CN1014775B - Process for manufacturing inverse microlatices - Google Patents
Process for manufacturing inverse microlaticesInfo
- Publication number
- CN1014775B CN1014775B CN 85105947 CN85105947A CN1014775B CN 1014775 B CN1014775 B CN 1014775B CN 85105947 CN85105947 CN 85105947 CN 85105947 A CN85105947 A CN 85105947A CN 1014775 B CN1014775 B CN 1014775B
- Authority
- CN
- China
- Prior art keywords
- counter
- rotating
- latex
- water
- microemulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The present invention relates to a new method for making micro-latex converted from a water-soluble polymer by a polymerizing method. The method comprises the steps that converted micro (drop-) latex which is made by a mixing method is polymerized; a water phase with water-soluble monomers for polymerization, alkali metal salt (such as organic phases of salt with C2 to C4 carboxylic acids) with at least one saturated aliphatic monocarboxylic acid, and a nonionic surface active agent or a mixture of nonionic surface active agents are mixed together to obtain the converted micro (drop-) latex, wherein the weight ratio of the usage amount of the alkali metal salt to the monomers for polymerization is 0.1/1 to 0.3/1. The generated micro-latex by reaction can be used for improving the production of hydrocarbons (in the aspect of an oil recovery submitting technology or a method for preventing water from flowing into a production well).
Description
The present invention relates to a kind ofly in the counter-rotating microemulsion, utilize the polyreaction of water-soluble vinyl monomer to prepare the method for the fine latex that reverses, and the counter-rotating fine latex that makes with this method.
The known counter-rotating latex that can in a kind of emulsion of reversing, make water-soluble polymkeric substance with polymerization process, used counter-rotating emulsion is to contain monomeric water, a kind of organic phase that one or more water-soluble confession (being total to) polymerizations are used by a kind of, and one or more tensio-active agents mix formed.
In this prescription, tensio-active agent nearly all is selected from the low nonionic surface active agent of possess hydrophilic property lipophilicity ratio (HLB), therefore can obtain a kind of emulsion of water-in-oil-type.It normally is made up of a kind of sorbitol monooleate or monostearate.On the other hand, narration once, the tensio-active agent of some hydrophilic-lipophilic balances higher (HLB 〉=7) is easy to form water-in-oil emulsion too.
The main shortcoming of counter-rotating latex is a deficient in stability, and the time one is of a specified duration, can cause a large amount of sedimentations of material.
On the other hand, prepare the method for the fine latex that reverses, also once recorded and narrated in formerly No. the 2524895th, the french patent application with positively charged ion or cats product.
At present, the applicant has found a kind of method with nonionic surface active agent manufacturing counter-rotating fine latex, and this method is than the method advanced person in the prior art, and it has improved the content of the water-soluble polymkeric substance in the counter-rotating fine latex.
According to the present invention, the method for making the fine latex of counter-rotating is shown by the following step usually:
(a) make stablizing and transparent microemulsion of a kind of water-in-oil-type by following blending method;
(1) a kind of polymeric vinyl monomer such as acrylamide and the monocarboxylic an alkali metal salt of a kind of saturated ester family such as aqueous solution of sodium acetate of being used for; With
(2) a kind of oil phase that contains a kind of hydrocarbon liquid (is 207-254 ℃ isoparaffin or the paraffinic hydrocarbons that contains 7,10 or 12 carbon atoms as boiling range) at least;
(3) have at least a kind of nonionic surface active agent to have the HLB(hydrophilic-lipophilic balance of this promoting agent) when the scope of value is the mixture of 8-11(use promoting agent, should consider the HLB of resultant).
(b) the counter-rotating microemulsion with step (a) gained carries out polymerization, till polymerization is finished, can generate a kind of stable and transparent counter-rotating fine latex of high-molecular weight that has.
According to the present invention, be used for making the prescription of the counter-rotating microemulsion of fine latex, water miscible vinyl monomer wherein can be particularly be made up of acrylamide, Methacrylamide or positive vinyl pyrrolidone, and the monocarboxylic an alkali metal salt of described saturated ester family can be following material: acetate, propionic acid or butyro-basic metal etc.In fact, better with sodium acetate.
In order to make a kind of counter-rotating microemulsion, need to use specific conditions usually.Its significant parameter is as follows: the character of the hydrophilic-lipophilic balance of surfactant concentrations, tensio-active agent or surfactant mixtures (HLB), temperature, this organic phase and the composition of water.
The monomer content of water is generally 20-80% and is generally 30-70%(by weight).
