CN103819582B - The preparation method of polymerized emulsion - Google Patents
The preparation method of polymerized emulsion Download PDFInfo
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- CN103819582B CN103819582B CN201410037729.6A CN201410037729A CN103819582B CN 103819582 B CN103819582 B CN 103819582B CN 201410037729 A CN201410037729 A CN 201410037729A CN 103819582 B CN103819582 B CN 103819582B
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Abstract
The invention discloses a kind of preparation method of polymerized emulsion, it comprises the steps: that S1. adds water in the first reaction vessel, and in the second reaction vessel, input table surface-active agent and some monomers, carry out pre-emulsification; S2. provide initiator, part initiator is mixed with described pre-emulsion, and mixed solution is added drop-wise in the first reaction vessel, then add remaining initiator in the first reaction vessel, obtain polymerized emulsion; S3. water-soluble solvent is joined in polymerized emulsion, pre-treatment is carried out to it; S4. sorbent material is joined in described mixing solutions, fully stir, the sorbent material removing then will added.The preparation method of polymerized emulsion of the present invention does not need the condition changing reaction, can guarantee that emulsion completes reaction with steady state, can not produce the problem that emulsion stability is destroyed.In addition, the preparation method of polymerized emulsion of the present invention also need not react for impelling residual monomer, and adds redox agent, causes the increase of impurity in emulsion.
Description
Technical field
The present invention relates to a kind of preparation method, particularly relate to a kind of preparation method of polymerized emulsion.
Background technology
Utilize the monomers such as vinylbenzene, vinyl acetate between to for plastic, vinyl cyanide can obtain the emulsion of being polymerized in an aqueous medium in the mode of emulsion polymerization, this emulsion can be widely used in the field such as coating, glue paste.But in emulsion preparation process, usually have fail react monomer residue in emulsion.When utilizing the emulsion remaining monomer to be coated with, the glue paste of coating can give off a peculiar smell, and like this, not only can pollute, but also can jeopardize the healthy of people work, living environment.
At present, the method for residual monomer in emulsion of removing has: (1) is by changing reaction conditions, reaction parameter, adding the chemical process of catalyzer etc.; (2) physical method that water vapour distills is passed into above-mentioned emulsion.
Wherein, chemical process needs to improve temperature of reaction, and add redox agent and carry out pressure reaction, the stability of this method on emulsion has impact, and the catalyzer added cannot be separated thus cause the decline of emulsion property, and the final residue monomer concentration of emulsion cannot be controlled at below 500ppm.Physical method then needs to pass into high-temperature vapor, heats and carry out wet distillation in outside, disperses stability to have a significant impact, causes emulsion to connect skin, particles aggregate gel to emulsion particle in water.So not only operability is poor, and resin emulsion solid content decline poor yields after process.
Therefore, the preparation method of the polymerized emulsion that a kind of improvement is provided is necessary for the problems referred to above.
Summary of the invention
In view of this, the invention provides a kind of preparation method of polymerized emulsion.
To achieve these goals, the preparation method of polymerized emulsion of the present invention comprises:
S1. in the first reaction vessel, add water, and heat up, in the second reaction vessel, input table surface-active agent and some monomers, carry out pre-emulsification, forms pre-emulsion;
S2., the aqueous solution of initiator is provided, the aqueous solution of part initiator is mixed with described pre-emulsion, form mixed solution, and mixed solution is added drop-wise in the first reaction vessel, in the first reaction vessel, add the aqueous solution of remaining initiator after dropwising again, obtain the polymerized emulsion containing residual monomer;
S3. water-soluble solvent water solubility being at least 10% joins in the polymerized emulsion in S2, carries out pre-treatment to polymerized emulsion, and polymerized emulsion and water-soluble solvent form mixing solutions;
S4. joined in described mixing solutions by sorbent material, fully stir, the sorbent material removing then will added, obtains final polymerized emulsion.
As a further improvement on the present invention, the mass ratio of described water-soluble solvent and polymerized emulsion is 1% ~ 10%.
As a further improvement on the present invention, the mass ratio of described sorbent material and polymerized emulsion is 0.5% ~ 10%.
As a further improvement on the present invention, the pre-treatment that described water-soluble solvent carries out is slot type process or continous way process.
As a further improvement on the present invention, the described pretreated time is at least 0.5h.
As a further improvement on the present invention, described sorbent material is gac, diatomite, silicate or aluminate.
As a further improvement on the present invention, when described sorbent material is gac, the particle diameter of described gac is less than 0.1mm.
As a further improvement on the present invention, the method removing sorbent material is filter type or centrifugation mode.
