CN103837440A - Method for testing influence of mass concentration on apparent viscosity of hydrophobic association polymer - Google Patents
Method for testing influence of mass concentration on apparent viscosity of hydrophobic association polymer Download PDFInfo
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- CN103837440A CN103837440A CN201210481845.8A CN201210481845A CN103837440A CN 103837440 A CN103837440 A CN 103837440A CN 201210481845 A CN201210481845 A CN 201210481845A CN 103837440 A CN103837440 A CN 103837440A
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Abstract
The invention discloses a method for testing the influence of the mass concentration on the apparent viscosity of a hydrophobic association polymer. The method comprises the following steps: 1, preparing the hydrophobic association polymer; 2, dissolving the hydrophobic association polymer in a solvent to form solutions having different mass concentrations; 3, respectively placing the hydrophobic association polymer solutions in experiment containers; 4, respectively placing the experiment containers in water baths having a same temperature; and 5, measuring the apparent viscosities of the hydrophobic association polymer solutions having different mass concentrations under a same stirring condition through a viscometer, and analyzing data to obtain the influence of the mass concentration of the hydrophobic association polymer on the apparent viscosity. The method can be successfully applied to test the influence of the mass concentration on the apparent viscosity of the hydrophobic association polymer, and has the advantages of accurate test result, simple test steps, and substantial reduction of the test cost.
Description
Technical field
The present invention relates to the method for testing of a kind of hydrophobic associated polymer mass concentration to apparent viscosity influence.
Background technology
Hydrophobic associated 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 supermolecule 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 little molecule, 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, solution viscosity declines, shear 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-rate of shear.Just because of its unique SOLUTION PROPERTIES, it may be applied in a lot of fields, as tertiary oil recovery, pharmacy, sun power conversion, cosmetics, coating, water treatment and drag reducer 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 XC 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, biosome 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 new 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 hydroxyethyl cellulose (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 polymerizations of hydrophobic associated polymer up to now.
Hydrophobic associated water-soluble polymer is by the atom difference that forms main chain, can be divided into carbochain and heteroatoms molecular backbone 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 acrylic 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 initiation 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 polymer solution, and reactant is not easy to mix.Hydroxyethyl cellulose (HEC) can be reacted with the hydrophobic compound with reactive group in this way, these hydrophobic compounds can be with the epoxy compound of chain alkyl, halogenated hydrocarbons, carboxylic acid halides, isocyanates etc., also can be at polyglycol (PEG) two termination hydrophobic groupings, but the amount of the general hydrophobic grouping of introducing is all little, because the high dissolubility that can significantly reduce water soluble polymer of content of hydrophobic monomers, and heteroatoms trunk polymer is compared with carbochain polymer, thermal stability 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 dissolubility of multipolymer, the anionic monomer that also can add other as acrylic acid (methacrylic acid), vinylsulfonate, 2-methyl-2-acrylamido propane sulfonic 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.
The architectural feature of hydrophobic associated water-soluble polymer is on the strand of polymkeric substance, to introduce a small amount of hydrophobic grouping.The polar group of hydrophilic segment can form hydrogen bond and show very strong affinity with hydrone.What form hydrophobic associated polymer molecule hydrophobic part is non-polar group, between they and hydrone, only has Van der Waals force, this acting force a little less than than the interaction hydrogen bond between hydrone many, thereby can not effectively replace with hydrone with interaction of hydrogen bond.The hydrophobic grouping of this type of solute molecule in dissolved state is present in water environment, and the approach that hydrophobic group is fled from water environment is that hydrophobic associated polymer molecule associates and forms aggregation together with hydrophobic group at the inner association body that forms of solution.Hydrophobic grouping, due to water insoluble, is close together under the driving of hydrone, also can be understood as conversely the effect that hydrophobic grouping is subject to association force and flocks together.
Because hydrophobic associated water-soluble polymer has unique structure, thereby there is good temperature resistance, anti-salt and the special solution property that is different from general polymerization thing such as anti-shearing.In recent years, the exploitation of hydrophobic associated water-soluble polymer new product, structure investigation, performance study become the emphasis of people's research gradually.The character of twin tail hydrophobic associated water-soluble polymer in solution also should have relation with external factor such as the internal factors such as the concentration of polymkeric substance, structure and composition, molecular weight and temperature, shear rate, solution ion strength, surfactants, is necessary it further to inquire into.
