CN101469040B - Polyelectrolyte for dispersing aqueous inorganic color stuffing and preparation thereof - Google Patents
Polyelectrolyte for dispersing aqueous inorganic color stuffing and preparation thereof Download PDFInfo
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- CN101469040B CN101469040B CN2007101733531A CN200710173353A CN101469040B CN 101469040 B CN101469040 B CN 101469040B CN 2007101733531 A CN2007101733531 A CN 2007101733531A CN 200710173353 A CN200710173353 A CN 200710173353A CN 101469040 B CN101469040 B CN 101469040B
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Abstract
The invention relates to macromolecular electrolyte for dispersing aquo-system inorganic pigment filler, which is obtained by taking acrylic monomers and alkaline-earth metal salts of carbonic acid as main raw materials and synthesizing the raw materials by a one-step method. The macromolecular electrolyte for dispersing the aquo-system inorganic pigment filler fully utilizes a great deal of heat energy emitted during reaction, simplifies the operating procedure, and improves the production efficiency.
Description
Technical field
The present invention relates to macromolecular material in the chemical industry field and preparation method thereof, specifically, relate to a kind of polymer electrolyte and one-step preparation process thereof that uses as aqueous coating color stuffing dispersion agent that be applicable to.
Background technology
So polymer electrolyte becomes the focus of people research, its reason be it can be effectively with inorganic color stuffing stable be dispersed in aqueous phase.U.S. Pat P4517098 proposes to solve with the sodium polymethacrylate salt brine solution deposition problems of particles such as lime carbonate in the process water, magnesiumcarbonate, calcium sulfate.USP2783200 points out and can handle mud thing and throw out in the boiler with methylacrylic acid or sodium salt of methacrylic acid, and USP3083916 points out that vinylformic acid and other monomer copolymerizations can improve dispersion efficiency, and USP4008164 points out can stop the deposition of calcium at aqueous phase with methylacrylic acid and acrylic acid multipolymer; USP3293152,3579455,3663448; 3699048,3766077,4004939; 4209398,4303568,4326980; All discussed at ROHM, in the sodium polymethacrylate salt, carried out to satisfy the different performance demand after the copolymerization through adding other monomers.
The article that Research in China is gathered propionic acid sodium salt dispersion agent compound method is also a lot, points out with S-WAT as chain-transfer agent in " chemical research " the 16th volume second phase like Huang Liangxian etc.Liu Jinhua etc. can make chain-transfer agent with inferior sodium phosphate " meticulous and specialty chemicals " the 14th volume the 1st interim pointing out.Huang Liangxian etc. pointed out with sodium sulfite anhy 96 as chain-transfer agent in " University Of Shanxi's journal natural science edition " the 28th volume fourth phase.Proposed to prepare the method for low molecular weight sodium polyacrylate salt among the CN92111424.9, and concluded the pros and cons of several frequently seen polymerization method with the ternary redox system.But above these polymerization methodses all are to adopt two-step approach, and promptly the first step is that monomer carries out polymerization earlier under the condition that initiator exists, and second step neutralized with alkali lye.Heat release is fast when it is pointed out that the Acrylic Acid Monomer auto-polymerization, and release of heat is high and inhomogeneous, and control molecular weight difficulty is big, so on technology, be difficult to grasp.
Summary of the invention
It is the polyelectrolyte for dispersing aqueous inorganic color stuffing and preparation method thereof of main raw material with the acrylic monomer that the present invention aims to provide a kind of; This polymer electrolyte is applicable to inorganic color stuffings such as the white titanium pigment that disperses in the water-borne coatings, talcum powder, kaolin, and is particularly very effective for free settling, the fine particle calcium carbonate at the knot end.When this polymer electrolyte is coated on the color stuffing surface; On each particle surface, form polymeric carboxylic negative ion layer; Cause between a plurality of particles with identical charges mutually exclusively, thereby prevented interparticle gathering and condense, thereby reached good dispersion stabilization.
