CN1250786A - Waste water recovering type process for synthesizing polyphenylamine series of polymers - Google Patents
Waste water recovering type process for synthesizing polyphenylamine series of polymers Download PDFInfo
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- CN1250786A CN1250786A CN 98121322 CN98121322A CN1250786A CN 1250786 A CN1250786 A CN 1250786A CN 98121322 CN98121322 CN 98121322 CN 98121322 A CN98121322 A CN 98121322A CN 1250786 A CN1250786 A CN 1250786A
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Abstract
The method for synthesizing polyaniline series polymer is to mix at first monomer, acid solution and oxidant allocated in the material preparing and through exothermic reaction to obtain granulated powder and waste water, separate by filtering, further neutralize the acidic powder with alkali liquor, and finally make it pass through filtering step again to remove water contained and further through baking and forming step to dry. When the prepn. method is cycled again, the waste water produced by previous prepn. and filtering step is recovered and repeatedly used in the materal preparing and mixing so as to lower consumption of acid solution; at same time, to remove acid solution by aid of waste water reuse, finally the produced powder possesses smaller grain size.
Description
The present invention relates to a kind of polyaniline synthetic method, particularly relate to a kind of waste water recovering type polyphenylamine series of polymers synthetic method.
As Fig. 1, shown in 2, fabrication steps in the past is the mixing step 11 of getting the raw materials ready in regular turn, filtration step 12, alkalinization step 13, refilter step 14 and drying forming step 15 etc., this mixing step 11 of getting the raw materials ready is the aniline with configuration, acid solution and oxygenant raw materials such as (as Ammonium Persulfate 98.5s), insert in the reactor 21 and mixed (reacting 2～3 hours), can be accompanied by emit (being thermopositive reaction) of heat in the reaction, because the thermopositive reaction meeting makes the some of mixing raw material generate other unwanted polymkeric substance, and lower required resultant output relatively, in order to solve the aforesaid drawbacks, outside this reactor 21, be provided with round-robin water coolant 22 again, to keep the thermopositive reaction temperature between 0～5 ℃, after the thermopositive reaction simultaneously, this reactor 21 can get granulous powder 16 and waste water 17, and its reaction formula is as follows:
As shown in Figure 1, 2, this filtration step 12 is waste water 17 and powder 16 that the mixing step 11 of getting the raw materials ready is produced, separated by filter (figure does not show), waste water 17 after the separation is discharged, this alkalinization step 13 is the neutralizations of being alkalized of powder 16 that filtration step is produced, and its reaction formula is:
This refilters step 14 is with contained moisture content in the alkalinization step 13 gained powder 16, filtered removal, this drying forming step 15 is dried the powder 16 of 14 gained after refiltering step, form the bigger electroconductive powder 16 of particle,, this electroconductive powder 16 forms lump because can linking mutually, therefore must grind to form powdery again, use to be further used as conductive material.
Though the electroconductive powder 16 of moulding can be used as the additive raw material of conductive material,
But, it has following shortcoming on manufacture method because of still having:
One, temperature is difficult for keeping, and is easy to generate by product:
Because each raw material can produce thermopositive reaction when mixing, it when produces heat release and the exothermic temperature situation can't accurately be controlled, therefore a mat water coolant comes the interior temperature maintenance of controlling reactor between 0～5 ℃, be difficult to stable to keep, and when temperature in a single day break away from 0～5 ℃ between, then generate other unwanted polymkeric substance (being by product) easily, and lower required powder output relatively.
Two, be easy to generate environmental issue:
Because aniline monomer contains toxic, though mixing with acid solution, mat aniline forms relevant acid solution, and the toxicity that the removal aniline monomer has, but because of the adding proportion of acid solution higher, therefore the waste water that the mixing step 11 of getting the raw materials ready is generated, wherein can contain unreacted acid solution completely, make and present acidity in the waste water and the incomplete color that responds, if with this direct discharging of waste water, the environmental issue of deriving easily, handled though but mat is provided with Waste Water Treatment, can be increased relevant equipment cost.