As a further improvement on the present invention, when the method for described removing sorbent material is filter type, in diatomite filtration layer, diatomaceous particle size range is: 50 ~ 1000 μm.
As a further improvement on the present invention, when the method for described removing sorbent material is filter type, in diatomite filtration layer, diatomaceous particle size range is: 100 ~ 400 μm.
Compared with prior art, the invention has the beneficial effects as follows: the preparation method of polymerized emulsion of the present invention does not need to change the condition of reaction, can guarantee that emulsion completes reaction with steady state, can not produce the problem that emulsion stability is destroyed.In addition, the preparation method of polymerized emulsion of the present invention also need not react for impelling residual monomer, and adds redox agent, causes the increase of impurity in emulsion.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, the accompanying drawing that the following describes is only some embodiments recorded in the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the method flow schematic diagram of preparation method one embodiment of polymerized emulsion of the present invention.
Embodiment
As shown in Figure 1, the present invention discloses a kind of preparation method of polymerized emulsion, and this preparation method comprises the steps:
S1. in the first reaction vessel, add water, and heat up, in the second reaction vessel, input table surface-active agent and some monomers, carry out pre-emulsification, forms pre-emulsion.
In present embodiment, can use and be equipped with stirring rake, condenser, the flask of dropwise adding tank is as the container reacted, thus the bottle of flask forms the first reaction vessel, and dropwise adding tank forms the second reaction vessel.When preparing polymerized emulsion, in flask, add 600 parts of water, be warming up to 80 DEG C.In dropwise adding tank, add 300 parts, water again, Sodium dodecylbenzene sulfonate 43 parts, methyl methacrylate 150 parts, butyl acrylate 500 parts, vinylbenzene 340 parts, methacrylic acid 10 parts carry out pre-emulsification, form pre-emulsion.
S2., the aqueous solution of initiator is provided, the aqueous solution of part initiator is mixed with described pre-emulsion, form mixed solution, and mixed solution is added drop-wise in the first reaction vessel, in the first reaction vessel, add the aqueous solution of remaining initiator after dropwising again, obtain the polymerized emulsion containing residual monomer.
Particularly, described initiator can be ammonium persulphate.When ammonium persulphate mixes with pre-emulsion, first, be that the ammonium persulphate of 5% mixes with pre-emulsion by the mass ratio of 60 parts, the mixed solution of formation was at the uniform velocity added drop-wise in flask in 4 hours.And then by the mass ratio of 40 parts be 5% ammonium persulphate join in flask, slaking 1 hour, obtaining solid content is 50%(mass parts) ACRYLIC EMULSION.
S3. water-soluble solvent water solubility being at least 10% joins in the polymerized emulsion in S2, carries out pre-treatment to polymerized emulsion, and polymerized emulsion and water-soluble solvent form mixing solutions.Wherein, the pretreated time is at least 0.5h, during pre-treatment, can carry out at normal temperatures, also can carry out in a heated condition.
S4. joined in described mixing solutions by sorbent material, fully stir, the sorbent material removing then will added, obtains final polymerized emulsion.
Wherein, described sorbent material is gac, diatomite, silicate or aluminate.Preferably, described sorbent material is gac, and now, described gac is the active carbon powder that particle diameter is less than 0.1mm, compares granular carbon, and the surface-area of Powdered Activated Carbon is large, so rate of adsorption is fast, efficiency is high, effective.When carrying out adsorption treatment, can carry out at normal temperatures, also can carry out in a heated condition.During heating, warm temperature is as the criterion, preferably more than 60 DEG C to be no more than 80 DEG C.Because easily there is skinning more than 80 DEG C of emulsions, be unfavorable for production operation.
It should be noted that, above-mentionedly utilize water-soluble solvent to carry out pretreated object to polymerized emulsion to be, because residual monomer is esters of acrylic acid or Tri-n-butyltin methacrylate, it mostly is high hydrophobic oleophilic oil material, according to octanol water partition coefficient in emulsion, most residual monomer is arranged in emulsion particle, but not is present in aqueous phase, when direct use sorbent material adsorbs, solid-liquid can not directly contact, and adsorption effect is not bery desirable.And after adding water-soluble solvent, residual monomer can be drawn in solvent phase, sorbent material and solvent contacts, greatly, adsorption effect improves greatly for the residual monomer in solvent and adsorbent contact probability.
