CN102453191A - Method for preparing salt resistance enhanced inverse emulsion polymer by controlling hydrophobic monomer content - Google Patents
Method for preparing salt resistance enhanced inverse emulsion polymer by controlling hydrophobic monomer content Download PDFInfo
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- CN102453191A CN102453191A CN2010105194895A CN201010519489A CN102453191A CN 102453191 A CN102453191 A CN 102453191A CN 2010105194895 A CN2010105194895 A CN 2010105194895A CN 201010519489 A CN201010519489 A CN 201010519489A CN 102453191 A CN102453191 A CN 102453191A
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Abstract
The invention discloses a method for preparing a salt resistance enhanced inverse emulsion polymer by controlling hydrophobic monomer content. The preparation method comprises the steps of: preparing an oil phase, preparing a water phase, mixing the oil phase and the water phase for emulsification, conducting stirring for reaction so as to obtain a polymer. The method of the invention changes the hydrophobic monomer content during preparation so as to effectively enhance salt resistance.
Description
Technical field
The present invention relates to a kind of inverse emulsion polymer preparation method that hydrophobic monomer content increases salt resistance that controls.
Background technology
Letex polymerization is the important method of synthetic high polymer, can when keeping high reaction rate, obtain high molecular weight product, and reaction system is a dispersion system, is easy to conduct heat, and is convenient to realize continuous operation.Letex polymerization is medium with water, production safety, and environmental pollution is little, and is with low cost, and used equipment and production technique are simple, easy to operate, and handiness is big, and particularly in the occasion of directly using latex, letex polymerization more has its unique advantage.
Because emulsion polymerization has its valuable holding a little, so competitively develop emulsion polymerization technology countries in the world.At present, the investigators in this field are doing a lot of work aspect the letex polymerization theoretical investigation, have obtained gratifying progress, and very big achievement has been arranged.The raising of letex polymerization theoretical level has promoted the development of latex polymer and polymer emulsion industrial production technology greatly, shows that the output of latex polymer increases year by year; Quality improves constantly; Kind is increasing, and Application Areas enlarges day by day, and its production technique also is gradually improved rationally.In addition; Emulsion polymerization technology is also being constantly brought forth new ideas; Derived the new branch of many letex polymerizations; Many new emulsion polymerisation process occur, had the letex polymerization etc. of the polymer emulsion of special-shaped emulsion particle structure (like hud typed, gradient type, fabric of island-in-sea type, strawberry type, snowman's type, hollow type etc.) like the positive letex polymerization in inverse emulsion polymerization, the non-aqueous media, dispersion polymerization, emulsion polycondensation, emulsifier-free emulsion polymerization, micro-emulsion polymerization, reactive polymer microgel, polymer emulsion interpenetrating(polymer)networks, radiation-induced emulsion polymerization, emulsion tactic polymerization and preparation.The appearance of these New Emulsion polymerization methods has greatly enriched the content of letex polymerization, has also proposed many new problems for the theoretical investigation of letex polymerization.
Inverse emulsion polymerization is a branch of new developing in the letex polymerization research field.Conventional letex polymerization is that oil-soluble monomer is scattered in the water by the effect emulsification of water soluble emulsifier, by water-soluble or oil-soluble initiator initiated polymerization, obtains polymer particles and is scattered in oil-in-water (O/W) the type milk sap in the water.And inverse emulsion polymerization is that water-soluble monomer is soluble in water, is scattered in the polymerization that forms water-in-oil-type (W/O) emulsion in the non-polar liquid and carry out by means of emulsifying agent then, and this polymerization can be adopted oil soluble or water soluble starter.Inverse emulsion polymerization is that water-soluble monomer provides an ideal polymerization method.Can select any and the immiscible organic liquid of water as the dispersion medium of reversed-phase emulsion, be generally hydro carbons, halocarbon etc.The advantage of inverse emulsion polymerization is: 1. speed of response is very fast; 2. system temperature evenly should be controlled; 3. the higher and narrow distribution of resulting polymers molecular weight; 4. the solid content of product higher (>=25%) has overcome the low and poorly soluble shortcoming of suspension polymerization product of solution polymerization solid content, has good solvability; 5. need not handle and directly to be used for TOR oil phase.
