CN103833903A - Twin-tailed hydrophobic association polymer - Google Patents

Abstract

The invention discloses a twin-tailed hydrophobic association polymer. The twin-tailed hydrophobic association polymer is obtained through mixing and a reaction of raw materials comprising 50-60% of a twin-tailed hydrophobic monomer, 10-25% of sodium dodecyl sulfate, 1-4% of AM, 2-4% of acrylic acid, 1-2% of an initiator, 1-3% of urea, 0.1-0.3% of sodium bicarbonate, and the balance EDTA. The twin-tailed hydrophobic association polymer has the advantages of excellent performances, simple synthesis step, low synthesis cost and very high market popularization value.

Description

A kind of twin tail hydrophobic associated polymer

Technical field

The present invention relates to a kind of twin tail hydrophobic associated polymer.

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, 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.

Summary of the invention

The object of the invention is to overcome the shortcoming and defect of above-mentioned prior art, a kind of twin tail hydrophobic associated polymer is provided, the excellent property of this twin tail hydrophobic associated polymer, synthesis step is simple, and synthetic cost is low, has very high market popularization value.

Object of the present invention is achieved through the following technical solutions: a kind of twin tail hydrophobic associated polymer, by twin tail hydrophobic monomer, sodium lauryl sulphate, AM, vinylformic acid, EDTA, urea, sodium bicarbonate, initiator hybrid reaction forms, according to mass percent meter, described twin tail hydrophobic monomer accounts for 50%～60% of total amount, sodium lauryl sulphate accounts for 10%～25% of total amount, AM accounts for 1%～4% of total amount, vinylformic acid accounts for 2%～4% of total amount, initiator accounts for 1%～2% of total amount, urea accounts for 1%～3% of total amount, sodium bicarbonate accounts for 0.1%～0.3% of total amount, surplus is EDTA.

According to mass percent meter, described twin tail hydrophobic monomer accounts for 55% of total amount, and sodium lauryl sulphate accounts for 20% of total amount, AM accounts for 3% of total amount, and vinylformic acid accounts for 3% of total amount, and initiator accounts for 1.5% of total amount, urea accounts for 2% of total amount, and sodium bicarbonate accounts for 0.2% of total amount, and surplus is EDTA.

According to mass percent meter, described twin tail hydrophobic monomer accounts for 50% of total amount, and sodium lauryl sulphate accounts for 10% of total amount, AM accounts for 1% of total amount, and vinylformic acid accounts for 2% of total amount, and initiator accounts for 1% of total amount, urea accounts for 1% of total amount, and sodium bicarbonate accounts for 0.1% of total amount, and surplus is EDTA.

According to mass percent meter, described twin tail hydrophobic monomer accounts for 60% of total amount, and sodium lauryl sulphate accounts for 25% of total amount, AM accounts for 4% of total amount, and vinylformic acid accounts for 4% of total amount, and initiator accounts for 2% of total amount, urea accounts for 3% of total amount, and sodium bicarbonate accounts for 0.3% of total amount, and surplus is EDTA.

In sum, the invention has the beneficial effects as follows: excellent property, synthesis step is simple, and synthetic cost is low, has very high market popularization value.

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 1:

The twin tail hydrophobic associated polymer of one the present invention relates to, formed by twin tail hydrophobic monomer, sodium lauryl sulphate, AM, vinylformic acid, EDTA, urea, sodium bicarbonate, initiator hybrid reaction, according to mass percent meter, described twin tail hydrophobic monomer accounts for 50%～60% of total amount, sodium lauryl sulphate accounts for 10%～25% of total amount, AM accounts for 1%～4% of total amount, vinylformic acid accounts for 2%～4% of total amount, initiator accounts for 1%～2% of total amount, urea accounts for 1%～3% of total amount, sodium bicarbonate accounts for 0.1%～0.3% of total amount, and surplus is EDTA.

Embodiment 2:

The present embodiment is only with enforcement 1 difference: according to mass percent meter, described twin tail hydrophobic monomer accounts for 55% of total amount, sodium lauryl sulphate accounts for 20% of total amount, AM accounts for 3% of total amount, vinylformic acid accounts for 3% of total amount, and initiator accounts for 1.5% of total amount, and urea accounts for 2% of total amount, sodium bicarbonate accounts for 0.2% of total amount, and surplus is EDTA.

Embodiment 3:

The present embodiment is only with enforcement 1 difference: according to mass percent meter, described twin tail hydrophobic monomer accounts for 50% of total amount, sodium lauryl sulphate accounts for 10% of total amount, AM accounts for 1% of total amount, vinylformic acid accounts for 2% of total amount, and initiator accounts for 1% of total amount, and urea accounts for 1% of total amount, sodium bicarbonate accounts for 0.1% of total amount, and surplus is EDTA.

Embodiment 4:

The present embodiment is only with enforcement 1 difference: according to mass percent meter, described twin tail hydrophobic monomer accounts for 60% of total amount, sodium lauryl sulphate accounts for 25% of total amount, AM accounts for 4% of total amount, vinylformic acid accounts for 4% of total amount, and initiator accounts for 2% of total amount, and urea accounts for 3% of total amount, sodium bicarbonate accounts for 0.3% of total amount, and surplus is EDTA.

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 (4)

1. a twin tail hydrophobic associated polymer, it is characterized in that, formed by twin tail hydrophobic monomer, sodium lauryl sulphate, AM, vinylformic acid, EDTA, urea, sodium bicarbonate, initiator hybrid reaction, according to mass percent meter, described twin tail hydrophobic monomer accounts for 50%～60% of total amount, sodium lauryl sulphate accounts for 10%～25% of total amount, AM accounts for 1%～4% of total amount, vinylformic acid accounts for 2%～4% of total amount, initiator accounts for 1%～2% of total amount, urea accounts for 1%～3% of total amount, and sodium bicarbonate accounts for 0.1%～0.3% of total amount, and surplus is EDTA.

2. the twin tail hydrophobic associated polymer of one according to claim 1, it is characterized in that, according to mass percent meter, described twin tail hydrophobic monomer accounts for 55% of total amount, and sodium lauryl sulphate accounts for 20% of total amount, AM accounts for 3% of total amount, vinylformic acid accounts for 3% of total amount, and initiator accounts for 1.5% of total amount, and urea accounts for 2% of total amount, sodium bicarbonate accounts for 0.2% of total amount, and surplus is EDTA.

3. the twin tail hydrophobic associated polymer of one according to claim 1, it is characterized in that, according to mass percent meter, described twin tail hydrophobic monomer accounts for 50% of total amount, and sodium lauryl sulphate accounts for 10% of total amount, AM accounts for 1% of total amount, vinylformic acid accounts for 2% of total amount, and initiator accounts for 1% of total amount, and urea accounts for 1% of total amount, sodium bicarbonate accounts for 0.1% of total amount, and surplus is EDTA.

4. the twin tail hydrophobic associated polymer of one according to claim 1, it is characterized in that, according to mass percent meter, described twin tail hydrophobic monomer accounts for 60% of total amount, and sodium lauryl sulphate accounts for 25% of total amount, AM accounts for 4% of total amount, vinylformic acid accounts for 4% of total amount, and initiator accounts for 2% of total amount, and urea accounts for 3% of total amount, sodium bicarbonate accounts for 0.3% of total amount, and surplus is EDTA.