CN103408698A - In-situ redox initiation for preparing polyacrylamide water-drum water dispersion - Google Patents
In-situ redox initiation for preparing polyacrylamide water-drum water dispersion Download PDFInfo
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Abstract
The invention belongs to the technical field of water-soluble high-polymer dispersion synthesis, and particularly relates to a polymerization method of an anionic polyacrylamide water-drum water dispersion. The in-situ redox initiation method for preparing the polyacrylamide water-drum water dispersion comprises the following steps: carrying out copolymerization reaction to prepare seed polymer SP, and preparing the polyacrylamide water-drum water dispersion from the seed polymer SP, wherein the molecular weight of the seed polymer SP is controlled at (1.5-2.5)*10<6>, the seed polymer contains a tertiary amine group used as a reduction group, and the raw materials for preparing the polyacrylamide water-drum water dispersion contain an oxidant for performing redox reaction with the reduction group to form free radical. Thus, the invention ensures the prepared product to have high flowability, high storage stability and high molecular weight; and meanwhile, the invention does not need special heat transfer and mixing equipment, thereby greatly lowering the preparation cost.
Description
Technical field
The invention belongs to the water-soluble polymer dispersion synthesis technical field, relate in particular to a kind of anionic polyacrylamide water bag aqueous dispersions polymerization process.
Background technology
At present, the polyacrylamide industrial process comprises solution polymerization, inverse suspension polymerization and inverse emulsion polymerization.The product that the production method of solution polymerization obtains is powder, high viscosity problem in production process, similar with inverse suspension polymerization, owing to finally needing to dry granulation, unavoidably need to introduce drying-granulating equipment, increase production cost, produce dust in producing simultaneously, also there is problems such as dissolving difficulty in final product.And inverse suspension polymerization and reverse emulsion polymerization are aborning in a large number with an organic solvent and tensio-active agent, itself easily produces secondary pollution to environment.In order to overcome above defect, people have developed aqueous dispersion polymerization (aqueous dispersion polymerization, also be referred to as the water polymerization of water bag or double-aqueous phase polymerization) preparation method, this method is preparing product and without aftertreatment directly, production efficiency is high, products therefrom dissolves fast, and itself is environmentally friendly without organic solvent.
Tradition water bag water polymerization process, the crucial polymer chain for radical polymerization formation of its process is timely and effectively from Precipitation system, form primary particle, adsorb rapidly simultaneously stablizer, form stable emulsion particle, this post-polymerization carries out in mutually at external phase and particle respectively, simultaneously monomer dynamic assignment between two-phase.In the method category, investigators from shortening the phase-splitting time, improve condition of phase separation, improve the aspects such as emulsion particle stability water bag aqueous dispersions synthetic carried out to improvement in various degree, in to a certain degree, controlled final product viscosity, improved product stability and dispersion liquid solid content.As the patent No., be CN101649024A(2010-4-21) Chinese patent by adding the copolymerization of esters of acrylic acid hydrophobic monomer, promote to separate out phase-splitting, add simultaneously and have surface-active function monomer, improve early stage stabilization efficiency, when but product prepared by the method adds water in actual use, dissolve and become slow, be not suitable for the heavy industrialization application; In addition, as the patent No., be CN1519259A(2004-8-11) Chinese patent by the one package stabilizer that adopts non-ionic type polymer and multicomponent alcoholics compound, improve stabilising effect it is not clearly by multicomponent alcoholics compound for the stabilizing effect of raising anion-polyacrylamide that but this patent adds the method for carrying out modification.
In aforesaid method, reaction process in early stage and traditional dispersion polymerization are similar, be mainly solution polymerization, but after traditional dispersion polymerization nucleation, due to the affinity of monomer and emulsion particle far away higher than the affinity of monomer and reaction medium, therefore monomer and the oligopolymer overwhelming majority swell in emulsion particle, and transfer reaction is mainly carried out at inside particles, due to the acting in conjunction of gel effect, blanketing effect and enrichment effect, speed of reaction is very fast, and the molecular weight that obtains simultaneously polymkeric substance is also very high.But in aqueous dispersion polymerization, monomer and oligopolymer contain a large amount of amide groups, polarity is very large, the affinity of itself and emulsion particle and reaction medium is more or less the same, and much larger than emulsion particle, so monomer and oligopolymer part still are present in external phase due to the reaction medium amount, this causes three consequences: the monomer oligopolymer that mainly polymerization forms in external phase at first, system viscosity sharply increases, and makes the heat transfer of reacting and stirs more difficult control, needs special polymerization unit; Secondly, a large amount of monomers are present in external phase and can delay polymkeric substance and separate out, and cause system viscosity in polymerization process further to increase, and affect production stability; Again, monomer is less at particle phase interior polymeric proportion, and rate of polymerization and molecular weight are relatively low.