People have studied the difference of the difference of inverse emulsion polymerization and conventional emulsion polymerization, particularly mechanism of nucleation and polymerization kinetics aspect widely.Inverse emulsion polymerization is that water-soluble monomer provides a polymerization method with high rate of polymerization and high molecular weight product.Research with water-soluble polymerss such as SEPIGEL 305 and verivate, ROHM and its esters is starting point; The important effects of aspect play more and more such as the research of inverse emulsion polymerization is industrial in modern times and civilian; Especially water-soluble high molecular weight polymkeric substance is widely used in tackiness agent, the thickening material in the textile industry; Flocculation agent in oil and the paper industry, thickening material and toughener, and in the application of industries such as coating, medicine.Inverse emulsion polymerization has the vast market development prospect, and growth momentum is powerful, has caused domestic and international polymer scholar's great attention.The present situation of China's inverse emulsion polymerization technology is far below external advanced level at present, and therefore, the research work of carrying out the letex polymerization aspect has importance and urgency.
The mechanism of nucleation of inverse emulsion polymerization is the problem that remains to be furtherd investigate.Emulsifying stage in monomer solution-emulsifying agent-accurate ternary system of organic solvent exists polyphase equilibrium, possibly not form micella in the system, also possibly form sphere or lamellar micelle, and monomer solution is therein by solubilising.The mesomorphic phase and the monomer droplet that also possibly have the emulsifying agent enrichment in the system simultaneously, the size of monomer droplet in different systems with different agitation conditions under widely different.When adding oil soluble or water soluble starter, balancing each other also can change.Along with the polymerization process variation of temperature, emulsifying agent also will change in the solubleness of oil phase and water, and balancing each other of each component is moved, and these factors all will influence the mechanism of nucleation of polymerization process.
In big quantity research, following several kinds of mechanism of nucleation are arranged to acrylic amide (AM) inverse emulsion polymerization.First kind of mechanism of nucleation is the micella nucleation.For example under the system of oil-soluble initiator and aromatic hydrocarbon solvent, study, the result shows that particle is nucleation in reversed phase micelle, and the polymerization kinetics behavior is similar to conventional emulsion polymerization, and the total speed of polymerization is higher than corresponding solution polymerization system significantly.
Second kind of mechanism of nucleation of inverse emulsion polymerization is monomer droplet nucleation.Generally speaking, the scatter stage of reversed-phase emulsion system can be distributed to the monomer droplet between the drop size of microemulsion and conventional emulsions.The monomer droplet size of conventional emulsions system is between 10～100 μ m, and the mean diameter that it has been generally acknowledged that reversed-phase emulsion system monomer droplet can make the monomer droplet reach about 0.1～0.4 μ m about 1 μ m under certain conditions.Vanderhoff finds that under his experiment condition the monomer droplet is 20nm, the actual yardstick that has reached microemulsion.At oil-soluble initiator and aliphatic hydrocarbon is in the inverse emulsion polymerization system of external phase, and the mensuration of dynamic light scattering has confirmed not have in the system reversed phase micelle to exist, and the size of particles of disperse phase is almost constant in the polymerization process, and this is the strong evidence of droplet nucleation.This process belongs to the anti-phase microsuspension or rather.Visioli has also studied the inverse emulsion polymerization of AM in o-Xylol, and he thinks no matter adopt oil-soluble initiator or water soluble starter, polymerization all occurs in the monomer droplet.
The third mechanism of nucleation thinks that the inverse emulsion polymerization process is micella and monomer droplet nucleation while and deposits.Vanderhoff has studied the inverse emulsion polymerization of AM the earliest, thinks it is that micella or monomer droplet all are the places of particle nucleation.Because the monomer droplet is less, in system, occupies very big surface-area, they can become the part of particle nucleation with the monomer micella competition of solubilising.Stupan, Kova think that also the mechanism of inverse emulsion polymerization is relevant with temperature, and showing as polymerization process is the synthesis result of the little suspension dual mode of reversed-phase emulsion and anti-phase.
Carry out the research work of inverse emulsion polymerization aspect; Help to be well understood to the influence factor of polymer emulsion stable mechanism, mechanism of nucleation, kinetics and polymericular weight in theory; For the appropriate design polymerization technology is provided fundamental basis; In practice, help lend some impetus to polyacrylamide Products Development and application, promote the development of China's fine chemistry industry industry.