Alkali-metal carboxylate salt and monomeric weight ratio are generally 0.1/1 to 0.3/1.
Sometimes, water also can contain sodium hydroxide or potassium hydroxide, through adjusting the quantity of described product carefully, can obtain a kind of hydrolysis polyacrylamide, this uses particularly advantageous to some, especially for improving the oil recovery aspect.Another kind of technology is to be hydrolyzed after polyreaction.
The selection of organic phase for making the required minimum surface surfactant concentration of a kind of microemulsion that reverses, has great influence.This organic phase can be made up of the mixture of a kind of hydrocarbon polymer or multiple hydrocarbon polymer.In order to obtain the prescription (content of tensio-active agent is lower) of cheap manufacturing counter-rotating microemulsion, the most handy paraffinic hydrocarbons and/or isoparaffin, or their mixture.
Selecting water as much as possible is high person with hydrocarbon polymer weight ratio mutually, in the hope of through after the polymerization, can obtain a kind of microemulsion of high polymers content.In fact, the scope of this ratio can be between 0.5 to 3/1.
In other words, be between 8 to 11 in order to make hydrophilic-lipophilic balance (HLB) scope, should select one or more tensio-active agents.Because in fact, outside this scope, maybe can not obtain the fine latex that reverses, or need a quite a large amount of tensio-active agent, do not meet economic requirement.In addition, in the HLB of defined scope, employed amount of surfactant must be enough to make a kind of fine latex of counter-rotating.Surfactant concentrations is too low, then can form similar in appearance to the prepared counter-rotating latex of prior art, and this mode is not a content of the present invention.
In the HLB scope of being considered, the ratio that the Cmin of tensio-active agent accounts in each component of this microemulsion changes with the variation of HLB value.The value of HLB is between 8.5-9.5 the time, and the lower limit approximately is in the 9%(weight concentration) the most favourable; The value of HLB is during in 8 to 8.5 scope and from 9.51 to 11 scope, and lower concentration limit is higher usually.For example, be about for the HLB value under 10 the situation, the Cmin of tensio-active agent is about 20%(weight).
About the upper limit of surfactant concentrations, consider from economic reason, need it is limited in below 25% of weight of this counter-rotating microemulsion all the components.
In the process of preparation counter-rotating microemulsion, must control the temperature of mixture carefully, this is owing to consider when nonionic surface active agent exists that the counter-rotating microemulsion is to the susceptibility of temperature.When surfactant concentrations more near when obtaining a kind of needed minimum content of microemulsion of counter-rotating, Temperature Influence is bigger.
In order to reduce needed amount of surfactant, in order to make temperature extremely minimum, make the preparation of microemulsion temperature as far as possible simultaneously near the selected temperature of polyreaction for the influence limit of the stability of this counter-rotating microemulsion.
Water-soluble vinyl monomer in the above-mentioned counter-rotating microemulsion is by photochemical polymerization or thermopolymerization, this method comprises: with the photochemical initation polyreaction, for example by ultraviolet radiation, or utilize a kind of thermopolymerization of free radical generation body, as utilize Diisopropyl azodicarboxylate etc. hydrophobic or as the thermopolymerization of crossing hydrophilic free radical generation bodies such as (two) vitriolate of tartar.
Polyreaction takes place very soon, and when for example utilizing photochemical polymerization, in several minutes, monomer aggregates into stable and transparent fine latex quantitatively, and its particle half has a kind of narrow distribution range through being 20-50 millimicron (nm).
According to the present invention, be scattered in the size of the particle in this counter-rotating fine latex, can measure with the method for quasi-elastic light scattering.The light source of this kind light scattering apparatus is made up of a kind of argon ion spectrum physics laser apparatus that operates in 488 millimicrons (nm).The time correlation function relevant with scattering strength is to utilize a kind ofly to have the digital correlator of 72 channels to record.The intensity related data is to utilize the method for accumulation numerical value to handle, and wherein provides the average decimal reduction time＜Γ-1 of this related function〉and variance V.The latter measures the distribution range of this decimal reduction time, and its value is given by following formula:
V＝（<Γ>
2-<Γ
2>）/<Γ>
2
(＜Γ herein
2It is the square second time that distributes.
For the low polymers soln of polymolecularity, V is as first approximation for its variance, with the polydispersity index MW/Mn(weight molecular weight/number-average molecular weight that is provided by the following relationship formula) relevant, its relational expression is as follows:
Mw/Mn＝1+4V
Selected activation method when the molecular weight of prepared polymkeric substance depends on polyreaction, if polymerization temperature maintains below 30 ℃, photochemical activation helps aggregating into the polymkeric substance of very high molecular weight.With regard to the counter-rotating fine latex that is intended for preparing the recovery that improves hydrocarbon polymer, when the polymkeric substance of the very high molecular weight of needs, always at first consider this activation method.