Three, particle is big:
In the past polyaniline synthetic method through the mixing step of getting the raw materials ready, filtration step, alkalinization step, refilter fabrication steps such as step, drying forming step after, the powder particle that it generated is bigger, therefore, this powder must be ground to certain for small particle size again when using, could become a conductive coating paint with solvent, otherwise the macrobead powder is not easy to mix with coating, increases the difficulty on making.
Certainly, in the aforementioned generation powder process, but mat adds suspension agent the powder of generation can not attracted each other, with elimination macrobead phenomenon, but the interpolation of suspension agent can increase cost, and in the powder suspension agent may residually be arranged.
Four, equipment cost height:
Except aforementioned second institute carries and need set up the Waste Water Treatment equipment, polyaniline synthetic method also need be provided with cooling water circulation equipment in the past, in reactor 21, react and maintain between 0～5 ℃ to keep raw materials such as aniline, acid solution and oxygenant, avoid other undesirable substance to be polymerized, therefore increased the expense cost of treatment of cooling water recycle unit.
Five, waste material:
Because when raw materials such as aniline, acid solution and oxygenant are mixed, its acid solution is failed fully and aniline reaction, causes partly that acid solution still residues in the waste water, after environmental protection equipment is handled, promptly discharge in outside, cause the waste of material.
The object of the present invention is to provide a kind of waste water recovering type polyphenylamine series of polymers synthetic method, and waste water reclamation can be reused,, have the effect that reduces expense cost and protect environment to avoid polluting simultaneously to improve the resultant quality.
The objective of the invention is to be achieved through the following technical solutions:
A kind of waste water recovering type polyphenylamine series of polymers synthetic method, its manufacturing method thereof mainly get the raw materials ready in regular turn mixing step, filtration step, alkalinization step, refilter step and drying forming step.The raw materials such as monomer, acid solution and oxygenant that this mixing step of getting the raw materials ready is about to earlier purchase are mixed according to certain weight ratio, carry out thermopositive reaction and handle, and can get granular powder and waste water by thermopositive reaction; The waste water that abovementioned steps produces can be separated through this filtration step; This alkalinization step is neutralized the tart powder that filtration step produces with alkali lye; After refiltering step through this more at last, further that the powder of gained after this alkalinization step is contained ingress filter is removed; This drying forming step is further dried powder forms electroconductive powder, therefore just finishes single circulation processing procedure.Be characterized in:
When circulating processing procedure once more, it is in the still recyclable and repeated use of waste water that this filtration step produces, and in the feasible processing procedure that circulates once more, its acid solution consumption reduces, to reduce expense cost.Simultaneously, in the waste water residual acid solution toxic substance, but also mat waste water is reused and with its removal, is avoided environmental pollution.And the powder diameter that utilizes the waste water repeated use to make also can be less.
In above-mentioned synthetic method, this mixing step of getting the raw materials ready is to handle under the normal temperature state, uses and reduces the product that thermopositive reaction produces.
In the above-mentioned synthetic method, oxygenant is persulphate, vitriol, iodate or chlorination metal-salt.
In the above-mentioned synthetic method, monomer is the alkyl benzene amine or the alcoxyl aniline of aniline or its aniline derivatives.
In the above-mentioned synthetic method, acid solution is hydrochloric acid, sulfuric acid, alkyl benzene sulphonate (ABS), Phenylsulfonic acid or alkylsurfuric acid.
In the above-mentioned synthetic method, the weight ratio of monomer, acid solution and oxygenant is 1: 10～25: 1～4.
Waste water recovering type polyphenylamine series of polymers synthetic method of the present invention is owing to take technique scheme, thereby has following advantage and effect:
One, no coupling product produces: waste water recovering type polyphenylamine series of polymers synthetic method of the present invention, because temperature of reaction need not be controlled between 0～5 ℃, therefore, when each raw material mixes or reacts, reaction is than being easier to control, simultaneously can be because of the exothermic temperature reactions change does not generate other unwanted polymkeric substance (being by product) yet, relatively, the powder output of its generation can not reduce yet.
