailed hydrophobic monomers; weighing the twin-tailed hydrophobic monomers and sodium dodecyl sulfate, and placing the twin-tailed hydrophobic monomers 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, wherein the monomer concentration is controlled in a range of 25-35%; adjusting the pH value, and adding sodium bicarbonate; stirring, and adding an initiator; introducing an inert gas under a water bath condition, and reacting 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 drier 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 monomer concentration in the synthesis process is controlled to improve the intrinsic viscosity of a target product.
Description
Technical field
The present invention relates to a kind of synthesis technique of the twin tail hydrophobic associated polymer of controlling monomer concentration.
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, the cationic surfactivity hydrophobic monomer 2-methylacryoyloxyethyl-dimethyl dodecyl bromination amine (MEDMDA) synthesizing with oneself again has afterwards obtained hydrophobic associated water-soluble polymer with AM copolymerization, 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 twin tail hydrophobic associated polymer of controlling monomer concentration, monomer concentration will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable monomer concentration, 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 of controlling monomer concentration 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 monomer concentration 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 of controlling monomer concentration, 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 stir it is dissolved completely, and control monomer concentration be 25%～35%;
(e) regulate monomer concentration, 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, isothermal reaction, obtains 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 monomer concentration.
Described rare gas element is nitrogen.
In described step (d), controlling monomer concentration is 28%.
In described step (d), regulating monomer concentration is 30%.
In described step (d), regulating monomer concentration is 32%.
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 monomer concentration in building-up process, thereby improve the intrinsic viscosity of target product.
Brief description of the drawings
?fig. 1 is the schematic diagram of different monomers concentration 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 of controlling monomer concentration 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 stir it is dissolved completely, and control monomer concentration be 25%～35%;
(e) regulate monomer concentration, 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, isothermal reaction, obtains 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 monomer concentration.
Described rare gas element is nitrogen.
In described step (d), controlling monomer concentration is 28%.
In described step (d), regulating monomer concentration is 30%.
In described step (d), regulating monomer concentration is 32%.
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 twin tail hydrophobic associated polymer of controlling monomer concentration, monomer concentration will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable monomer concentration, the synthesis technique of the twin tail hydrophobic associated polymer of controlling monomer concentration is seemed to particularly important.In order to obtain best monomer concentration, the present invention has done the impact experiment of different monomers concentration on product performance viscosity number, experimental result as shown in Figure 1, result is known as shown in Figure 1: along with the increase of total monomer, intrinsic viscosity first increases and then decreases, when total monomer is 30%, intrinsic viscosity maximum, polymericular weight is the highest.When monomer concentration is too low, between monomer, the probability of contact and collision is little, be unfavorable for the growth of molecular chain, and speed of reaction is slow, and the time is long, and polymerization is incomplete.The rising of monomer concentration is conducive to the carrying out of reaction, and maximum value appears in copolymer.In the time that monomer concentration continues to increase, polymerization liberated heat can not be removed in time, in polymerization system, temperature raises, polymerization velocity is accelerated, chain termination speed and chain transport velocity are accelerated simultaneously, the further growth of Inhibitory molecules amount, makes polymer intrinsic viscosity reduce relative molecular mass and reduces, solvability variation.Monomer content is higher, and this phenomenon is more obvious.Therefore, this experiment total monomer is decided to be 30%.
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 controlling the twin tail hydrophobic associated polymer of monomer concentration, 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 stir it is dissolved completely, and control monomer concentration be 25%～35%;
(e) regulate monomer concentration, 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, isothermal reaction, obtains 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 of control monomer concentration 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 of control monomer concentration according to claim 1, is characterized in that, described solvent is distilled water.
4. the synthesis technique of the twin tail hydrophobic associated polymer of control monomer concentration according to claim 1, is characterized in that, in described step (e), by NaOH solution regulator solution monomer concentration.
5. the synthesis technique of the twin tail hydrophobic associated polymer of control monomer concentration 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 of control monomer concentration according to claim 1, is characterized in that, in described step (d), controlling monomer concentration is 28%.
7. the synthesis technique of the twin tail hydrophobic associated polymer of control monomer concentration according to claim 1, is characterized in that, in described step (d), regulating monomer concentration is 30%.
8. the synthesis technique of the twin tail hydrophobic associated polymer of control monomer concentration according to claim 1, is characterized in that, in described step (d), regulating monomer concentration is 32%.
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Application publication date: 20140604 |