Another object of the present invention provides the method for the synthetic above-mentioned polymer electrolyte of a kind of single stage method; It can overcome the shortcoming of two-step approach noted earlier; And it has made full use of the great amount of heat energy of emitting in the reaction process, has simplified operation steps, has improved production efficiency.
The present invention is that this will realize, the characteristic of described polyelectrolyte for dispersing aqueous inorganic color stuffing is that in weight percent, the synthesizing formula of this polymer electrolyte is formed and comprised:
Acrylic monomer 25～35%;
Inorganic carbonate 15～30%;
Chain-transfer agent 0.1～5%;
Initiator 0.3～0.5%;
Solvent 40～50%.
Wherein, Described acrylic monomer is meant vinylformic acid, methylacrylic acid and water-soluble monomer thereof, is selected from a kind of in methylacrylic acid, methylacrylic acid β hydroxyl ethyl ester, methylacrylic acid β hydroxypropyl acrylate, vinylformic acid, propenoic acid beta hydroxyl ethyl ester, propenoic acid beta hydroxypropyl acrylate, ethyl propenoate, the Jia Jibingxisuanyizhi or several combination.Described inorganic carbonate is meant the alkaline earth salt of carbonic acid, comprises yellow soda ash, salt of wormwood or Quilonum Retard.Described chain-transfer agent is selected from one or more in sodium sulfite anhy 96, Thiovanic acid, mercaptoethanol, mercaprol, inferior sodium phosphate, the ortho phosphorous acid.Described initiator is an ammonium persulphate.Described solvent is a deionized water.
Dispersion requirement according to the water-borne coatings inorganic color stuffing the present invention is to provide the oligopolymer with following structure and polymerization degree:
The n polymerization degree is 10～70 in
following formula;
The n polymerization degree is 10～70 in
following formula;
＝10～70；
＝10～70。
According to the present invention, above-mentioned polyelectrolyte for dispersing aqueous inorganic color stuffing is to adopt the one-step synthesis process preparation, and the characteristic of this synthesis technique is; Be the aqueous solution of inorganic carbonate is added still earlier as one of reactant at the bottom of, be added dropwise to the bottom to acrylic monomer, make it soon to be neutralized to acrylate; Have the lower acrylate of partial solubility to separate out with crystalline form earlier in the system, and the acrylate that is dissolved in the water carry out polymerization under action of evocating, along with the increase of the polymerization degree; Impel the acrylate of crystalline state constantly soluble in water, and then carry out polymerization, carry out so repeatedly; Finally make the aqueous solution of water-soluble fabulous polyacrylic salt; The polymerization degree of polymkeric substance is controlled with water-soluble chain transfer agent, and after polymerization was accomplished, free monomer radical was removed through the reaction heat in the reaction process.
That is to say; The present invention adopts single stage method to synthesize to gather (methyl) vinylformic acid (sodium, potassium, lithium) salt brine solution [followingly to be the convenient meter of narration; With " (methyl) vinylformic acid is represented methyl-prop diluted acid or vinylformic acid], this is different from the two step method described in the background technology in front.This technology is applicable to the synthetic of (methyl) vinylformic acid and multipolymer, water-soluble (methyl) propenoate and multipolymer thereof, (methyl) acrylate (sodium, potassium, lithium) aqueous solution.One-step synthesis process is with yellow soda ash, and salt of wormwood, the aqueous solution of Quilonum Retard etc. add at the bottom of the still earlier as one of reactant; Then water-soluble (methyl) propenoate and multipolymer thereof are added dropwise to the bottom, make it soon to be neutralized to (methyl) acrylate, have lower (methyl) acrylate of partial solubility to separate out with crystalline form earlier in the system; (methyl) acrylate that is dissolved in the water then carries out polymerization under action of evocating, it is soluble in water to gather (methyl) acrylate, along with the increase of the polymerization degree; Impel (methyl) acrylate of crystalline state constantly soluble in water; And then carry out polymerization, and carry out so repeatedly, finally can make water-soluble fabulous gathering (methyl) vinylformic acid (sodium; Potassium, lithium) aqueous solution.The polymerization degree of superpolymer can be controlled with water-soluble chain transfer agent.After polymerization was accomplished, free monomer radical can and add the oxidation reductive agent through reacting by heating and remove.Utilize the step-by-step polymerization of sodium acrylate salt brine solution to be easy to control molecular weight, heat release is even after the heat release, can control molecular weight preferably.