It is stable and transparent that method of the present invention provides, the counter-rotating fine latex that contained water-soluble polymer content is high, wherein the content of water-soluble polymers is about the weight as 10-35%(); Be generally 10-25%(weight).
Can be used as various uses according to the prepared counter-rotating fine latex of method of the present invention, be particularly useful for the technical elements of following oil production: improve hydrocarbon polymer recovery, bottom fixed, drilling mud production, during oil mining stream and as filling up well finishing liquid or fracturing fluid in the waterproof.
In general, the recovery method that utilizes the aqueous solution of polymkeric substance to improve oil plant comprises described solution is injected the oil field, injects well by at least one, by the rock stratum circulation with reclaim the hydrocarbon polymer of being discharged by at least one recovery well.
The method of utilizing counter-rotating fine latex of the present invention to improve employed water-in-oil type emulsion in the recovery method of oil plant and the prior art there is no very big difference.The counter-rotating fine latex that the present invention considered is auto-reverse, in general, not as previous described certain methods, needs to add a kind of auxiliary tensio-active agent and impels counter-rotating.The use of these fine latexes is as after through water dilution, is the ratio of 50-5000ppm at multipolymer with respect to the weight ratio of total water, preferably uses under the ratio with 100-2000ppm.The test of carrying out in the laboratory has demonstrated the efficient of these counter-rotating fine latexes.
Prevent that water from flowing into the method for production well, be included in the part oil field that desire handles that inject a kind of aqueous solution of polymkeric substance by recovery well, this aqueous solution is with soluble in water made according to counter-rotating fine latex of the present invention.Polymkeric substance is adsorbed on the well formation wall on every side of injecting its aqueous solution in large quantities.Then, when described oil well put into production again, oil and/or gas passed processed area selectively and the water yield has been lowered.
Except these were used, the water-soluble polymkeric substance with microemulsion makes can also be used as:
-separate and hang the solid condensing agent of breast in liquid;
Flotation aid in the-paper pulp production and row's drop auxiliary agent; Or
Flocculation agent in the-water treatment.
Counter-rotating fine latex with method of the present invention is made can be used for the moulding of glass fibre equally, leather industry or paint aspect.
Following Example has illustrated the present invention, by any way the present invention is limited to described scope but should not be considered as it, example 1,4, and 10,11,15 and 16 usefulness are made comparisons, and are not content of the present invention.
Example 1(comparative example)
A kind of initial boiling point that adds 300g in containing the 250g aqueous solution of 106g acrylamide is 207 ℃ and final boiling point is 254 ℃ an isoparaffin cut, mixture with the nonionic surface active agent of 157g, this mixture is made up of 22g Sorbitol Powder six oleic acid esters, blended result, formed HLB are 9.3.
The Diisopropyl azodicarboxylate of 0.32g is added the monophasic mixture of above-mentioned gained, outgased 30 minutes, 19 ℃ of polymerizations 15 minutes under ultraviolet radiation, the result obtains a kind of muddiness and unsettled latex then.
Example 2
Repeat example 1, except the sodium acetate with 15.9g adds the aqueous phase, all conditions are all constant.After the polyreaction, obtain a kind of stable and transparent counter-rotating fine latex, recording its particle radii with the quasi-elastic light scattering method is the 37nm(millimicron), variance is 3%.
By in acetone, precipitating and using acetone and methanol wash continuously, can obtain a kind of polyacrylamide (all counter-rotatings), in the time of 25 ℃, recording its limiting viscosity in containing the salt solution of 5.85g/l is 920cc/g.
Example 3
Repeat example 2, contain the sodium acetate of 25.3g except making aqueous phase, a tangent condition is all constant.Can obtain a kind of stable and transparent fine latex, its character is very near the characteristic of being mentioned in the example 2.
R=38nm, variance=3%
The limiting viscosity that records this polyacrylamide by the condition of example 2 is 847cc/g.
Example 4(comparative example)
When repeating example 2, through obtaining a kind of unsettled latex after the polyreaction with the sodium acetate content of 4.5g.