Summary of the invention
The object of the invention is to overcome the shortcoming and defect of above-mentioned prior art, the method of testing of a kind of hydrophobic associated polymer mass concentration to apparent viscosity influence is provided, this method of testing can be successfully applied to the test of hydrophobic associated polymer mass concentration to apparent viscosity influence, and test result is accurate, testing procedure is simple, greatly reduces testing cost.
Object of the present invention is achieved through the following technical solutions: the method for testing of a kind of hydrophobic associated polymer mass concentration to apparent viscosity influence, comprises the following steps:
(a) first, prepare hydrophobic associated polymer;
(b) then, hydrophobic associated polymer is become to the solution of different quality concentration by dissolution with solvents;
(c) hydrophobic association polymer solution of getting respectively different quality concentration is placed in experiment container;
(d) experiment container is placed in respectively to the water-bath of uniform temp;
(e) under the stirring condition of identical speed, record the apparent viscosity of the hydrophobic association polymer solution of different quality concentration by viscosity meter, by analyzing data, thereby draw the impact of hydrophobic associated polymer mass concentration on apparent viscosity.
Described experiment container is beaker.
Described bath temperature is 25 DEG C.
Described viscosity is counted the fast rotational viscosimeter of ZNN-D6 type six.
The mass concentration of described hydrophobic associated polymer is respectively 1.0g/L, 2.0g/L, 3.0g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L.
In sum, the invention has the beneficial effects as follows: can be successfully applied to the test of hydrophobic associated polymer mass concentration to apparent viscosity influence, and test result is accurate, testing procedure is simple, greatly reduces testing cost.
Brief description of the drawings
?fig. 1 is the apparent viscosity schematic diagram of different hydrophobic associated polymer mass concentrations.
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 method of testing of a kind of hydrophobic associated polymer mass concentration the present invention relates to apparent viscosity influence, comprises the following steps:
(a) first, prepare hydrophobic associated polymer;
(b) then, hydrophobic associated polymer is become to the solution of different quality concentration by dissolution with solvents;
(c) hydrophobic association polymer solution of getting respectively different quality concentration is placed in experiment container;
(d) experiment container is placed in respectively to the water-bath of uniform temp;
(e) under the stirring condition of identical speed, record the apparent viscosity of the hydrophobic association polymer solution of different quality concentration by viscosity meter, by analyzing data, thereby draw the impact of hydrophobic associated polymer mass concentration on apparent viscosity.
Described experiment container is beaker.
Described bath temperature is 25 DEG C.
Described viscosity is counted the fast rotational viscosimeter of ZNN-D6 type six.
The mass concentration of described hydrophobic associated polymer is respectively 1.0g/L, 2.0g/L, 3.0g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L.
As shown in Figure 1, as shown in Figure 1: aqueous solution apparent viscosity continues to increase with the increase of polymer concentration, in the time that its concentration reaches certain value, its aqueous solution apparent viscosity sharply rises the result being recorded by said method.This phenomenon shows, due to adding of hydrophobic grouping on AM macromolecular chain, makes to produce hydrophobic association effect between large molecular coil, forms a kind of supramolecular structure-dynamic physical cross-linked network, thereby has greatly improved the apparent viscosity of aqueous solutions of polymers.In addition, it can also be seen that from Fig. 1, in the viscosity-concentration curve of aqueous solution, when hydrophobic monomer (DC) consumption is in 0.4%～1.2% polymer solution, about polymer concentration C=5.0g/L, hydrophobic monomer (DC) consumption 2.0% time, polymer concentration C=4.0g/L left and right.On curve, there is a turning point separately respectively, after this point, solution apparent viscosity increases and sharply increases with polymer concentration, and we call critical association concentration C * concentration corresponding this point conventionally, corresponding polymer concentration when being solution apparent viscosity and sharply increasing.In the time of C < C*, the apparent viscosity of HPAM solution is a little more than hydrophobic associated water-soluble polymer P(AM/NaAA/DC) apparent viscosity of solution; In the time of C > C*, the apparent viscosity of hydrophobic associated water-soluble polymer solution is far away higher than the apparent viscosity of HPAM aqueous solution, and apparent viscosity sharply increases with the increase of concentration.This is mainly because below critical association concentration, because the content of hydrophobic grouping in aqueous solution is lower, hydrophobic grouping self-association trend is larger, to form in molecule and associate at solution internal main, polymer macromolecule chain is occurred curling, hydrodynamic volume reduces, thereby causes under same concentrations, and the apparent viscosity of hydrophobic associated polymer aqueous solution is lower than the apparent viscosity of HPAM aqueous solution; More than critical association concentration due to the increase of hydrophobic associated polymer concentration, be conducive to intermolecular hydrophobic association, in the inner supramolecular structure forming taking Interpolymer Association as master of solution, increase hydrodynamic volume, make hydrophobic associated polymer show good tackify characteristic.The reason of hydrophobic associated water-soluble polymer the exists critical value that viscosity rises to that Here it is.