The advantage of above-mentioned one-step synthesis process is conspicuous:
1. low when liberated heat is than (methyl) acroleic acid polymerization in (methyl) vinylformic acid (sodium, potassium, lithium) polymerization process, and the solubleness of (methyl) vinylformic acid (sodium, potassium, lithium) in water is lower than (methyl) vinylformic acid.The former can be considered polymerization under lower concentration, and the latter carries out under higher concentration, and reaction is violent, and is wayward, and MWD is uneven.Otherwise the polymerization process of (methyl) vinylformic acid (sodium, potassium, lithium) is easy to control, even molecular weight distribution.
2. generate carbonic acid gas in (methyl) vinylformic acid and carbonic acid (sodium, potassium, the lithium) N-process; The gaseous volatilization process is an endothermic process, this process and (methyl) vinylformic acid (sodium, potassium; Lithium) the polymeric exothermic process is convenient to take away heat of polymerization when carrying out synchronously, and stable polymerization reaction is carried out.And all being better than use oxyhydroxide with the product colour outward appearance that carbonic acid (sodium, potassium, lithium) neutralization obtains neutralizes.
3. when (methyl) vinylformic acid rate of addition is very fast, can convert excessive (methyl) vinylformic acid (sodium, potassium, lithium) to crystal (methyl) vinylformic acid (sodium; Potassium, lithium), this can not increase water-soluble that part of (methyl) vinylformic acid (sodium, potassium; Lithium) concentration, when the polymerization degree increases, crystal (methyl) vinylformic acid (sodium; Potassium, lithium) can be dissolved because monomer concentration in the solution is not enough, thus play the effect of regulating polymerization velocity.
4. the notable attribute of single stage method is its technology mode, and having made full use of the great amount of heat energy that discharges in the reaction process comes the trigger monomer polymerization, and has simplified operation steps, has improved production efficiency, and this obviously is superior to two-step process.This method has reached energy saving purposes, is very suitable for industrial production.
Embodiment
With embodiment the present invention is further specified below, but the present invention is in no way limited to these embodiment.
Embodiment 1
Adopt the synthetic preparation of the inventive method sodium polymethacrylate aqueous solution dispersion agent, concrete reaction formula is:
In the following formula: n is the polymerization degree, gets n=23, Mw=2486 in this example.
The prescription that reaction is formed
Component (1) yellow soda ash 35.2g
Ammonium persulphate 0.55g
Deionized water 80g
Amount to 115.75g
Component (2) methylacrylic acid 57g
Inferior sodium phosphate 0.5g
Deionized water 5.5g
Amount to 60g
Device and operating process that this example is used are following:
Adorn controlled fast whisking appliance on the 500ml ground four-hole boiling flask, load onto TM, reflux condensing tube, constant pressure funnel on other each mouthfuls respectively.Component (1) is dropped in the reaction flask, begin to drip component (2) under stirring.Initial reaction stage, because of the sodium polymethacrylate salt that generates does not reach capacity, reaction solution is clear; When splashing into methylacrylic acid more for a long time, sodium methacrylate reaches hypersaturated state, and it is muddy that reaction solution is; Along with further carrying out of polyreaction; System is separated out sodium salt of methacrylic acid, is accompanied by a large amount of heat releases, discharges a large amount of dioxide gass simultaneously.Because of emitting of dioxide gas, temperature of reaction system is constant basically.After methylacrylic acid drips off, become clear, along with carbon dioxide releasing amount reduces gradually, system viscosity begins to increase to some extent.Specific as follows:
Reaction solution places 40 ℃ of baking ovens to react
Can know from this routine experimental result:
1. the inventive method is used for the methylacrylic acid polymerization, and it is very slowly steady that reaction is carried out, and is convenient to the controlled polymerization process, when arriving requirement of products viscosity (molecular weight), can make reaction terminating.