Particularly, the mass ratio of described water-soluble solvent and polymerized emulsion is 1% ~ 10%, and wherein, when the usage quantity of water-soluble solvent is less than 1%, then bad to the effect of residual monomer extraction, when being greater than 10%, then the stability of emulsion declines.In addition, the pre-treatment that described water-soluble solvent carries out is slot type process or continous way process.Wherein, described slot type is treated to: after adding all resins emulsion that need process in a kettle., required sorbent material is added this reactor, stir process removes sorbent material after the scheduled time, by emulsion discharging, is generally used for process in a small amount; What is called is treated to continuously: sorbent material is made adsorption tower, and the resin emulsion that need process feeds to adsorption tower one end, and the adsorption tower the other end then discharges the emulsion handled well, until sorbent material lost efficacy or to predetermined duration of service, was generally used for a large amount of process.When for single-channel type process, the treatment time is more than 0.5 hour, is preferably more than 1.0 hours.When for continous way process, the treatment time is more than 0.5 hour, is preferably more than 1.0 hours.
The mass ratio of described sorbent material and polymerized emulsion is 0.5% ~ 10%.Wherein, when the consumption of described sorbent material is less than 0.5%, then adsorption effect not rationality, when the consumption of described sorbent material is greater than 10%, then economy is poor.
Further, the method for above-mentioned removing sorbent material is filter type or centrifugation mode.When the method for described removing sorbent material is filter type, in diatomite filtration layer, diatomaceous particle size range is: 50 ~ 1000 μm, is preferably 100 ~ 400 μm.When adopting centrifugation mode, select rotating speed according to centrifugal radius, be separated into standard not affect the stable of emulsion particle.
Below in conjunction with several specific embodiment, S3 step in the preparation method of polymerized emulsion of the present invention and S4 step are illustrated.
Embodiment 1
In the present embodiment, corresponding to S3, S4 step, polymerized emulsion is ACRYLIC EMULSION, and water-soluble solvent is ethanol, the active carbon powder of sorbent material to be model be " too pavilion K " (manufacture of futamura society).
In the 100g ACRYLIC EMULSION prepared, add ethanol 1g mixing 1h, carry out pre-treatment, then dropping into model be the active carbon powder 1g of " too pavilion K ", stirs after 0.5 hour, adds pressure filtration after the diatomite 5g of 50 μm, removes gac.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Embodiment 2
In the present embodiment, corresponding to S3, S4 step, polymerized emulsion is ACRYLIC EMULSION, and water-soluble solvent is ethanol, the sorbent material active carbon powder that to be model be " too pavilion K ".
In the 100g ACRYLIC EMULSION prepared, add ethanol 10g mixing 1h, carry out pre-treatment, then dropping into model be the active carbon powder 1g of " too pavilion K ", stirs after 0.5 hour, adds pressure filtration after the diatomite 5g of 100 μm, removes gac.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Embodiment 3
In the present embodiment, corresponding to S3, S4 step, polymerized emulsion is ACRYLIC EMULSION, and water-soluble solvent is ethanol, the sorbent material active carbon powder that to be model be " too pavilion K ".
In the 100g ACRYLIC EMULSION prepared, add ethanol 10g mix 1 hour, carry out pre-treatment, then dropping into model be the active carbon powder 10g of " too pavilion K ", stirs after 0.5 hour, adds pressure filtration after the diatomite 5g of 400 μm, removes gac.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Embodiment 4
In the present embodiment, corresponding to S3, S4 step, polymerized emulsion is ACRYLIC EMULSION, and water-soluble solvent is ethanol, the active carbon powder of sorbent material to be model be " egression WH2CK " (manufacture of JEChem society).
To in the 100g ACRYLIC EMULSION prepared, add ethanol 10g and mix 1 hour, carry out pre-treatment, then drop into the active carbon powder 1g that model is " egression WH2C ", stir after 3 hours, use whizzer to be removed by granular carbon.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Embodiment 5
In the present embodiment, corresponding to S3, S4 step, polymerized emulsion is ACRYLIC EMULSION, and water-soluble solvent is acetone, the sorbent material active carbon powder that to be model be " too pavilion K ".
To in the 100g ACRYLIC EMULSION prepared, add acetone 10g and mix 1 hour, carry out pre-treatment, then dropping into model be the active carbon powder 1g of " too pavilion K ", stirs after 0.5 hour, adds pressure filtration after the diatomite 5g of 1000 μm, removes gac.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Below in conjunction with comparative example, comparative illustration is carried out to the beneficial effect of preparation method of the present invention.
Comparative example 1
To the 1000g ACRYLIC EMULSION prepared, be 65 DEG C in temperature, under pressure is 20kPa, pass into steam treatment 3 hours with the speed of 500g/h.Then residual butyl acrylate and cinnamic concentration is tested with GC.