Summary of the invention
The objective of the invention is for solving the problems of the technologies described above, provide the in-situ oxidation reduction to cause and prepare polyacrylamide water bag aqueous dispersions, the inventive method is carried out step by step, at first the synthetic seed polymer that contains tertiary amine group (as potential reduction group), then this seed polymer is formed to seed dispersion liquid (micron or submicron-scale particle-stabilised be scattered in system in) by polymerizing condition, issuing estranged being separated, using the required monomer of polymerization and as the component of oxygenant, add in the seed dispersion liquid prepared and carry out polymerization again, effectively to guarantee to prepare low viscosity and the stability of system in polyacrylamide water bag aqueous dispersions preparation process, thereby guarantee that the product of preparing possesses high molecular, high workability and high storage stability, the inventive method does not need special heat transfer and whipping device simultaneously, greatly reduces preparation cost.The present invention for achieving the above object, by the following technical solutions
In-situ oxidation reduction initiation prepares polyacrylamide water bag aqueous dispersions, and it comprises following preparation process successively:
1) prepare the raw material that seed polymer SP prepares seed polymer SP and comprise mix monomer, polymerization initiator I
aAnd deionized water, wherein, described mix monomer is comprised of monomer A, monomers B, monomer C and monomer D; The quality of described monomer A accounts for the 60-80% of described mix monomer total mass; The quality of described monomers B accounts for the 10-30% of described mix monomer total mass; The quality of described monomer C accounts for the 5-10% of described mix monomer total mass, and the quality of described monomer D accounts for the 0.05-1% of described mix monomer total mass; Described seed polymer SP is at initiator I by described mix monomer
aAnd copolyreaction occurs under the condition that exists of deionized water make after cooling; Described initiator I
aFor water-soluble azo class initiator, be selected from azo diisobutyl amidine hydrochloride (V-50) or azo two isobutyl imidazoline salt hydrochlorates (VA-044); During described copolyreaction, described mix monomer total mass accounts for 5～15% of copolyreaction Raw total mass; Described initiator I
aAccount for 0.05～0.5% of described mix monomer total mass; The temperature of reaction of described copolyreaction is controlled to be 30-50 ℃, and the reaction times is controlled to be 24-36 hour; Described monomer A is acrylamide or Methacrylamide; Described monomers B be in vinylformic acid, methyl-prop diluted acid, allyl sulphonic acid, 2-acrylamide-2-methylpro panesulfonic acid and their sodium salt one or more; Described monomer C is meaned by following general formula 1:
In general formula 1, R
1, R
2Represent independently respectively H or CH
3, X represents O, CH
2O, CH
2CH
2O or COO; N=5～25;
Described monomer D is one or more of structure shown in general formula 2 or general formula 3, and wherein, general formula 2 and general formula 3 are expressed as respectively:
In general formula 2 and general formula 3, R
3For H or CH
3, R
5For H or CH
3, R
4, R
6For N (CH
3)
2, N (CH
2CH
3)
2Or
The molecular weight control of described seed polymer SP is 1.5 * 10
6～2.5 * 10
6.