Two, no environmental protection problem: because the alkyl benzene amine or the alcoxyl aniline of aniline or its aniline derivatives, and acid solution etc. all has relative toxicity, though therefore mat aniline (or the alkyl benzene amine of its aniline derivatives or alcoxyl aniline) mixes the formation aniline salt with acid solution, make toxicity that each monomer had reach the purpose of removal, but but higher because of the adding proportion of acid solution, therefore in the waste water that the mixing step 31 of getting the raw materials ready is generated, still contain suitable unreacted hydrochloric acid soln completely, make and present acidity and color state is arranged in the waste water, but, the present invention is when waste water is reused again, the hydrochloric acid soln that is contained in the waste water still can react with the monomer that new processing procedure is added, until the acid solution approach exhaustion, even therefore directly discharging after processing procedure is finished, can not produce environmental issue yet, can reduce the processing of environment-protection wastewater thus yet.
Three, equipment cost is low: because manufacturing method thereof need be kept temperature of reaction between 0～5 ℃ in the past, to avoid the generation of other low-molecular weight polymer, therefore processing procedure need be set up Waste Water Treatment equipment in the past, and also need be provided with the treatment of cooling water recycle unit, temperature maintenance when in reactor, carrying out thermopositive reaction to keep raw materials such as monomer, acid solution and oxygenant, on the contrary, manufacturing method thereof of the present invention, it at room temperature can react, so the cooling apparatus that need not be correlated with, so can reduce manufacturing cost.
Four, particle is little: the present invention is through the mixing step 31 of getting the raw materials ready, filtration step 32, alkalinization step 33, after refiltering fabrication steps such as step 34 and drying forming step 35, what it generated is the bigger powder of particle diameter, but, when aforementioned each step circulation time once more, the waste water that utilizes this filtration step 32 to produce can reclaim repeated use again, the powder diameter of its gained is littler than powder diameter in the past, therefore, if when making an addition in the coating as addition material, be easy to make and be evenly distributed and be not easy sedimentary conductive coating paint with solvent, more increase follow-up interpolation blended easiness, and spray the simplicity of loading onto.
Five, save material: when being mixed because of raw materials such as monomer, acid solution and oxygenants, its acid solution is also failed complete reaction, therefore partly acid solution can residue in the waste water, and waste water is to take to reclaim to reuse in the present invention, so the ratio regular meeting that the consumption of acid solution is added in each processing procedure is along with reduction, therefore, the present invention can reach the purpose of saving material and cost at the not further effectively utilization of acid solution of complete reaction.
The present invention is described in detail below in conjunction with drawings and Examples:
Fig. 1 is polyaniline processing flow figure in the past.
Fig. 2 is the mixing step processing procedure synoptic diagram of getting the raw materials ready of polyaniline in the past.
Fig. 3 is the schema of preferred embodiment of the present invention.
Fig. 4～7th, the thermal stability test chart of preferred embodiment of the present invention.
Fig. 8 is that the infrared spectrum of preferred embodiment of the present invention is measured chart.
As shown in Figure 3, waste water recovering type polyphenylamine series of polymers synthetic method of the present invention comprises the mixing step 31 of getting the raw materials ready, filtration step 32, alkalinization step 33, refilters step 34 and drying forming step 35, this mixing step 31 of getting the raw materials ready is to purchase raw materials such as monomer, acid solution and oxygenant in advance, this monomer can be the alkyl benzene amine or the alcoxyl aniline of aniline or its aniline derivatives, and oxygenant can be persulphate, vitriol, iodized salt or iron(ic) chloride etc.In addition, again raw materials such as aforesaid monomer, acid solution and oxygenant are added in room temperature in the reactor (figure do not show) and react,, can get the granulous powder and contain not the complete reaction waste water 37 of acid solution completely by thermopositive reaction.This filtration step 32 is separated waste water 37 and powder 36 that the mixing step 31 of getting the raw materials ready is produced, waste water 37 after the separation can re-use in circulation processing procedure next time, re-uses the mixing step 31 of getting the raw materials ready in the processing procedure that next time circulates after just this waste water 37 reclaims.This mode can reduce the acid solution consumption and reduce cost, simultaneously also can be with the not monomer of complete reaction removal in the waste water 37.This alkalinization step 33 is with filtration step 32 acid powders that produces 36, by the alkali lye neutralization of being alkalized; This refilters step 34 is contained moisture content in the powder with alkalinization step 33 gained, is filtered removal; And this drying forming step 35 is dried the powder 36 that refilters step 34 back gained, forms the less electroconductive powder 36 of particle diameter.