2. well-known, during two step method aqueous polymerization methylacrylic acid,, prepare polymethyl acrylic acid because the quick growth of its molecular weight can be separated out it very soon from aqueous phase, must in solvent, carry out, then neutralize again and remove solvent.The one-step technology that adopts the present invention to propose can be simplified synthesis technique.
3. the polymethyl acrylic acid high molecular free radical is longer in the low temperature aqueous phase survival time, utilizes its collision of radical slowly, makes that increasing molecular weight extremely is easy to control, and after reaching molecular weight, heating can be accomplished whole polymerization process rapidly.
4. polymethyl acrylic acid has lower wetting ability than ROHM, and its sodium-salt aqueous solution then solution viscosity than polyacrylic acid sodium salt is big.Its difference is that methyl is arranged on the main chain, and this makes it different with polyacrylic acid sodium salt on dispersing property.
Product specification
This routine sodium polymethacrylate salt brine solution dispersion agent application in the white titanium pigment water-based system:
Dispersing method: high speed dispersion (2000 rev/mins) 60 minutes
Dispersion results: system viscosity 75mPa.s, dispersion system do not have after following 7 days at 40 ℃ and sink to the bottom, and remain unchanged.
This routine sodium polymethacrylate salt brine solution dispersion agent dispersed kaolin in water-based system, talcum powder, the effect of light calcium carbonate:
Embodiment 2
According to the inventive method methylacrylic acid-vinylformic acid is carried out copolymerization, reaction formula is following:
N in the following formula
1, n
2Be the polymerization degree, when doing the dispersion agent use, n
1+ n
2Between 20～70, the polymerizable molecular amount is with n
1+ n
2=n and changing, if n value is one regularly, promptly molecular weight is when certain value, methylacrylic acid and vinylformic acid are transformable in the polymkeric substance at this moment, perhaps can suitably adjust n by performance requriements
1And n
2Value.It is 23 that this convention is decided the n value, and the calculating molecular weight of this moment is 2486.
This example prescription MA
0.1-AA
0.5630(methylacrylic acid and acrylic acid mol ratio are 0.1: 0.5630 in the prescription).
Schedule of operation:
2/3rds deionized water in the above-mentioned prescription is dropped in the reaction flask, stir and slowly add soda ash light down, all after the dissolving; Be cooled to 40 ℃, drop into ammonium persulphate, after the dissolving; Be cooled to 30 ℃; Begin to splash into methylacrylic acid, vinylformic acid, the mixing solutions of inferior sodium phosphate and remaining 1/3rd water.Reaction time of origin, temperature are starting point to begin dripping monomer.Reaction control is carried out at a lower temperature, to investigate the feasibility of temperature of reaction and technology of the present invention.
3.5 hours altogether, then put into 40 ℃ of thermostat containers, continue reaction.
Under temperature of reaction constant condition, still ceaselessly reacting to each other between the high molecular free radical in this reaction system, explain that under coldcondition, the inferior sodium phosphate chain transfer is not obvious.This is explanation just, but with the sodium-salt aqueous solution of the higher methylacrylic acid-PEMULEN TR2 of low-temp reaction synthetic molecular weight.
This example is used for the test that white titanium pigment disperses:
Dispersing method: high speed dispersion (2000 rev/mins) 60 minutes.
Dispersion results: system viscosity 66mPa.s, dispersion system is at 40 ℃ of viscosity no changes after following 7 days; The fineness no change; State is mobile, no sedimentation phenomenon.
Embodiment 3
In embodiment 1 and 2, owing to carry out polyreaction at low temperatures, radical fails to work with chain-transfer agent and disappear, so polymerization reaction system can be proceeded under 40 ℃ of conditions, molecular weight continues to increase.This example proposes a solution at this point: the first improves the temperature of reaction of system, impels high molecular free radical to work with chain-transfer agent, and molecular weight is no longer increased; Its two, when improving temperature of reaction, add redox agent radical disappeared, to keep the stable viscosity of final product.