2) prepare the raw material that polyacrylamide water bag aqueous dispersions prepares described polyacrylamide water bag aqueous dispersions and comprise seed polymer SP, monomer A, monomers B, inorganic salt E, dispersion stabilizer Stb, oxygenant I
bAnd deionized water; At first will account for the raw materials quality mark is the seed polymer SP of 5-10%, accounting for the raw materials quality mark is 10-20% inorganic salt E, accounting for the raw materials quality mark is that 1-3% dispersion stabilizer Stb and deionized water are uniformly mixed 30-40min under 15-40 ℃, obtain the seed dispersion liquid, then in this seed dispersion liquid, add monomer A and monomers B and pass into nitrogen, then under same temperature and agitation condition, continue to mix 30-40min, finally add oxygenant I
bAnd under 25-40 ℃, reacted 5～10 hours, cool to room temperature just makes described polyacrylamide water bag aqueous dispersions, and wherein, described inorganic salt E is sodium ion salt, ammonium ion salt or lithium ion salt; The total mass of described monomer A and monomers B accounts for the 10-20% of described raw material total mass; Described monomer A accounts for the 20-80% of monomer A and the total amount of substance of monomers B; Described oxygenant I
bFor Potassium Persulphate, ammonium persulphate or Sodium Persulfate and their arbitrary combination, described in itself and step 1), the mass ratio of monomer D is 2:1～1:2; Described dispersion stabilizer Stb is comb-grafted copolymer, and the molecular weight of described comb-grafted copolymer is 10000～100000, and it is meaned by following general formula (4):
In general formula (3), R
1For H or CH
3, R
2For H or CH
3, R
7For H or CH
3X is O, CH
2O, CH
2CH
2O or COO; M is H or basic metal or alkaline-earth metal ions; A:b:c=(2.5～7.5): (2.5～5): 1; The n value is 5～25.
The preparation method of dispersion agent of the present invention can be referring to patent CN103059216A (2013-04-24): make described comb-grafted copolymer by the copolyreaction of three kinds of monomer generation free radical additions, described three kinds of monomers are: 2-acrylamide-2-methylpro panesulfonic acid (general formula 4), and monomer shown in general formula of the present invention 2 and general formula 5;
Monomer C-structure of the present invention is as shown in general formula 1, its Main Function is as a kind of reactive space protection monomer, help to improve seed polymer SP forms after next step phase-splitting emulsion particle stability, simultaneously can reduce a minute phase reagent inorganic salt E consumption, but monomer C consumption is unsuitable too many, otherwise easily cause emulsion particle to be difficult for next step dispersion stabilizer Stb added of absorption, make on the contrary the emulsion particle stability decreases; Therefore the used in amounts of monomer C will will meet the rational proportioning of maintenance under other control condition with the used in amounts of inorganic salt E and dispersion stabilizer Stb, in the present invention, the consumption of monomer C and inorganic salt E and dispersion stabilizer Stb is through studying gained for a long period of time according to the inventor, this ratio not only can reduce the consumption of inorganic salt E, can also guarantee the performance that product of the present invention is final simultaneously.In addition, monomer D of the present invention is a kind of or several arbitrarily of structure shown in general formula 2 or general formula 3, and its Main Function is to provide the tertiary amine group with reductibility, and the oxygenant added with subsequent step forms redox system, its consumption crosses that to produce at least free radical few, and reaction conversion ratio is lower; Consumption is crossed the probability that can strengthen at most monomer polymerization in external phase, and product props up rate and crosslinking rate raising simultaneously, be unfavorable for the practical application of product, so the consumption of monomer D passes through according to the inventor the guaranteed quality product of the present invention that studies for a long period of time.
In the present invention, the preparation feedback of product carries out in two steps, this reaction first stage introduces the unsaturated monomer copolymerization that contains tertiary amine group of minute quantity in seed polymer, tertiary amine group just is fixed on inside particles after it separates out into particle, now add again the second batch monomer, and the micro amount of oxygen agent is as (Potassium Persulphate) KPS, (ammonium persulphate) APS etc., oxygenant is by diffusing into inside particles, will form redox system with tertiary amine group, in the inside particles original position, produce free radical, and consumption inside particles monomer carries out transfer reaction, in particle phase and external phase, the swelling equilibrium of monomer is broken simultaneously, monomer will constantly diffuse into the particle phase from external phase, until monomer completely consumed in external phase.This is equivalent to the monomer droplet warehouse in letex polymerization has been become and usingd whole external phase as the monomer warehouse, be the polymerization unit transferring raw material of inside particles continually, because the initiator system of polymerization is fixed on inside particles, therefore polyreaction also is limited in inside particles, so just can effectively reduce the viscosity of system in polymerization process.
The present invention is 1.5 * 10 by the molecular weight control of seed polymer SP
6～2.5 * 10
6If molecular weight is too little phase-splitting is comparatively difficult, need to add more inorganic salt; The too high gel that easily forms when preparing seed polymer of molecular weight.Therefore, in seed polymer SP building-up process, the contriver is by the reasonable control to synthetic material composition and proportioning and synthesis condition, and by these materials, interacting under certain condition and react forms molecular weight required for the present invention 1.5 * 10
6～2.5 * 10
6Seed polymer SP, to meet the demand of follow-up synthetic polyacrylamide water bag aqueous dispersions, and then guarantee the quality of the finished product.In addition, follow-up while preparing polyacrylamide water bag aqueous dispersions, by the reasonable control of selection, rational proportion and the synthesis condition of step seed polymer SP and other composition before, and by these materials, interact under certain condition and react and form the product that the present invention finally possesses high workability (viscosity is 97cP), high storage stability (25 ℃ be greater than 12 months-) and high molecular (up to 1,960 ten thousand).
The present invention has adopted the in-situ oxidation reduction to cause the preparation method in seed polymer SP preparation process, by tertiary amine group being fixed on to the inside particles that seed polymer SP separates out, add again second batch monomer and micro amount of oxygen agent as (Potassium Persulphate) KPS, (ammonium persulphate) APS etc., now oxygenant is by diffusing into inside particles, will form redox system with tertiary amine group, in the inside particles original position, produce free radical and consume the inside particles monomer and carry out transfer reaction, in particle phase and external phase, the swelling equilibrium of monomer is broken simultaneously, monomer will constantly diffuse into the particle phase from external phase, until monomer completely consumed in external phase.The method can improve speed of reaction and molecular weight product simultaneously.
Finally, the present invention is owing to adopting the method that substep is controlled and the in-situ oxidation reduction combines, namely in the inside particles original position, produce free radical, locus of polymerization is mainly at inside particles, and therefore, whole reaction process viscosity is low, good fluidity, do not need special heat transfer and whipping device, so cost of manufacture and difficulty reduce greatly, facilitate large industrial production; The product of producing by method of the present invention simultaneously, because over-all properties is greatly improved, has therefore enlarged the use range of anionic polyacrylamide water bag aqueous dispersions.
The preparation method of seed polymer of the present invention is in order to reach the effect of product of the present invention, therefore, although the method is conventional means in the synthetic field of polymer chemistry, this technology is converted in the preparation of anionic polyacrylamide water bag aqueous dispersions report.In addition, in the preparation of ion polyacrylamide water bag aqueous dispersions, using the difficulty of this technology is different from purpose and other Polymer Synthesizing fields.In addition, research just obtains effect of the present invention to the contriver through long-term experiment, and namely needing the molecular weight of the described seed polymer SP prepared by strict technique means control the present invention is 1.5 * 10
6～2.5 * 10
6Other field that is controlled at of this molecular weight does not have, without any the enlightenment in other field, can using in the preparation of anionic polyacrylamide water bag aqueous dispersions yet and reach effect of the present invention, neither the limited number of time experiment can reach, is not more those skilled in the art's conventional means.
The preparation method of anionic polyacrylamide water bag aqueous dispersions of the present invention can be for the process of any production anionic polyacrylamide water bag aqueous dispersions, and the cited preferred embodiment of the present invention is the preferred embodiment of the inventor through the gained that studies for a long period of time.
As preferably, the temperature of reaction of the described copolyreaction of step 1) is controlled to be 35-40 ℃.
As preferably, the reaction times of the described copolyreaction of step 1) is controlled to be 24-28 hour.
While as preferably, step 2), stirring, stir speed (S.S.) is 150-300r/min.
As preferably, described inorganic salt E is ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate or sodium tartrate and their arbitrary combination.
The invention has the beneficial effects as follows:
1, in the present invention, the preparation feedback of product carries out in two steps, this reaction first stage introduces the unsaturated monomer copolymerization that contains tertiary amine group of minute quantity in seed polymer, tertiary amine group just is fixed on inside particles after it separates out into particle, now add again the second batch monomer, and the micro amount of oxygen agent is as (Potassium Persulphate) KPS, (ammonium persulphate) APS etc., oxygenant is by diffusing into inside particles, will form redox system with tertiary amine group, in the inside particles original position, produce free radical, and consumption inside particles monomer carries out transfer reaction, so just can effectively reduce the viscosity of system in polymerization process, speed of reaction and molecular weight product have been improved simultaneously.
2, the inventor, by the reasonable control to synthetic material composition and proportioning and synthesis condition, is 1.5 * 10 by the molecular weight control of seed polymer SP
6～2.5 * 10
6The seed polymer SP of this molecular weight can meet the demand of follow-up synthetic polyacrylamide water bag aqueous dispersions, and then guarantees that the quality of the finished product namely possesses high workability (viscosity is 97cP), high storage stability (25 ℃ are greater than 12 months) and high molecular (up to 19,600,000).
3, the present invention is owing to adopting the substep control method to combine with the in-situ oxidation reduction, namely in the inside particles original position, produce free radical, locus of polymerization is mainly at inside particles, whole reaction process viscosity is low, good fluidity, do not need special heat transfer and whipping device, so cost of manufacture and difficulty reduce greatly, facilitate large industrial production; The product of producing by method of the present invention simultaneously, because over-all properties is greatly improved, has therefore enlarged the use range of anionic polyacrylamide water bag aqueous dispersions.
4, in each reactions steps of the present invention, raw materials used composition, proportioning and processing step are all that the inventor is through studying gained for a long period of time, each processing step closely cooperates and mutually is connected and interacts, especially the consumption of monomer C of the present invention and monomer D is controlled, be the essential condition that affects polymerization success of the present invention, itself and other control condition combine and reach the described effect of product of the present invention.
Embodiment
This specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the modification that there is no creative contribution as required after reading this specification sheets, but as long as in claim scope of the present invention, all are subject to the protection of patent law.
Concrete enforcement is divided into two portions, first by synthesis example, prepares seed polymer SP and dispersion stabilizer Stb, then prepares anionic polyacrylamide water bag aqueous dispersions by embodiment.In synthesis example and embodiment, raw materials used and code name is shown in Table 1.
In synthesis example of the present invention, the molecular weight of seed polymer and dispersion agent is used aqueous gel permeation chromatography (GPC) to measure.Condition determination is as follows:
Gel column: Shodex SB806+803 two root chromatogram column series connection
Eluant: 0.1M NaNO
3Solution
Moving phase speed: 1.0ml/min
Injection: the 20 μ l0.5% aqueous solution
Detector: Shodex RI-71 type differential refraction detector
Standard substance: polyoxyethylene glycol GPC standard specimen (Sigma-Aldrich, molecular weight 1010000,478000,263000,118000,44700,18600,6690,1960,628,232)
Raw materials used and code name in table 1 synthesis example and embodiment
| Material name | Be called for short |
| Acrylamide | A-1 |
| Methacrylamide | A-2 |
| Vinylformic acid | B-1 |
| Methacrylic acid | B-2 |
| Sodium allyl sulfonate | B-3 |
| The 2-acrylamide-2-methylpro panesulfonic acid | B-4 |
| Allyl polyether (n=5) | C-1 |
| Methoxy poly (ethylene glycol) monomethacrylates (n=10) | C-2 |
| Allyl polyether (n=20) | C-3 |
| Methoxy poly (ethylene glycol) mono acrylic ester (n=25) | C-4 |
| DMAM | D-1 |
| DMMAM | D-2 |
| DEAM | D-3 |
| DMAEMA | D-4 |
| DEAEMA | D-5 |
| PREMA | D-6 |
| Ammonium sulfate | E-1 |
| Sodium sulfate | E-2 |
| Lithium Sulphate | E-3 |
| Sodium-chlor | E-4 |
| Ammonium chloride | E-5 |
| Trisodium Citrate | E-6 |
| Sodium tartrate | E-7 |
| Azo diisobutyl amidine hydrochloride (V-50) | I a-1 |
| Azo two isobutyl imidazoline salt hydrochlorates (VA-044) | I a-2 |
[0048]?
| Potassium Persulphate (KPS) | I b-1 |
| Ammonium persulphate (APS) | I b-2 |
| Sodium Persulfate (SPS) | I b-3 |
Synthesis example A1(seed polymer SP1's is synthetic)
In the glass reactor that thermometer, agitator, nitrogen ingress pipe and reflux exchanger are housed, add 15 grams (A-1), 7.5 gram (B-1), 2.5 gram (C-1), 1.25 milligram (D-1) and 475 gram deionized waters, while stirring, use the nitrogen purging reaction vessel, and be warming up to 40 ℃, then add 1.25 milligrams of (I
a-1), insulation reaction was cooled to room temperature after 30 hours, obtained seed polymer SP1.
Synthesis example A2-A12(seed polymer SP1-SP12's is synthetic)
Step according to synthesis example A1 prepares SP1-SP12 of the present invention, feeds intake according to the described ratio of table 2.
Ingredient proportion and the molecular weight of table 2 seed polymer SP
Synthesis example B1(dispersion agent Stb1's is synthetic)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 100 ml deionized water, while stirring, use the nitrogen purging reaction vessel, and be warming up to 75 ℃, then by 80 milliliters, 30 grams (B-4) and 7 grams (B-1) and 5 grams (C-1) and water, make the mix monomer aqueous solution, it is splashed into to reactor, time for adding is 2 hours, and drip simultaneously 10% ammonium persulfate initiator solution 20 grams, time for adding is 5 hours, dropwise rear insulation reaction and be cooled to room temperature in 5 hours, obtain dispersion agent Stb1, its molecular weight is 15000.
Synthesis example B2-B4(dispersion agent Stb2-Stb4's is synthetic)
Step according to synthesis example B1 prepares Stb2-Stb4 of the present invention, feeds intake according to the described ratio of table 3.
Ingredient proportion and molecular weight prepared by table 3 dispersion agent Stb
Embodiment
Embodiment is the synthetic method of anionic polyacrylamide water bag aqueous dispersions of the present invention (APD).
In the embodiment of the present invention, the molecular weight of all anionic polyacrylamide water bag aqueous dispersions adopts viscosity method to measure according to GB17514-2008.Before measuring, must process sample, to remove inorganic salt and the complete monomer of unreacted in sample, concrete treating processes is as follows: anionic polyacrylamide water-dispersion breast is soluble in water, be made into mass concentration and be 2% the aqueous solution, then be poured in aqueous ethanolic solution (volume ratio of dehydrated alcohol and the aqueous solution is 3:1) and be settled out polymkeric substance, then use washing with acetone.This process triplicate, then by throw out 40 ℃ of lower vacuum-dryings.The monitoring of polymerization process medium viscosity is for using syringe abstraction reaction liquid every 15min, with SNB AI intelligence Brookfield viscometer, No. 27 rotor is measured cloth network gram Field (Brookfield) viscosity, the peak viscosity of assaying reaction and product final viscosity under 30RPM.
Embodiment 1's is synthetic)
In the glass reactor that thermometer, agitator, nitrogen ingress pipe and reflux exchanger are housed, add 25 grams (SP1), 75 grams (E-1) and 5 grams (E-4), 5 grams (Stb1) and 340 gram deionized waters, stir and fully mix 30min under 37 ℃, stir speed (S.S.) is 300r/min, then add 40 grams (A-1) and 10 grams (B-1), logical nitrogen, be incubated 35 ℃ and continue to mix 35min, adds 2.5 milligrams of initiator I
b-1, insulation reaction was cooled to room temperature after 8 hours, obtained anionic polyacrylamide water bag aqueous dispersions APD1.
Embodiment 2-12's is synthetic)
Step according to embodiment 1 prepares APD2-APD12 of the present invention, feeds intake according to the described ratio of table 4, and relevant nature is in Table 5.
Table 4 water bag aqueous dispersions prepares each reactant ingredient proportion
The sign of table 5 polyacrylamide water bag aqueous dispersions
Attached: the chemical structure of tertiary amine monomers and title
Claims (5)
1. in-situ oxidation reduction initiation prepares polyacrylamide water bag aqueous dispersions, and it is characterized in that: it comprises following preparation process successively:
1) prepare the raw material that seed polymer SP prepares seed polymer SP and comprise mix monomer, polymerization initiator I
aAnd deionized water, wherein, described mix monomer is comprised of monomer A, monomers B, monomer C and monomer D; The quality of described monomer A accounts for the 60-80% of described mix monomer total mass; The quality of described monomers B accounts for the 10-30% of described mix monomer total mass; The quality of described monomer C accounts for the 5-10% of described mix monomer total mass, and the quality of described monomer D accounts for the 0.05-1% of described mix monomer total mass; Described seed polymer SP is at initiator I by described mix monomer
aAnd copolyreaction occurs under the condition that exists of deionized water make after cooling; Described initiator I
aFor water-soluble azo class initiator, be selected from azo diisobutyl amidine hydrochloride (V-50) or azo two isobutyl imidazoline salt hydrochlorates (VA-044); During described copolyreaction, described mix monomer total mass accounts for 5～15% of copolyreaction Raw total mass; Described initiator I
aAccount for 0.05～0.5% of described mix monomer total mass; The temperature of reaction of described copolyreaction is controlled to be 30-50 ℃, and the reaction times is controlled to be 24-36 hour; Described monomer A is acrylamide or Methacrylamide; Described monomers B be in vinylformic acid, methyl-prop diluted acid, allyl sulphonic acid, 2-acrylamide-2-methylpro panesulfonic acid and their sodium salt one or more; Described monomer C is meaned by following general formula 1:
In general formula 1, R1, R2 represent respectively H or CH independently
3, X represents O, CH
2O, CH
2CH
2O or COO; N=5～25;
Described monomer D is one or more of structure shown in general formula 2 or general formula 3, and wherein, general formula 2 and general formula 3 are expressed as respectively:
In general formula 2 and general formula 3, R
3For H or CH
3, R
5For H or CH
3, R
4, R
6For N (CH
3)
2, N (CH
2CH
3)
2Or
The molecular weight control of described seed polymer SP is 1.5 * 10
6～2.5 * 10
6.
2) prepare raw material that polyacrylamide water bag aqueous dispersions prepares described polyacrylamide water bag aqueous dispersions comprise seed polymer SP, monomer A, monomers B,, inorganic salt E, dispersion stabilizer Stb, oxygenant I
bAnd deionized water; At first will account for the raw materials quality mark is the seed polymer SP of 5-10%, accounting for the raw materials quality mark is 10-20% inorganic salt E, accounting for the raw materials quality mark is that 1-3% dispersion stabilizer Stb and deionized water are uniformly mixed 30-40min under 15-40 ℃, obtain the seed dispersion liquid, then in this seed dispersion liquid, add monomer A and monomers B and pass into nitrogen, then under same temperature and agitation condition, continue to mix 30-40min, finally add oxygenant I
bAnd under 25-40 ℃, reacted 5～10 hours, cool to room temperature just makes described polyacrylamide water bag aqueous dispersions, and wherein, described inorganic salt E is sodium ion salt, ammonium ion salt or lithium ion salt; The total mass of described monomer A and monomers B accounts for the 10-20% of described raw material total mass; Described monomer A accounts for the 20-80% of monomer A and the total amount of substance of monomers B; Described oxygenant I
bFor Potassium Persulphate, ammonium persulphate or Sodium Persulfate and their arbitrary combination, described in itself and step 1), the mass ratio of monomer D is 2:1～1:2; Described dispersion stabilizer Stb is comb-grafted copolymer, and the molecular weight of described comb-grafted copolymer is 10000～100000, and it is meaned by following general formula (4):
In general formula (3), R
1For H or CH
3, R
2For H or CH
3, R
7For H or CH
3X is O, CH
2O, CH
2CH
2O or COO; M is H or basic metal or alkaline-earth metal ions; A:b:c=(2.5～7.5): (2.5～5): 1; The n value is 5～25.
2. in-situ oxidation reduction initiation prepares polyacrylamide water bag aqueous dispersions as claimed in claim 1, and it is characterized in that: the temperature of reaction of the described copolyreaction of step 1) is controlled to be 35-40 ℃.
3. in-situ oxidation reduction initiation prepares polyacrylamide water bag aqueous dispersions as claimed in claim 1, and it is characterized in that: the reaction times of the described copolyreaction of step 1) is controlled to be 24-28 hour.
4. in-situ oxidation reduction causes and prepares polyacrylamide water bag aqueous dispersions as claimed in claim 3, it is characterized in that: step 2) described in while stirring stir speed (S.S.) be 150-300r/min.
5. in-situ oxidation reduction initiation prepares polyacrylamide water bag aqueous dispersions as claimed in claim 4, and it is characterized in that: described inorganic salt E is ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate or sodium tartrate and their arbitrary combination.
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| CN103408698B (en) | 2015-08-26 |
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