Be the reusable feasibility of proof waste water, and the electroconductive powder of its generation also has preferable speciality, by following description of test as can be known:
Processing procedure for the first time:
The mixing step 31 of getting the raw materials ready of this experimental example is prepared monomer (is example with aniline), acid solution (example hydrochloric acid, sulfuric acid, alkyl benzene sulphonate (ABS), Phenylsulfonic acid or alkylsurfuric acid) and oxygenant raw materials such as (as Ammonium Persulfate 98.5s) in advance, its weight ratio is: 1: 10～25: 1～4, and at room temperature the reaction times is 0.5～4 hour.Reaction procedure is as follows: and after thermopositive reaction generates granular powder 36 and waste water 37, more in regular turn through follow-up waste water 37 and powder 36 isolating filtration steps 32, with powder acidic solution neutral alkalinization step 33 (its neutral reaction formula is as follows:
Where R is H ,-(CH
2)
nCH
3Or-O (CH
2)
nCH
3. n is 0,1, or 2.), refiltered step 34 with what the moisture content of powder 36 further removed, and the drying forming step 35 of at last powder 36 being dried etc., just can get electroconductive powder 36 for use, and powder 36 particle diameters of aforementioned processing procedure gained are bigger, the electroconductive powder 36 of aforementioned generation is after the test of TGA thermotolerance, its temperature is lost curve as shown in Figure 4, and with after its electroconductive powder 36 process infrared spectrums (FTIR) mensuration, its spectrogram is shown in the I among Fig. 8.
The processing procedure second time that waste water recycles:
The waste water 37 of aforementioned processing procedure gained is reclaimed repeated use once more, just this waste water 37 adds in the mixing step 31 of getting the raw materials ready, because still contain the not acid solution of complete reaction in this waste water 37, so aniline, acid solution and oxygenant raw materials of purchasing at this mixing step 31 of getting the raw materials ready such as (as Ammonium Persulfate 98.5s), the interpolation weight of its acid solution will be low than the processing procedure first time, and keep at room temperature that the reaction times is 0.5～4 hour.Again according to filtration step 32, the alkalinization step 33 of processing procedure for the first time, refilter step 34 and drying forming step 35, just can generate less electroconductive powder 36 for use.Moreover, the electroconductive powder 36 that is generated after TGA thermotolerance test, its calorific loss curve as shown in Figure 5, and with this electroconductive powder 36 through behind infrared spectrum analysises, its spectrogram is shown in the II among Fig. 8.
The processing procedure for the third time that waste water recycles:
The 100 processing procedure that waste water recycles:
Will last time waste water 37 that processing procedure is produced reclaim and use, the interpolation weight of its acid solution can comparatively reduce, while in its following reaction times of room temperature (0.5～4 hour), and follow-up filtration step 32, alkalinization step 33, to refilter step 34 and drying forming step 35 etc. all identical, and electroconductive powder 36 particle diameters that generate can be little than preceding first procedure also, and after the electroconductive powder 36 that generates is tested through the TGA thermotolerance, its testing wire as shown in Figure 7, and with after these electroconductive powder 36 process infrared spectrums (FTIR) analyses, its spectrogram is shown in the IV among Fig. 8.
Sustainable n time of the waste water access times of this processing procedure, and the processing procedure of previous experiments example is only so that the 100 processing procedure is example.
Via the processing procedure of the foregoing description as can be known, the mixing step 31 of getting the raw materials ready of waste water recovering type polyphenylamine series of polymers synthetic method of the present invention, raw materials such as its aniline of purchasing, acid solution and oxygenant, its weight ratio is: 1: 10～25: 1～4, and at room temperature the reaction times is 0.5～4 hour, last more in regular turn through follow-up filtration step 32, alkalinization step 33, refilter step 34 and drying forming step 35 etc., go out than the littler electroconductive powder 36 of the particle diameter of polyaniline synthetic method gained in the past for use with regard to plastic.In addition,, reduce the acid solution addition of successive process, therefore can imitate consumption and the expense cost that reduces material because the waste water 37 of this manufacturing method thereof after filtration step 32 separates can constantly be reused again.