This example is used MA
0.2-AA
0.4630Prescription (methylacrylic acid and acrylic acid mol ratio are 0.2: 0.4630 in the prescription) carries out the viscosity controller test:
Do two experiments with this prescription, first adopts low temperature (30 ℃～40 ℃ of normal temperature) condition, and second is carried out under 80 ℃ of comparatively high tempss.The working method of two real tests is with embodiment 2.
The result of test is:
Can know from reaction result: polymerized product at low temperatures, radical is not removed.Reaction is proceeded under 40 ℃, and system viscosity has bigger increase.After 80 ℃ were reacted down, system viscosity had increased when reaction finishes, and during 40 ℃ of storages, viscosity no longer increases.It is thus clear that, reaction system through 80 ℃ of processing after, viscosity increases very soon, but in when storage, system viscosity no longer increases and reaches stable.
Embodiment 4
Multipolymer according to acrylic acid synthesizing β hydroxypropyl acrylate of the present invention or ethyl ester and methylacrylic acid.
This example adopts the control method of embodiment 3, with improving controlling reaction temperature system viscosity and the chain transfer that improves chain-transfer agent.Investigate the suitability of the inventive method simultaneously to this kind system.
This routine overall structure is:
N in the following formula
1, n
2Be the polymerization degree,, require n as dispersion agent
1+ n
2=n is between n=20～70
This example is set n
1+ n
2=23.
Use HPA
0.02-MA
0.446Prescription carries out aggregation test, HPA content=6.3% (total solids meter).
The operating procedure process:
The part deionized water is dropped in the reaction flask, slowly add soda ash light, dissolution process heat release under stirring; After dissolving is accomplished; Be cooled to 80 ℃, beginning drips chain-transfer agent ortho phosphorous acid sodium water solution, the mixed solution of ammonium persulfate aqueous solution and Propylene glycol monoacrylate and methylacrylic acid simultaneously.The polymerization process heat release, temperature of reaction is controlled with temperature automatically controlled water-bath and material dropping speed jointly, reacts after about 3～4 hours and reaches required viscosity.Reaction is carried out 40 ℃ of thermal stability tests after accomplishing.
Test-results
Move in 40 ℃ of thermostatic chambers, investigate reaction system stability
| Time (hour) | Temperature (℃) | System viscosity |
| 144 | ?40 | 197mpa.s |
Carry out distributed test with this routine final product to the water-based white titanium pigment:
Dispersing method: high speed dispersion (2000 rev/mins) 60 minutes.
Test-results: system viscosity 147mpa.s;
40 ℃ of thermostabilitys: do not have sedimentation, caking, thickening phenomenon after 7 days.
Embodiment 5
Gather (methyl) potassium acrylate salt brine solution according to the inventive method is synthetic, this routine overall structure formula is:
In the following formula, n is the polymerization degree, gets 10,20,30,40,50 in this example.Synthetic compositing formula:
Schedule of operation:
The part deionized water is dropped in the reaction flask, slowly add salt of wormwood under stirring, the dissolution process heat release, dissolving is cooled to 80 ℃ after accomplishing, and beginning drips chain-transfer agent inferior sodium phosphate and acrylic acid aqueous solution, ammonium persulfate aqueous solution simultaneously.The dropping time is about 1 hour.Temperature of reaction is controlled with temperature automatically controlled water-bath and material dropping speed jointly, keeps 80 ℃, reacts about 3～4 hours.Cooling, discharging, viscosimetric.
Test-results:
Product solid content=40%; Viscosity 16mPa.s (40 ℃).
Above-mentioned product carries out the stably dispersing property testing:
Dispersing method: high speed dispersion (2000 rev/mins) 60 minutes.
Test-results: system viscosity 133mpa.s, system fineness 20 μ m;
40 ℃ of thermostabilitys: do not have sedimentation, caking, thickening phenomenon after 7 days.
Embodiment 6
According to the inventive method, synthesize and gather (methyl) vinylformic acid lithium aqueous solution, this routine structural formula is:
In the following formula: n is the polymerization degree, gets n=10,20,30,40,50 in this instance ... 100.