For with a series of twin tail hydrophobic associated polymer, more than critical association concentration, along with the increase of hydrophobic monomer (DC) content, the apparent viscosity of copolymer solution also increases, and this is mainly due to more than critical association concentration, and the association between hydrophobic grouping is mainly taking Interpolymer Association as main, along with the increase of content of hydrophobic monomers, Interpolymer Association strengthens, and hydrodynamic volume increases, and shows as the corresponding increase of apparent viscosity.And below critical association concentration, along with the increase of DC content, the apparent viscosity of aqueous copolymers solution declines on the contrary, this is mainly due to below critical association concentration, association between hydrophobic grouping is mainly to associate as main in molecule, along with the increase of content of hydrophobic monomers, in molecule, associates and strengthens, cause strand curling, in macroscopic view, show as the corresponding decline of apparent viscosity.This explanation, more than critical association concentration, hydrophobic association effect strengthens along with the increase of content of hydrophobic monomers, but hydrophobic grouping content is higher, form all corresponding increases of probability of associating in intermolecular and molecule, and the interior association of molecule can weaken the effect of the viscosity increase producing because of Interpolymer Association, because Interpolymer Association effect is better than association in molecule, so now remain taking Interpolymer Association as main, reduce but show as viscosity increasing degree in macroscopic view.
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 (5)
1. the method for testing of hydrophobic associated polymer mass concentration to apparent viscosity influence, is characterized in that, comprises the following steps:
(a) first, prepare hydrophobic associated polymer;
(b) then, hydrophobic associated polymer is become to the solution of different quality concentration by dissolution with solvents;
(c) hydrophobic association polymer solution of getting respectively different quality concentration is placed in experiment container;
(d) experiment container is placed in respectively to the water-bath of uniform temp;
(e) under the stirring condition of identical speed, record the apparent viscosity of the hydrophobic association polymer solution of different quality concentration by viscosity meter, by analyzing data, thereby draw the impact of hydrophobic associated polymer mass concentration on apparent viscosity.
2. the method for testing of hydrophobic associated polymer mass concentration according to claim 1 to apparent viscosity influence, is characterized in that, described experiment container is beaker.
3. the method for testing of hydrophobic associated polymer mass concentration according to claim 1 to apparent viscosity influence, is characterized in that, described bath temperature is 25 DEG C.
4. the method for testing of hydrophobic associated polymer mass concentration according to claim 1 to apparent viscosity influence, is characterized in that, described viscosity is counted the fast rotational viscosimeter of ZNN-D6 type six.
5. the method for testing of hydrophobic associated polymer mass concentration according to claim 1 to apparent viscosity influence, it is characterized in that, the mass concentration of described hydrophobic associated polymer is respectively 1.0g/L, 2.0g/L, 3.0g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021103175A (en) * | 2016-03-07 | 2021-07-15 | フルエンス アナリティクス， ファーマリー アドヴァンスド ポリマー モニタリング テクノロジーズ， インコーポレイテッドＦＬＵＥＮＣＥ ＡＮＡＬＹＴＩＣＳ， ｆｏｒｍｅｒｌｙ ＡＤＶＡＮＣＥＤ ＰＯＬＹＭＥＲ ＭＯＮＩＴＯＲＩＮＧ ＴＥＣＨＮＯＬＯＧＩＥＳ， ＩＮＣ． | Device and method for specifying simultaneously intrinsic viscosity of polymer and non-newtonian behavior |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021103175A (en) * | 2016-03-07 | 2021-07-15 | フルエンス アナリティクス， ファーマリー アドヴァンスド ポリマー モニタリング テクノロジーズ， インコーポレイテッドＦＬＵＥＮＣＥ ＡＮＡＬＹＴＩＣＳ， ｆｏｒｍｅｒｌｙ ＡＤＶＡＮＣＥＤ ＰＯＬＹＭＥＲ ＭＯＮＩＴＯＲＩＮＧ ＴＥＣＨＮＯＬＯＧＩＥＳ， ＩＮＣ． | Device and method for specifying simultaneously intrinsic viscosity of polymer and non-newtonian behavior |
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Application publication date: 20140604 |