Particularly, by the result who tests the powder 36 process TGA thermotolerances tests that generate as can be known, this electroconductive powder 36 can be subjected to the influence of heat, the weight of this powder 36 is alleviated because of ardentization, by the calorific loss curve of Fig. 4～7 as can be known, the temperature-averaging that its weight begins to alleviate is on about 370 ℃, and this proof utilizes waste water 37 to reuse the powder 36 of manufacturings, is not subjected to repeatedly processing procedure and influences original heat-resistant quality.In addition, show that shown in I, the II of Fig. 8, spectral line such as III, IV, its characteristic crest is constant, therefore proves that this powder 36 has identical chemical property with infrared spectrum (FTIR) analytical results.So, by the test of aforesaid thermotolerance and infrared spectrum analysis result as can be known, utilize the method for waste water 37 repeated application in processing procedure, can't influence the characteristic of its powder, on the contrary, its powder of making 36 particles are littler, also can use as the interpolation of other material.
Claims (6)
1. a waste water recovering type polyphenylamine series of polymers synthetic method comprises the mixing step of getting the raw materials ready, filtration step, alkalinization step, refilters step and drying forming step; This mixing step of getting the raw materials ready is to purchase raw materials such as monomer, acid solution and oxygenant in advance, and each raw material is mixed, and carries out thermopositive reaction and handles, to reflect granular powder and waste water; This filtration step is separated waste water and powder that the mixing step of getting the raw materials ready produces; This alkalinization step is alkalized the powder that filtration step produces, and the acid-reaction that powder is is neutralized; This refilters step is contained moisture content in the powder with gained after the alkalinization step, is filtered removal again; This drying forming step is dried refiltering after the step powder of gained, forms electroconductive powder; It is characterized in that:
Aforementioned each step is circulation time once more, and the waste water that its filtration step produces can reclaim repeated use again, and the acid solution addition of the mixing step of getting the raw materials ready of the feasible processing procedure that circulates once more reduces, and simultaneously the toxic substance in the waste water is removed.
2. waste water recovering type polyphenylamine series of polymers synthetic method as claimed in claim 1, it is characterized in that: this mixing step of getting the raw materials ready is to handle under the normal temperature state, uses and reduces the product that thermopositive reaction produces.
3. waste water recovering type polyphenylamine series of polymers synthetic method as claimed in claim 1 is characterized in that: this oxygenant is persulphate, vitriol, iodate or chlorination metal-salt.
4. waste water recovering type polyphenylamine series of polymers synthetic method as claimed in claim 1 is characterized in that: this monomer is the alkyl benzene amine or the alcoxyl aniline of aniline or its aniline derivatives.
5. waste water recovering type polyphenylamine series of polymers synthetic method as claimed in claim 1, it is characterized in that: this acid solution is hydrochloric acid, sulfuric acid, alkyl benzene sulphonate (ABS), Phenylsulfonic acid or alkylsurfuric acid.
6. waste water recovering type polyphenylamine series of polymers synthetic method as claimed in claim 1, it is characterized in that: the weight ratio of this monomer, acid solution and oxygenant is 1: 10～25: 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121322 CN1250786A (en) | 1998-10-09 | 1998-10-09 | Waste water recovering type process for synthesizing polyphenylamine series of polymers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121322 CN1250786A (en) | 1998-10-09 | 1998-10-09 | Waste water recovering type process for synthesizing polyphenylamine series of polymers |
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|---|---|
| CN1250786A true CN1250786A (en) | 2000-04-19 |
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| CN 98121322 Pending CN1250786A (en) | 1998-10-09 | 1998-10-09 | Waste water recovering type process for synthesizing polyphenylamine series of polymers |
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1998
- 1998-10-09 CN CN 98121322 patent/CN1250786A/en active Pending
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