Synthetic compositing formula is following:
The part deionized water is dropped in the reaction flask, slowly add Quilonum Retard under stirring, the dissolution process heat release, dissolving is cooled to 80 ℃ after accomplishing, and beginning drips chain-transfer agent inferior sodium phosphate and acrylic acid aqueous solution, ammonium persulfate aqueous solution simultaneously.The dropping time is about 1 hour.Temperature of reaction is controlled with temperature automatically controlled water-bath and material dropping speed jointly, keeps 80 ℃, reacts about 3～4 hours.Cooling, discharging, viscosimetric.
Test-results:
Product solid content=40%; Viscosity 179mPa.s (40 ℃).
Above-mentioned product carries out the stably dispersing property testing:
Dispersing method: high speed dispersion (2000 rev/mins) 60 minutes.
Test-results: system viscosity 208mPa.s, system fineness 20 μ m;
40 ℃ of thermostabilitys: do not have sedimentation, caking, thickening phenomenon after 7 days.
Claims (6)
1. the preparation method of a polyelectrolyte for dispersing aqueous inorganic color stuffing is characterized in that, in weight percent, the synthesizing formula of this polymer electrolyte is formed and comprised:
Acrylic monomer 25～35%;
Inorganic carbonate 15～30%
Chain-transfer agent 0.1～5%;
Initiator 0.3～0.5%;
Solvent 40～50%
The polymerization degree n of described polymer electrolyte=10～70, and have one of following structure:
The polymerization degree is n=n in the following formula
1+ n
2
The preparation method of this polymer electrolyte adopts one-step synthesis process, be exactly the aqueous solution of inorganic carbonate is added still earlier as one of reactant at the bottom of, be added dropwise to the bottom to acrylic monomer; Make it soon to be neutralized to acrylate, have the lower acrylate of partial solubility to separate out with crystalline form earlier in the system, and the acrylate that is dissolved in the water carries out polymerization under action of evocating; Increase along with the polymerization degree; Impel the acrylate of crystalline state constantly soluble in water, and then carry out polymerization, carry out so repeatedly; Finally make the aqueous solution of water-soluble fabulous polyacrylic salt; The polymerization degree of polymkeric substance is controlled with water-soluble chain transfer agent, and after polymerization was accomplished, free monomer radical was removed through the reaction heat in the reaction process.
2. the preparation method of polyelectrolyte for dispersing aqueous inorganic color stuffing according to claim 1; It is characterized in that described acrylic monomer is to be selected from a kind of in methylacrylic acid, methylacrylic acid β hydroxyl ethyl ester, methylacrylic acid β hydroxypropyl acrylate, vinylformic acid, propenoic acid beta hydroxyl ethyl ester, propenoic acid beta hydroxypropyl acrylate, ethyl propenoate, the Jia Jibingxisuanyizhi or several combination.
3. the preparation method of polyelectrolyte for dispersing aqueous inorganic color stuffing according to claim 1 is characterized in that, described inorganic carbonate is yellow soda ash, salt of wormwood or Quilonum Retard.
4. the preparation method of polyelectrolyte for dispersing aqueous inorganic color stuffing according to claim 1; It is characterized in that described chain-transfer agent is selected from one or more in sodium sulfite anhy 96, Thiovanic acid, mercaptoethanol, mercaprol, inferior sodium phosphate, the ortho phosphorous acid.
5. the preparation method of polyelectrolyte for dispersing aqueous inorganic color stuffing according to claim 1 is characterized in that, described initiator is an ammonium persulphate.
6. the preparation method of polyelectrolyte for dispersing aqueous inorganic color stuffing according to claim 1 is characterized in that, described solvent is a deionized water.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085568A (en) * | 1992-10-14 | 1994-04-20 | 中国科学院长春应用化学研究所 | Preparation of low molecular weight water-soluble polymers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085568A (en) * | 1992-10-14 | 1994-04-20 | 中国科学院长春应用化学研究所 | Preparation of low molecular weight water-soluble polymers |
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