Example 5
Isoparaffin cut in 470g such as the example 1 and the surfactant mixtures in the 150g example 1 are added in the aqueous solution that contains 142g acrylamide and 34.5g sodium acetate of 378g.With the monophasic mixture of gained 20 ℃ of irradiations 15 minutes and carry out polymerization under ultraviolet radiation.The radius of prepared counter-rotating fine latex is 42.3nm, and variance is 5%.The limiting viscosity of the polymkeric substance of gained is 772cc/g in the time of 25 ℃.
Example 6
Surfactant mixtures in the example 1 of isoparaffin cut in 300g such as the example 1 and 150g is added in the aqueous solution that contains 218g acrylamide and 60.5g sodium acetate of 550g.20 ℃ of irradiations 15 minutes and carry out polymerization under ultraviolet radiation, this method draws a kind of stable and transparent fine latex with the monophasic mixture of gained.The limiting viscosity of this polyacrylamide of emanating out by example 2 described methods in the time of 25 ℃ is 878cc/g.
Example 7
Surfactant mixtures in the example 1 of 419g dodecane and 216g is added in the aqueous solution that contains 143g acrylamide and 21.4g sodium acetate of 365g.With the monophasic mixture heating up to 45 of gained ℃, kept three hours, this method can get a kind of stable and transparent counter-rotating fine latex.Polyacrylamide wherein is 635cc/g 25 ℃ limiting viscosity.
Example 8
Repeat example 7, but replace dodecane with decane, other conditions are all constant.Through after the polyreaction, can obtain a kind of counter-rotating fine latex, the limiting viscosity of polyacrylamide wherein is 533cc/g.
Example 9
Repeat example 7, except replacing the dodecane with heptane, other conditions are all constant.Through after the polyreaction, can get a kind of stable and transparent counter-rotating fine latex, the limiting viscosity of polyacrylamide wherein in the time of 25 ℃ is 453cc/g.
Example 10(comparative example)
Repeat example 7, except replacing the dodecane with toluene, other conditions are all constant, obtain a kind of unsettled emulsion before polymerization.
Example 11(comparative example)
Except the sodium-chlor of weight such as using replaces the sodium acetate, repeat example 2 under all constant situation of all conditions, through after the polyreaction, can obtain a kind of muddiness and unsettled latex.
Example 12-14
Condition according to example 5, the ratio of each tensio-active agent being changed, for different HLB(hydrophilic-lipophilic balances) value can record in order to obtain a kind of minimum content of the stable and transparent needed tensio-active agent of counter-rotating fine latex after polymerization.
The gained outcome record is in following table:
Obtain a kind of stable and transparent fine latex
The amount of surfactant * of the minimum that example HLB is required
12 9 9
13 9.3 9
14 10 20
* represent with whole initially weight percents of components with respect to this microemulsion.
Example 15(comparative example)
Repeat example 5, remove the ratio that changes two kinds of tensio-active agents, the HLB of formation is equaled outside 7.5, all conditions is all constant, under these conditions, even add the tensio-active agent of a large amount of (greater than 45% weight), all can not obtain any counter-rotating microemulsion.
Example 16(comparative example)
All conditions in the example 5 is all constant, but makes the HLB of formation equal 11.5 the ratio change of two kinds of tensio-active agents, under these conditions, even add the tensio-active agent of a large amount of (greater than 25% weight), all can not obtain any counter-rotating microemulsion.
Example 17
With the isoparaffin cut in the 530g example 1 and 101g by 20.3 Sorbitol Powder sesquioleate and 80.7g polyoxyethylene sorbitol six oleic acid esters composite surfactant mixture be added in the aqueous solution that contains 145g acrylamide and 18.6g sodium acetate of 369g.
The formed HLB of surfactant mixture is 8.9.
The Diisopropyl azodicarboxylate of 0.48g is added in the single-phase mixture of above-mentioned gained, outgased 30 minutes, simultaneously in the time of 19 ℃, irradiation 30 minutes under ultraviolet radiation and carry out polymerization, this method can obtain the low transparent counter-rotating fine latex of a kind of viscosity.
Example 18
497g made in 1 used surfactant mixture (HLB=8.9) adds in the aqueous solution that contains 168g acrylamide and 20.2g sodium acetate of 404g in the employed isoparaffin cut and 99g example 17.
Polyreaction is undertaken by the condition in the example 17.Can obtain a kind ofly containing 16.8%(approximately by weight) the transparent counter-rotating fine latex of high molecular polymer.