In the preparation process of inverse emulsion polymer, hydrophobic monomer content has very big influence to salt resistance, how to confirm the hydrophobic monomer content an of the best, is problem demanding prompt solution.
Summary of the invention
The objective of the invention is to overcome the shortcoming and defect of above-mentioned prior art, provide a kind of control hydrophobic monomer content that can effectively strengthen salt resistance to increase the inverse emulsion polymer preparation method of salt resistance.
The object of the invention is realized through following technical proposals: control hydrophobic monomer content increases the inverse emulsion polymer preparation method of salt resistance, may further comprise the steps:
(a) kerosene and emulsifying agent Span-80 are joined in the there-necked flask, install reaction unit, water-bath is transferred to temperature of reaction and keeps constant temperature, whisking appliance stirs kerosene and emulsifying agent dissolves to abundant, as oil phase;
(b) take by weighing monomer acrylic amide, 2-acrylic amide-2-methyl propane sulfonic acid, hydrophobic monomer and place beaker, measure zero(ppm) water with graduated cylinder and pour in the beaker, and by mass percentage, hydrophobic monomer accounts for 0.6%～1.0% of monomer total amount; With the glass stick stirring it is fully dissolved, use in the sodium hydroxide again and monomer solution; The ammonium persulphate for preparing, aqueous solution of sodium bisulfite are joined respectively in the monomer solution, stir, this solution is as water;
(c) continue to stir down, aqueous phase solution is added dropwise in the there-necked flask that oil phase is housed, under the effect of high-speed stirring, make its emulsification with the glass stick drainage;
(d) after the emulsification, stirring reaction in water bath with thermostatic control obtains thickness oyster white latex, i.e. inverse emulsion polymer.
In the said step (d), said inverse emulsion polymer is directly used.
In the said step (d), said inverse emulsion polymer repeatedly cleans through ethanol and acetone and makes its deposition, the drier white powder product that gets in thermostat container.
In the said step (b), by mass percentage, by mass percentage, hydrophobic monomer accounts for 0.6% of monomer total amount.
In sum, the invention has the beneficial effects as follows:, thereby can effectively strengthen salt resistance through the hydrophobic monomer content in the change preparation process.
Description of drawings
Fig. 1 is the influence curve figure of hydrophobic monomer content of the present invention to salt resistance.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is done further detailed description, but embodiment of the present invention is not limited only to this.
Embodiment:
The control hydrophobic monomer content that the present invention relates to increases the inverse emulsion polymer preparation method of salt resistance, may further comprise the steps:
(a) kerosene and emulsifying agent Span-80 are joined in the there-necked flask, install reaction unit, water-bath is transferred to temperature of reaction and keeps constant temperature, whisking appliance stirs kerosene and emulsifying agent dissolves to abundant, as oil phase;
(b) take by weighing monomer acrylic amide, 2-acrylic amide-2-methyl propane sulfonic acid, hydrophobic monomer and place beaker, measure zero(ppm) water with graduated cylinder and pour in the beaker, and by mass percentage, hydrophobic monomer accounts for 0.6%～1.0% of monomer total amount; With the glass stick stirring it is fully dissolved, use in the sodium hydroxide again and monomer solution; The ammonium persulphate for preparing, aqueous solution of sodium bisulfite are joined respectively in the monomer solution, stir, this solution is as water;
(c) continue to stir down, aqueous phase solution is added dropwise in the there-necked flask that oil phase is housed, under the effect of high-speed stirring, make its emulsification with the glass stick drainage;
(d) after the emulsification, stirring reaction in water bath with thermostatic control obtains thickness oyster white latex, i.e. inverse emulsion polymer.
In the said step (d), said inverse emulsion polymer is directly used.
In the said step (d), said inverse emulsion polymer repeatedly cleans through ethanol and acetone and makes its deposition, the drier white powder product that gets in thermostat container.
In the said step (b), by mass percentage, by mass percentage, hydrophobic monomer accounts for 0.6% of monomer total amount.
