CN103833913A - Synthesis technology of twin-tailed hydrophobic associating polymer with control of surfactant using amount] - Google Patents
Synthesis technology of twin-tailed hydrophobic associating polymer with control of surfactant using amount] Download PDFInfo
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- CN103833913A CN103833913A CN201210471661.3A CN201210471661A CN103833913A CN 103833913 A CN103833913 A CN 103833913A CN 201210471661 A CN201210471661 A CN 201210471661A CN 103833913 A CN103833913 A CN 103833913A
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Abstract
The invention discloses synthesis technology of twin-tailed hydrophobic associating polymer for controlling amount of surfactant. The synthesis technology comprises: preparing a twin-tailed hydrophobic monomer; weighing the twin-tailed hydrophobic monomer and sodium dodecyl sulfate, putting in a reaction vessel, wherein the mol ratio between sodium dodecyl sulfate and twin-tailed hydrophobic monomer is 10-30; adding a solvent and stirring; under the condition of an ice-bath, adding AM, acrylic acid , EDTA, and urea, and stirring for dissolution; adding sodium bicarbonate for adjusting the pH value; stirring and adding an initiator; injecting inert gas under the condition of a water bath, performing a constant temperature reaction to obtain polymer gel; adding water for swelling and dissolving, adding acetone for deposition, and washing; removing residual water; drying in vacuum and crushing; putting into a drier for later use. According to the invention, the twin-tailed hydrophobic associating polymer is synthesized successfully. The invention is characterized in excellent performance, simple synthesis steps, greatly reduced synthesis cost, improved intrinsic viscosity of the object product through controlling amount of the surfactant.
Description
Technical field
The present invention relates to a kind of synthesis technique of twin tail hydrophobic associated polymer of control surface promoting agent consumption.
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 take 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 of control surface promoting agent consumption, dosage of surfactant will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable dosage of surfactant, 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 twin tail hydrophobic associated polymer of control surface promoting agent consumption 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 dosage of surfactant 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 twin tail hydrophobic associated polymer of control surface promoting agent consumption, 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, the mol ratio of described sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 10～30;
(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 dosage of surfactant, 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 dosage of surfactant.
Described rare gas element is nitrogen.
In described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 15.
In described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 20.
In described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 25.
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 dosage of surfactant in building-up process, thereby improve the intrinsic viscosity of target product.
Accompanying drawing explanation
?fig. 1 is the schematic diagram of different surfaces promoting agent consumption 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 the twin tail hydrophobic associated polymer of a kind of control surface promoting agent consumption 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, the mol ratio of described sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 10～30;
(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 dosage of surfactant, 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 dosage of surfactant.
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 of control surface promoting agent consumption, dosage of surfactant will directly have influence on the intrinsic viscosity of the target product synthesizing, so, determine a suitable dosage of surfactant, the synthesis technique of the twin tail hydrophobic associated polymer to control surface promoting agent consumption seems particularly important.In order to obtain best dosage of surfactant, the present invention has done the impact experiment of different surfaces promoting agent consumption on product performance viscosity number, in polyreaction, the mol ratio of dosage of surfactant and hydrophobic monomer consumption is called to SMR value, in test, fixing hydrophobic monomer charging capacity, investigate the impact of dosage of surfactant on polymerization reaction system by changing SMR value, experimental result as shown in Figure 1, result is known as shown in Figure 1: along with the increase of SMR value, it is large that the intrinsic viscosity of product presents first change, then the trend diminishing.Along with the variation of SMR value, dosage of surfactant is larger on the impact of product property viscosity number.In this polymerization reaction system, the effect of tensio-active agent is to make the micella inside of hydrophobic monomer solubilising in its formation, to participate in polyreaction.The number of micella is relevant with the consumption of tensio-active agent with size.In the situation that keeping hydrophobic monomer charging capacity constant, in the time that SMR value is little, the consumption of tensio-active agent is few, is not enough to form the solubilization micelle of hydrophobic monomer in the aqueous solution, thereby reaction can not normally be carried out.In this polyreaction, because colliding, long-chain free radical and solubilization micelle cause hydrophobic monomer polymerization.In the time that SMR value is excessive, polyreaction will be difficult to occur.When SMR value is 20, be 20 o'clock by the mol ratio of surfactant SDS consumption and hydrophobic monomer consumption, the intrinsic viscosity maximum of this polyreaction, the molecular weight maximum of resulting polymers.
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 of control surface promoting agent consumption, 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, the mol ratio of described sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 10～30;
(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 dosage of surfactant, 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 surface promoting agent consumption 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 surface promoting agent consumption 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 surface promoting agent consumption according to claim 1, is characterized in that, in described step (e), by NaOH solution regulator solution dosage of surfactant.
5. the synthesis technique of the twin tail hydrophobic associated polymer of control surface promoting agent consumption 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 surface promoting agent consumption according to claim 1, is characterized in that, in described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 15.
7. the synthesis technique of the twin tail hydrophobic associated polymer of control surface promoting agent consumption according to claim 1, is characterized in that, in described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 20.
8. the synthesis technique of the twin tail hydrophobic associated polymer of control surface promoting agent consumption according to claim 1, is characterized in that, in described step (b), the mol ratio of sodium lauryl sulphate and twin tail hydrophobic monomer consumption is 25.
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Application publication date: 20140604 |