Claims (3)
1, a kind of method of making the counter-rotating fine latex is characterized in that comprising the following steps:
(a), prepare a kind of counter-rotating microemulsion (belonging to water-in-oil-type) with following mixing of materials:
A kind of aqueous solution that contains acrylamide and sodium acetate, acrylamide accounts for the 20-80% of solution weight, and the weight ratio of sodium acetate and acrylamide is 0.1/1 to 0.3/1;
A kind of oil phase that contains a kind of isoparaffin fraction (207-254 ℃) or a kind of paraffinic hydrocarbons (containing 7,10 or 12 carbon atoms) at least; With
The mixture of a kind of nonionic surface active agent or multiple nonionic surface active agent, HLB are 8-11, and its consumption is about more than 9% of each component gross weight of counter-rotating microemulsion; With
(b) the counter-rotating microemulsion with step (a) gained carries out polymerization by the polymeric condition.
2, according to the process of claim 1 wherein that the monomer solution in the step (a) and the weight ratio of oil phase are 0.5 to 3/1.
3, according to the method for claim 1 or 2, wherein tensio-active agent in the step (a) or surfactant mixture are below 25% or 25% with respect to the weight percent of all components of described counter-rotating microemulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85105947 CN1014775B (en) | 1984-07-13 | 1985-08-07 | Process for manufacturing inverse microlatices |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8411140A FR2567525B1 (en) | 1984-07-13 | 1984-07-13 | PROCESS FOR THE PREPARATION OF INVERTED MICROLATEX AND THE INVERTED MICROLATEX OBTAINED |
| CN 85105947 CN1014775B (en) | 1984-07-13 | 1985-08-07 | Process for manufacturing inverse microlatices |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85105947A CN85105947A (en) | 1987-02-25 |
| CN1014775B true CN1014775B (en) | 1991-11-20 |
Family
ID=25741932
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85105947 Expired CN1014775B (en) | 1984-07-13 | 1985-08-07 | Process for manufacturing inverse microlatices |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1014775B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3294829A4 (en) * | 2015-05-13 | 2019-01-09 | Ecolab USA Inc. | Invertible water-in-oil latices and methods of use |
-
1985
- 1985-08-07 CN CN 85105947 patent/CN1014775B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85105947A (en) | 1987-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1131243C (en) | Process for producing water-soluble anionic dispersion polymers | |
| CN87106918A (en) | The method that is used for the control polymer gel speed of oil-gas mining construction | |
| CA1255840A (en) | Process for preparing water soluble copolymers inverted microlatex: microlatex thus obtained and its use for enhancing hydrocarbon production | |
| GB2118200A (en) | Microlatexes | |
| DE2508346A1 (en) | PROCESS FOR THE PRODUCTION OF WATER-SOLUBLE, PRACTICAL LINEAR POLYMERISATE WITH HIGH MOLECULAR WEIGHT AND A POLYMERISATE PRODUCED BY THE PROCESS | |
| CN86108237A (en) | Comprise the resin combination that has improved dispersed clay | |
| CN102432749B (en) | Amphipol and application thereof | |
| CN103906711A (en) | Concentration of suspensions | |
| CN1903974A (en) | Nano-water soluble microgel oil displacing material and its preparation method | |
| CN1869139A (en) | Ultraviolet light solidfication water polyurethane acrylate paint resin and its preparation method | |
| CN1662627A (en) | Use of anionic dispersion polymers as viscosity modifiers in aqueous drilling fluids | |
| EP2738191B1 (en) | Amphiphilic macromolecule and use | |
| CN1043332A (en) | Well treatment solution and be used for the additive of this treatment solution | |
| CN1473167A (en) | Preparation method of polymer latex resin pulverulent body | |
| DE102004013750A1 (en) | Anionic water-in-water polymer dispersions, process for their preparation and their use | |
| CN114790379A (en) | Double-chamber microcapsule for drilling fluid and preparation method and application thereof | |
| CN1014775B (en) | Process for manufacturing inverse microlatices | |
| GB2161492A (en) | The manufacture of inverse microlattices | |
| RU2749268C9 (en) | Method for obtaining polyacrylamide hydrogel | |
| CN1008442B (en) | Process for manufacturing inverse microlatices of hydrosoluble copolymers | |
| CN1250590C (en) | Photo polymerization method of trielement copoly water soluble polymer reversed phase microemulsion using acrylamide as maia body | |
| CN1061033A (en) | The gel acid that acidifying strata is used | |
| US3753962A (en) | Recovery of a water soluble polymer powder from an aqueous gel of said polymer | |
| EP4110838A1 (en) | Water-soluble associative amphoteric polymer as a rheology modifier for subterranean treatments | |
| CN1752124A (en) | The method for preparing vibrin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |