Background technology
The constructional feature of polyacrylamide and complete kind make it to be widely applied in the every field of national economy, enjoy the title of " all trades auxiliary agent ".In China, owing to petroleum resources shortage, water resources shortage, the forest reserves lack, the application of polyacrylamide in oil, water treatment and papermaking three large fields is even more important, and has strategic importance.
The method of synthetic polyacrylamide comprises solution polymerization, inverse suspension polymerization and inverse emulsion polymerization.Solution polymerization later stage viscosity is very high, stirring and heat radiation are very difficult, need to use special equipment drying to make powder, complicated technical process tends to cause the polyacrylamide chain to occur crosslinked and degraded waits side reaction, simultaneously the dry powder type polyacrylamide dissolves difficulty before use, needs for a long time and special dissolution equipment.The polyacrylamide of emulsion-type has good solvability, but this kind method need to be used a large amount of hydrocarbon organic solvents and tensio-active agent, easily environment is caused secondary pollution.
Aqueous dispersion polymerization (aqueous dispersion polymerization also is referred to as the water polymerization of water bag or double-aqueous phase polymerization) is because production efficiency is high, the technique environmental protection, and product dissolving and flocculating property excellence become various countries' research emphasis.European patent EP 0183466 and EP0657478, US Patent No. A4929655 and USA5006590 have all described in the aqueous solution that contains multivalent anions salt and polymer stabilizer, pass through acrylamide, acrylyl oxy-ethyl-trimethyl salmiac, the copolymerization of acrylyl oxy-ethyl dimethyl benzyl ammonium chloride obtains water-in-water emulsion, but its system viscosity in the process of preparation is very high, all proposes high requirement to stirring and conducting heat.
Water bag water polymerization key is in time Precipitation from system of the polymer chain that forms by radical polymerization, forms primary particle, and rapid absorption dispersion agent forms stable emulsion particle simultaneously, avoids causing gel because system viscosity explodes.CN1884324A reduces acrylamide solubleness by introducing the hydrophobic monomer copolymerization, makes it in time to separate out, and adopts simultaneously cationic polymers and polymerized polyalcohol one package stabilizer to improve stabilising effect.CN101016352A then adopts the cationic monomer that contains benzyl to reduce acrylamide solubleness; CN1709945A adopts the one package stabilizer of addition polymerization cationic polymers and condensation polymerization cationic polymers, because the condensation polymer molecular weight is low, therefore has better stabilising effect.
This shows that the selection of dispersion agent is to the reaction important, above-mentioned patent all adopts the multipolymer (such as acrylyl oxy-ethyl-trimethyl salmiac and acrylamide copolymer) of linear cation high molecular (mainly being the polyacrylamide oxy-ethyl-trimethyl salmiac) or cationic monomer and non-ionic monomer as dispersion agent, utilize polymer adsorption to stablize emulsion particle in the sterically hindered effect that particle surface produces, this requires dispersion agent to have higher molecular weight (usually 50~1,000,000), so that enough steric hindrances to be provided, this brings series of problems: at first, reaction is carried out in high salt medium, the too high dispersion agent of molecular weight is difficult to fast dissolving, its molecular chain is in the state of rolling up, and greatly reduces its adsorption rate and stabilization; Secondly, the too high initial reaction stage system viscosity that causes of dispersant molecule amount is larger, adds that macromolecular chain is difficult to diffusion motion, and the adsorption rate of initial reaction stage dispersion agent is very slow, often makes the polymerization failure because can not in time stablizing the emulsion particle of separating out; Again, cation dispersing agent is with a large amount of positive charges, there is electrostatic repulsion in it with the emulsion particle of separating out, adsorb slower, initial reaction stage particularly, emulsion particle positively charged higher (because the reactivity ratio difference of cationic monomer and non-ionic monomer causes) repel very strongly, dispersion agent is difficult to play stabilization, it is poly-and and make polymerization failed that initial reaction stage very easily produces particle.
Summary of the invention
The technical problem to be solved in the present invention is; too high so that the adsorption rate of dispersion agent is very slow because of molecular weight for the dispersion agent that adopts in the polyacrylamide water-in-water emulsion preparation process in the prior art; stabilization is poor; more may separate out emulsion particle or emulsion particle and very easily produce particle and gather also and cause polymerization unsuccessfully to wait defects because can not in time stablize in that initial reaction stage is normal; a kind of preparation method of cationic polyacrylamide water-in-water emulsion is provided; in this preparation method, adopted a kind of molecular weight; positive charge density is low; the sterically hindered strong comb-grafted copolymer of side chain is as dispersion agent; it is little that this dispersion agent has viscosity; diffusion is rapid with absorption; the advantages such as stably dispersing is effective; and the molecular structure of this dispersion agent is adjustable; system can design different structure to hetero-polymer; with strong points; effectively reduced polymerization system viscosity; improved the stability of product solid content and water-in-water emulsion, and the cationic polyacrylamide water-in-water emulsion that utilizes preparation method of the present invention to obtain also to have dissolution rate fast; the advantages such as molecular weight height and good fluidity.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of cationic polyacrylamide water-in-water emulsion, and preparation process is as follows:
(1) non-ionic monomer A, cationic monomer B, inorganic salt C and dispersion agent D are joined in the reactor in proportion, being dissolved in water obtains reaction solution, and regulating pH is 4.0 ~ 5.5; Wherein, inorganic salt C accounts for 25-40wt%, and non-ionic monomer A and cationic monomer B account for 15-30wt% altogether, and dispersion agent D accounts for 1-3wt%, and surplus is water;
(2) reaction solution that step (1) is obtained is warming up to 30-50 ° of C, and logical nitrogen deoxygenation adds initiator I, carries out polyaddition reaction; The add-on of initiator I accounts for the 0.01-0.05wt% of the middle non-ionic monomer A of step (1) and cationic monomer B gross weight;
(3) insulation reaction is after 10 hours, cool to room temperature, and discharging makes the cationic polyacrylamide water-in-water emulsion;
Non-ionic monomer A is selected from acrylamide or Methacrylamide, and accounts for the 70-95mol% of non-ionic monomer A and cationic monomer B total amount;
Cationic monomer B adopts by the represented material of general formula (1):
Wherein A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, R
1Expression H or CH
3, R
2And R
3Represent independently of one another CH
3Or CH
2CH
3, R
4Expression H, CH
3, CH
2CH
3Or CH
2C
6H
5
Dispersion agent D is comb-shaped graft copolymer, and it adopts by the represented material of general formula (2):
Wherein, A represents O or NH, and B represents CH
2CH
2, CH
2CH
2CH
2Or CH
2CHOHCH
2, X represents O, CH
2O, CH
2CH
2O or COO, R
1, R
5, R
7Represent independently of one another H or CH
3, R
2And R
3Represent independently of one another CH
3Or CH
2CH
3, R
4Expression H, CH
3, CH
2CH
3Or CH
2C
6H
5, R
6Expression OH, NH
2Or N (CH
3)
2CH
2SO
3-, R
8Expression OH or CH
3
The span of dispersion agent D molecular weight is 10000~100000; A:b:c=(1~2): (0~2): 1; The n value is 5~25.
In technical scheme of the present invention, after in reactor, adding non-ionic monomer A, cationic monomer B, inorganic salt C and dispersion agent D, be dissolved in water again in the step (1) and obtain reaction solution, regulating pH is 4.0 ~ 5.5; If pH is greater than 5.5, the molecular weight of the product that obtains after then reacting by step (2) and step (3) can be on the low side, do not reach target product to the requirement of molecular weight, and speed of response is also slow, if pH is less than 4.0, then can accelerate the speed of polyaddition reaction, cause easily the generation of gel.
In technical scheme of the present invention, the reaction solution that in the step (2) step (1) is obtained is warming up to 30-50 ° of C, and logical nitrogen deoxygenation adds initiator I, carries out polyaddition reaction; The temperature of reaction of addition polymerization is relevant with the kind of initiator I, but in the art, reaction solution generally is warming up to 30-50 ° of C.In addition, in step (2), the add-on of initiator I accounts for the 0.01-0.05wt% of non-ionic monomer A and cationic monomer gross weight; If the consumption of initiator I is lower than 0.01wt%, then can cause polyreaction unstable, repeatability is lower; If the consumption of initiator I surpasses 0.05wt%, then can cause reaction gel or molecular weight on the low side, can not obtain stable cationic polyacrylamide water-in-water emulsion.
In technical scheme of the present invention, in the step (3) time of insulation reaction generally all in 10 hours, after the insulation reaction, cool to room temperature, discharging can make target product cationic polyacrylamide water-in-water emulsion.
In addition, the transformation efficiency of polyaddition reaction of the present invention surpasses 99.5%, and the product solid content is substantially equal to feed ratio, is approximately 15-30%.In addition, the enhanced dissolution rate of the cationic polyacrylamide water-in-water emulsion for preparing by technical scheme of the present invention, and have the advantages such as the high and good fluidity of molecular weight.
In technical scheme of the present invention, dispersion agent D is comb-shaped graft copolymer, its structure is shown in general formula (2), the span of its molecular weight is 10000 ~ 100000, a:b:c=(1~2): (0~2): 1, n value is 5~25, molecular weight, the viscosity of dispersant solution is little, and rate of diffusion and adsorption rate obviously improve in high salt, and the particle that initial reaction stage is separated out can play rapidly stabilization; Simultaneously, because graft side chain has larger steric hindrance, the relatively conventional linear polymeric of its stably dispersing effect is further promoted, and is conducive to the extended storage stability that polymerization reaction late stage maintenance system is stabilized and increased emulsion; In addition, carboxylic acid on the dispersion agent chain link or sulfonic acid group can strengthen dispersion agent with the adsorption between the positively charged emulsion particle, so that the positive charge density on dispersion agent surface reduces, the positive charge density that is the dispersion agent surface is low, also reduce the desorption of stablizer, had obvious effect for improving reaction later stage transformation efficiency, product solid content and electric charge degree.In addition, from general formula (2) as can be known, described dispersion agent D is comb-shaped graft copolymer, its molecular structure is adjustable, so just can design different structure for hetero-polymer system, and is with strong points, and the viscosity of this dispersion agent D is little, can effectively reduce polymerization system viscosity like this.
As a kind of improvement to technical scheme of the present invention, dispersion agent D is dissolved in water by monomer shown in cationic monomer B shown in the general formula (1), general formula (3) and the general formula (4) and obtains reaction solution, then issue living free radical polyaddition reaction in initiator I effect and make, its formula of (3) and general formula (4) are respectively:
Wherein, R
5And R
7Represent independently of one another H or CH
3, R
6Expression OH, NH
2Or N (CH
3)
2CH
2SO
3 -, R
8Expression OH or CH
3, X represents O, CH
2O, CH
2CH
2O or COO, n value scope is 5~25;
The molar ratio of monomer is a:b:c shown in general formula (1), general formula (3) and the general formula (4), and a, b and c are a, b and the c in the general formula (2).
In technical scheme of the present invention, by monomer shown in cationic monomer B shown in the general formula (1), general formula (3) and the general formula (4) the dispersion agent D that polyaddition reaction prepares occuring under initiator I effect is comb-grafted copolymer, the molecular structure of this dispersion agent D is adjustable, system can design different structure to hetero-polymer, with strong points, and can effectively reduce the viscosity of polymerization system.
As a kind of improvement to technical scheme of the present invention, n value scope is preferably 10 ~ 20.When the n value was 5 ~ 10, the adsorption rate of dispersion agent D was larger, so that the stability of the emulsion particle of early origin is stronger, early stage viscosity is also lower, but because side chain is shorter, the dispersion liquid viscosity that obtains at last can become large; If the n value is 20 ~ 25, the side chain of the dispersion agent D that then obtains is longer, and early stage dispersion effect is slightly poor, and the latex particle size of formation is slightly large, can affect to a certain extent its solvability like this.
As a kind of improvement to technical scheme of the present invention, in dispersion agent D preparation process, the quality summation of monomer accounts for the 15-40% of reaction system total mass shown in general formula (1), general formula (3) and the general formula (4).If the total concn of monomer mixed solution greater than 40%, then produces gel easily, if the total concn of monomer mixed solution is lower than 15%, then be difficult to obtain the target molecular weight product, and solid content also can be lower.
As a kind of improvement to technical scheme of the present invention, in dispersion agent D preparation process, the radical addition polymerization reaction is carried out under 30 ~ 50 ° of C, and the reaction times is controlled at 4-5 hour.Temperature of reaction depends on the decomposition temperature with initiator I; In addition, if the reaction times less than 4 hours, then monomer can not be converted into target product fully, has reduced transformation efficiency; If the reaction times is greater than 5 hours, then fully need not, in a word, the reaction times is controlled at 4-5 hour, so just can control better the transformation efficiency of monomer.
As a kind of improvement to technical scheme of the present invention, in dispersion agent D preparation process, take dropping mode separately to drip mixed solution and initiator by monomer shown in described general formula (1), general formula (3) and the general formula (4), and the time for adding of the two all is controlled at 1.5-2 hour.Take separately to drip the mode of monomer mixture and initiator, the homogeneity that easier like this control multipolymer chain link distributes and the stability of polyreaction can also avoid producing gel to a certain extent.
As a kind of improvement to technical scheme of the present invention, in dispersion agent D preparation process, initiator I is selected from a group in hydrogen peroxide and xitix, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium bisulfite, ammonium persulphate and S-WAT, Sodium Persulfate and sodium bisulfite or ammonium persulphate and the trolamine, and initiator I accounts for the 0.2-1wt% of monomer total amount.The consumption of initiator I is controlled at the 0.2-1wt% of monomer total amount, the molecular weight of easier like this control dispersion agent D, if the consumption of initiator I is too low, then polyreaction is unstable, if consumption is too high, then can cause the too low consequence of reaction gel or target molecular weight.
As a kind of improvement to technical scheme of the present invention, non-ionic monomer A is acrylamide.
As a kind of improvement to technical scheme of the present invention, inorganic salt C is sodium, ammonium, lithium ion salt, is selected from one or more arbitrary combination in ammonium sulfate, sodium sulfate, Lithium Sulphate, sodium-chlor, ammonium chloride, Trisodium Citrate, the sodium tartrate.In technical scheme of the present invention, cationic polyacrylamide water-in-water emulsion synthetic take inorganic salt solution as medium, used inorganic salt are necessary for the good solvent of monomer, the poor solvent of final polymkeric substance.
As a kind of improvement to technical scheme of the present invention, inorganic salt C is one or more arbitrary combination in ammonium sulfate, Lithium Sulphate or the sodium-chlor.When adopting above-mentioned several inorganic salt, the viscosity of the cationic polyacrylamide water-in-water emulsion of prepared acquisition is lower, simultaneously also so that the dissolution rate of cationic polyacrylamide water-in-water emulsion is faster.
In technical scheme of the present invention, initiator I can adopt one or both compound uses in water-soluble azo class initiator, the redox initiator.Water-soluble azo class initiator is selected from azo diisobutyl amidine hydrochloride or azo two isobutyl imidazoline salt hydrochlorates; Redox initiator is selected from a group in hydrogen peroxide and xitix, Potassium Persulphate and S-WAT, Potassium Persulphate and sodium bisulfite, ammonium persulphate and S-WAT, ammonium persulphate and sodium bisulfite or ammonium persulphate and the trolamine.In addition, when adopting water-soluble azo class initiator and redox initiator, both amount there are not special requirement, as long as total amount meets the demands.
Therefore, the invention has the beneficial effects as follows the preparation method that a kind of cationic polyacrylamide water-in-water emulsion is provided, in this preparation method, adopted a kind of molecular weight, positive charge density is low, the sterically hindered strong comb-grafted copolymer of side chain is as dispersion agent, it is little that this dispersion agent has a viscosity, diffusion is rapid with absorption, the advantages such as stably dispersing is effective, and the molecular structure of this dispersion agent is adjustable, system can design different structure to hetero-polymer, with strong points, effectively reduced polymerization system viscosity, improved the stability of product solid content and water-in-water emulsion, and the cationic polyacrylamide water-in-water emulsion that utilizes preparation method of the present invention to obtain also to have dissolution rate fast, molecular weight is high, good fluidity and the advantage such as easy to use.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
Used raw material and be called for short cationic polyacrylamide water-in-water emulsion brief note as shown in table 1, synthetic and be CPD in cationic polyacrylamide water-in-water emulsion Preparation Example of the present invention and dispersion agent D synthetic example.
Raw materials used in table 1 water-in-water emulsion Preparation Example and the dispersion agent synthetic example
In dispersion agent synthetic example of the present invention, dispersion agent D molecular weight uses aqueous gel permeation chromatography (GPC) to measure.Experiment condition is as follows:
Gel column: Shodex SB806+803 two root chromatogram columns series connection
Eluant: 0.1M NaNO
3Solution
Moving phase speed: 1.0ml/min
Injection: 20 μ l, 0.5% 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)
Dispersion agent synthetic example 1(dispersion agent D-1's is synthetic)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 18.2 grams (F-1), 0.15 gram hydrogen peroxide, 100 ml deionized water, use while stirring the nitrogen purging reaction vessel, be warming up to 45 ℃, then 9.68 grams (B-1) and 7.2 are restrained 80 milliliters in (E-1) and water, make the mix monomer aqueous solution, it is splashed into reactor, time for adding is 2 hours, and drips simultaneously 1% ascorbic acid solution, 20 grams, and time for adding is 2 hours, dropwise rear insulation reaction and be cooled to room temperature in 3 hours, obtain dispersion agent D-1, then adopt above-mentioned aqueous gel permeation chromatography (GPC) to measure, measurement result shows that its molecular weight is 17000.
Dispersion agent synthetic example 2-4(dispersion agent D-2 ~ D-4's is synthetic)
Step and method according to dispersion agent synthetic example 1 prepares dispersion agent D-2 ~ D-4, feed intake according to the described ratio of table 2, after obtaining dispersion agent D-2 ~ D-4, continue to adopt above-mentioned aqueous gel permeation chromatography (GPC) to measure, thereby obtain the molecular weight of dispersion agent D-2 ~ D-4.
Ingredient proportion and the molecular weight of the preparation of table 2 dispersion agent
The common dispersion agent D-5's of dispersion agent contrast synthetic example 1(is synthetic)
Thermometer is being housed, agitator, dropping funnel, in the glass reactor of nitrogen ingress pipe and reflux exchanger, add 100g acrylyl oxy-ethyl-trimethyl salmiac and 398g water, be warming up to 50 ℃, purge nitrogen after 30 minutes, adding 2g concentration is the aqueous solution of 5% initiator V-50, react stopped reaction after 20 hours, obtain polyacrylamide oxy-ethyl-trimethyl salmiac (dispersion agent D-5), in 25 ℃ of waters bath with thermostatic control take the 1.00mol/L sodium chloride aqueous solution as solvent, adopt Ubbelohde viscometer to measure the limiting viscosity number of PDAC according to GB17514-2008, (Polymer 1984 according to document, 25, (9), 1317-1322.) report relational expression calculating molecular weight is about 7.5 * 10
5Da.
The molecular weight of conventional dispersion agent generally between 50-150 ten thousand, and from dispersion agent contrast synthetic example 1 as can be known the molecular weight of common dispersion agent D-5 be 7.5 * 10
5Da, and show in the table 2, utilize the molecular weight of the dispersion agent that technical scheme of the present invention prepares between 10000-100000, can utilize thus the molecular weight of the dispersion agent of dispersant preparation method acquisition of the present invention, its soltion viscosity is little, molecule more easily moves, therefore have faster diffusion and adsorption rate, avoid initial reaction stage generation system gel, simultaneously, because graft side chain has larger tail resistance effect, the relatively conventional linear polymeric of its stably dispersing effect is further promoted.The dispersion agent that utilizes above-mentioned dispersion agent synthetic example to prepare carries out the preparation of cationic polyacrylamide water-in-water emulsion.
Cationic polyacrylamide water-in-water emulsion synthetic example 1(CPD-1)
In the glass reactor that thermometer, agitator, nitrogen ingress pipe and reflux exchanger are housed, add 65.09 grams (A-1), 9.91 gram (B-1), 100 grams (C-1) and 25 grams (C-4), 5 grams (D-2) and 295 gram deionized waters, regulation system pH value is 4.0~5.5, use while stirring the nitrogen purging reaction vessel, and be warming up to 35 ℃, then add 0.015 gram (I-1), insulation reaction was cooled to room temperature after 10 hours, obtained cationic polyacrylamide water-in-water emulsion CPD-1.
Cationic polyacrylamide water-in-water emulsion synthetic example 2-12(CPD-2 ~ CPD-12)
Step according to cationic polyacrylamide water-in-water emulsion synthetic example 1 prepares CPD-2-CPD-12 of the present invention, feeds intake according to the described ratio of table 3.
After utilizing above-mentioned steps to prepare cationic polyacrylamide water-in-water emulsion CPD1-12, adopt SNB AI intelligence Brookfield viscometer, No. 27 rotors are measured cloth network gram Field (Brookfield) viscosity of dispersion liquid under 10RPM, dispersion liquid viscosity is lower, illustrates that its flowability is better.In the embodiment of the invention, the intrinsic viscosity of all cationic polyacrylamides adopts viscosimetry to measure according to GB17514-2008, adopt document (Journal of Polymer Science Part C-Polymer Symposium, 1973, MH Equation for Calculating molecular weight 42:173-183.).Must process sample before measuring, to remove inorganic salt and the complete monomer of unreacted in the sample, concrete treating processes is as follows: the cationic polyacrylamide water-in-water emulsion is soluble in water, be made into mass concentration and be 2% the aqueous solution, then be poured in the aqueous ethanolic solution (volume ratio of dehydrated alcohol and the aqueous solution is 3:1) and be settled out polymkeric substance, use again washing with acetone.This process triplicate, then with throw out 40 ℃ of lower vacuum-dryings.The sample that dissolution time is measured 0.1g joins in the 9.9 gram water, adopts SNB AI intelligence Brookfield viscometer, and No. 21 rotor is measured soltion viscosity over time under 200RPM, writes down the time that viscosity reaches when stablizing to be dissolution time.
The cationic polyacrylamide water-in-water emulsion synthesizes comparative example 1
Use the synthetic cationic polyacrylamide water-in-water emulsion CPD-13 with the similar composition of CPD-1 of common dispersion agent D-5, according to above-mentioned detection method gained cationic polyacrylamide water-in-water emulsion CPD-13 is tested, dispersion liquid viscosity, molecular weight and the dissolution time of CPD-1 and CPD-13 are as shown in table 4 again.
As known from Table 3, the dispersion liquid viscosity of CPD-1 ~ CPD-13 is at 89 ~ 371mPaS, and molecular weight is 6,400,000-1,280 ten thousand, and dissolution time is 3-8min; From the contrast of table 3 and table 4 as can be known, compare with CPD-13, utilize the dispersion liquid viscosity of the cationic polyacrylamide water-in-water emulsion CPD-1 that technical scheme of the present invention prepares little, good fluidity, molecular weight is high, and dissolution time is short, and the speed of namely dissolving is fast.