Comparative example 2
To in the 100g ACRYLIC EMULSION prepared, dropping into model is the active carbon powder 1g of " too pavilion K ", stirs after 0.5 hour, adds pressure filtration after the diatomite 5g of 100 μm, eliminates gac.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
Comparative example 3
To in the 100g ACRYLIC EMULSION prepared, drop into the active carbon powder 1g that model is " egression WH2C ", stir after 3 hours, use whizzer to be removed by granular carbon.The emulsion GC of removing gac tests residual butyl acrylate and cinnamic concentration.
In the various embodiments described above and comparative example, GC is utilized to test the result of residual butyl acrylate and cinnamic concentration as shown in table 1 below:
Table 1
Thus, as can be seen from Table 1, the preparation method of polymerized emulsion of the present invention extracts out residual monomer in emulsion in advance by using water-soluble solvent, and utilize sorbent material to adsorb further, good effect is achieved to removing residual monomer, make levels of residual monomers in the polymerized emulsion of preparation maintain lower level, compare traditional method, there is larger advantage.
In sum: the preparation method of polymerized emulsion of the present invention does not need the condition changing reaction, can guarantee that emulsion completes reaction with steady state, can not produce the problem that emulsion stability is destroyed.In addition, the preparation method of polymerized emulsion of the present invention also need not react for impelling residual monomer, and adds redox agent, causes the increase of impurity in emulsion.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.Any Reference numeral in claim should be considered as the claim involved by limiting.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through suitable conjunction, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (8)
1. a preparation method for polymerized emulsion, is characterized in that, the preparation method of described polymerized emulsion comprises the steps:
S1. in the first reaction vessel, add water, and heat up, in the second reaction vessel, input table surface-active agent and some monomers, carry out pre-emulsification, forms pre-emulsion;
S2., the aqueous solution of initiator is provided, the aqueous solution of part initiator is mixed with described pre-emulsion, form mixed solution, and mixed solution is added drop-wise in the first reaction vessel, in the first reaction vessel, add the aqueous solution of remaining initiator after dropwising again, obtain the polymerized emulsion containing residual monomer;
S3. water-soluble solvent water solubility being at least 10% joins in the polymerized emulsion in S2, pre-treatment is carried out to polymerized emulsion, polymerized emulsion and water-soluble solvent form mixing solutions, and wherein, the mass ratio of described water-soluble solvent and polymerized emulsion is 1% ~ 10%;
S4. joined in described mixing solutions by sorbent material, fully stir, the sorbent material removing then will added, obtain final polymerized emulsion, wherein, the mass ratio of described sorbent material and polymerized emulsion is 0.5% ~ 10%.
2. the preparation method of polymerized emulsion according to claim 1, is characterized in that, the pre-treatment that described water-soluble solvent carries out is slot type process or continous way process.
3. the preparation method of polymerized emulsion according to claim 2, is characterized in that, the described pretreated time is at least 0.5h.
4. the preparation method of polymerized emulsion according to claim 1, is characterized in that, described sorbent material is gac, diatomite, silicate or aluminate.
5. the preparation method of polymerized emulsion according to claim 1, is characterized in that, when described sorbent material is gac, the particle diameter of described gac is less than 0.1mm.
6. the preparation method of polymerized emulsion according to claim 1, is characterized in that, the method for removing sorbent material is filter type or centrifugation mode.
7. the preparation method of polymerized emulsion according to claim 6, is characterized in that, when the method for described removing sorbent material is filter type, in diatomite filtration layer, diatomaceous particle size range is: 50 ~ 1000 μm.
8. the preparation method of polymerized emulsion according to claim 7, is characterized in that, when the method for described removing sorbent material is filter type, in diatomite filtration layer, diatomaceous particle size range is: 100 ~ 400 μm.
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Patent Citations (6)
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| US4151141A (en) * | 1977-11-16 | 1979-04-24 | The Dow Chemical Company | Process for continuously removing volatile organic material from aqueous dispersions of synthetic polymers |
| US5498693A (en) * | 1994-09-26 | 1996-03-12 | The Goodyear Tire & Rubber Company | Method of reducing the residual unsaturated monomer content of an aqueous dispersion of a saturated polymer |
| US5886140A (en) * | 1997-01-30 | 1999-03-23 | Centro De Investigacion Y Desarollo Technologico S.A. De C.V. | Chemical depletion process to substantially remove residual monomers in emulsion polimerization processes |
| CN1333297A (en) * | 1999-10-19 | 2002-01-30 | 阿托菲纳公司 | Electrochemistry method for removing residue monomer in emulsoid |
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| CN202509010U (en) * | 2012-02-15 | 2012-10-31 | 泉州德立化工有限公司 | Simple degassing treatment system for reaction kettle |
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