In order to confirm best hydrophobic monomer content; The present invention has carried out the influence test of hydrophobic monomer content to salt resistance; This test is at oil/water ratio that 1: 5, emulsifying agent Span-80 content in oil phase are 5%, the monomer mass mark is 50%, the initiator dosage is 0.5 ‰, the massfraction of hydrophobic monomer is respectively under 0.4%, 0.6%, 0.8% the condition and in 25 ℃ water-bath, carried out polyreaction 6 hours in the monomer; The polymer formulation of gained under the different hydrophobic monomer consumptions is become the solution of 2000mg/L; Add concentration again and be 10% sodium-chlor; Investigating the influence of different hydrophobic monomer consumptions to the multipolymer salt resistance, is index with the viscosity retention ratio, and the result is as shown in Figure 1.
Can find out that by Fig. 1 the viscosity retention ratio of polymers soln increases along with the increase of hydrophobic monomer content in the monomer, when the hydrophobic monomer dosage greater than 0.6% the time, salt resistance does not have noticeable change.Simultaneously, if the hydrophobic monomer dosage is too big, the solvability of hydrophobic associated polymer can be affected.
By on can know that hydrophobic monomer of the present invention accounts for 0.6%～1.0% of monomer total amount, and be preferably 0.6%.
The above only is preferred embodiment of the present invention, is not the present invention is done any pro forma restriction, and every foundation technical spirit of the present invention, any simple modification, equivalent variations to above embodiment did all fall within protection scope of the present invention.
Claims (4)
1. control hydrophobic monomer content increases the inverse emulsion polymer preparation method of salt resistance, it is characterized in that, may further comprise the steps:
(a) kerosene and emulsifying agent Span-80 are joined in the there-necked flask, install reaction unit, water-bath is transferred to temperature of reaction and keeps constant temperature, whisking appliance stirs kerosene and emulsifying agent dissolves to abundant, as oil phase;
(b) take by weighing monomer acrylic amide, 2-acrylic amide-2-methyl propane sulfonic acid, hydrophobic monomer and place beaker, measure zero(ppm) water with graduated cylinder and pour in the beaker, and by mass percentage, hydrophobic monomer accounts for 0.6%～1.0% of monomer total amount; With the glass stick stirring it is fully dissolved, use in the sodium hydroxide again and monomer solution; The ammonium persulphate for preparing, aqueous solution of sodium bisulfite are joined respectively in the monomer solution, stir, this solution is as water;
(c) continue to stir down, aqueous phase solution is added dropwise in the there-necked flask that oil phase is housed, under the effect of high-speed stirring, make its emulsification with the glass stick drainage;
(d) after the emulsification, stirring reaction in water bath with thermostatic control obtains thickness oyster white latex, i.e. inverse emulsion polymer.
2. control hydrophobic monomer content according to claim 1 increases the inverse emulsion polymer preparation method of salt resistance, it is characterized in that in the said step (d), said inverse emulsion polymer is directly used.
3. control hydrophobic monomer content according to claim 1 increases the inverse emulsion polymer preparation method of salt resistance; It is characterized in that; In the said step (d); Said inverse emulsion polymer repeatedly cleans through ethanol and acetone and makes its deposition, the drier white powder product that gets in thermostat container.
4. increase the inverse emulsion polymer preparation method of salt resistance according to claim 1,2 or 3 described control hydrophobic monomer content, it is characterized in that in the said step (b), by mass percentage, hydrophobic monomer accounts for 0.6% of monomer total amount.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418840A (en) * | 2015-12-04 | 2016-03-23 | 中国石油大学(华东) | Preparation method of hydrophobically associating polymer inverse emulsion |
| CN106866881A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer emulsion and preparation method thereof |
-
2010
- 2010-10-18 CN CN2010105194895A patent/CN102453191A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418840A (en) * | 2015-12-04 | 2016-03-23 | 中国石油大学(华东) | Preparation method of hydrophobically associating polymer inverse emulsion |
| CN106866881A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Hydrophobic association acrylamide copolymer emulsion and preparation method thereof |
| CN106866881B (en) * | 2015-12-14 | 2019-12-10 | 中国石油化工股份有限公司 | hydrophobic association acrylamide polymer emulsion and preparation method thereof |
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Application publication date: 20120516 |