CN105566514A - Ternary integrated rubber latex agglomeration process - Google Patents
Ternary integrated rubber latex agglomeration process Download PDFInfo
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- CN105566514A CN105566514A CN201410528316.8A CN201410528316A CN105566514A CN 105566514 A CN105566514 A CN 105566514A CN 201410528316 A CN201410528316 A CN 201410528316A CN 105566514 A CN105566514 A CN 105566514A
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Abstract
The present invention relates to a ternary integrated rubber latex agglomeration process, and belongs to the technical field of synthetic rubbers. According to the agglomeration process, a ternary integrated rubber latex is adopted as a raw material, sulfuric acid is adopted as a pH value adjusting agent, an ammonium sulfate aqueous solution is adopted as an agglomeration mother liquor, and a poly epichlorohydrin-dimethylamine and cellulose derivative complex is adopted as an agglomeration agent; and the steps comprise: adding the agglomeration agent to the agglomeration mother liquor, adding the raw material, adding the pH value adjusting agent, and carrying out agglomeration. According to the present invention, the composite agglomeration agent is used, such that the COD content in the production wastewater can be reduced during the ternary integrated rubber production; the composite agglomeration agent has good water solubility, and can be used within a wide pH value range; the particle size of the colloidal particles after the agglomeration is moderate, the average particle size is 0.5-2 cm, and the drying is easily achieved; and the metal-ion-free ammonium sulfate electrolyte is adopted as the agglomeration mother liquor, such that the ternary integrated rubber with characteristics of low metal ion content and low corrosion on metals can be produced.
Description
Technical field
The present invention relates to a kind of ternary integrated rubber emulsion condensation technique, belong to synthetic rubber technical field.
Background technology
The polymkeric substance of the emulsion copolymerization that the ternary integrated rubber of letex polymerization is vinylbenzene, isoprene, divinyl three kinds of monomers cause through free radical, the most important aspect of integrated rubber is incorporated in styrene-butadiene rubber(SBR) by isoprene, makes it have the performance of part natural rubber.The cohesion process of ternary integrated rubber latex uses traditional cohesion process in current letex polymerization, namely after emulsion polymerization completes, unreacted raw material is removed through degassed, enter cohesion unit, in condensing field, add flocculation agent condense, then, then after alkali cleaning, dehydration also drying obtain ternary integrated rubber product.Cohesion process condition is: condensation temperature 50 DEG C-60 DEG C, and make cohesion mother liquor with sodium chloride aqueous solution, take sulfuric acid as pH adjusting agent, flocculation agent is poly-epoxychloropropane dimethylamine.
The cohesion finishing process method of ternary integrated rubber emulsion of the prior art, exists following not enough:
Coagel particle large (median size 2.5cm-4cm), not easily drying, cause production energy consumption, production cost to improve; Chemical oxygen demand (COD) (being called for short COD) in waste discharge is higher, and the ternary integrated rubber metal ion content using sodium chloride aqueous solution do cohesion mother liquor to prepare is high.
Patent CN103160056 discloses a kind of preparation method of high performance butadiene-styrene-ispowder powder polymer, and comprise preparation and the condensation powdering step of graft latex, flocculation agent of the present invention is inorganic acid salt, and flocculation agent is mineral acid.
Patent CN103724460 discloses a kind of cohesion process of paracril latex, and this invention take poly-epoxychloropropane dimethylamine as flocculation agent, and making cohesion mother liquor with sodium chloride aqueous solution, take sulfuric acid as pH adjusting agent.
Patent CN103626924 discloses a kind of preparation method of liquid butadiene-acrylonitrrubber rubber with high nitrile content, comprises polymkeric substance preparation and emulsion condensation drying step, adds Mierocrystalline cellulose (methylcellulose gum or ethyl cellulose) in polymerization process.
It is high that flocculation agent used in above patent or flocculation agent condense the rubber-metal ion content, perishable metal die.
From current technical situation, the not open cohesion process for ternary integrated rubber latex in prior art.
Summary of the invention
The object of this invention is to provide a kind of technique that ternary integrated rubber emulsion is condensed, in flocculation process, micelle particle is moderate, median size is 0.5-2cm, time of drying shortens, reduce energy consumption, it adopts ammonium sulfate to do ionogen, and consumption is low and prepare the low ternary integrated rubber of metal ion content.
Ternary integrated rubber emulsion condensation technique of the present invention, for raw material with ternary integrated rubber latex, be pH adjusting agent with sulfuric acid, it is characterized in that: take ammonium sulfate solution as cohesion mother liquor, with the compound of poly-epoxychloropropane dimethylamine and derivatived cellulose for flocculation agent; Its step is in cohesion mother liquor, first adds flocculation agent, then adds raw material, finally add pH adjusting agent wherein and condense.
The composite mass ratio of described poly-epoxychloropropane dimethylamine and derivatived cellulose is 90 ~ 98:10 ~ 2.
Described derivatived cellulose is commercially available prod.Preferred lignin derivative, comprises acetyl xylogen, methyl xylogen, halogenation xylogen, nitration of lignin etc.
In described cohesion mother liquor, the mass ratio of ammonium sulfate, flocculation agent, raw material is 50 ~ 100:0.8 ~ 2:100, and raw material is with the weighing scale of the dry glue of ternary integrated rubber latex.
Described ternary integrated rubber emulsion condensation technique, comprises the following steps:
1. the preparation of mother liquor is condensed:
Accurately take ammonium sulfate 50 ~ 100 weight part, be dissolved in 20 weight part desalinations, de-oxygenised water, be made into cohesion mother liquor, for subsequent use;
2. the preparation of coagulant solution:
After poly-epoxychloropropane dimethylamine 90 ~ 98 mass parts being mixed with derivatived cellulose 10 ~ 2 mass parts, be diluted to the solution of solid content 10% with desalination, de-oxygenised water, for subsequent use; Poly-epoxychloropropane dimethylamine, derivatived cellulose be totally 100 mass parts;
3. the preparation of raw material:
The ternary integrated rubber latex being equivalent to the dry glue of 100 weight part is preheated to 50 ~ 60 DEG C, removes unconverted monomer;
4. the preparation of pH adjusting agent:
Preparation weight percent concentration is the sulphuric acid soln of 20%, for subsequent use;
5. the cohesion of latex:
Cohesion mother liquor step 1. prepared adds in condensing field, starts and stirs, and adds the coagulant solution containing 0.8 ~ 2 weight part flocculation agent that 2. step is prepared; Then 3. step is removed the ternary integrated rubber latex after unconverted monomer and be divided into 5 parts, divide and join for 5 times in cohesion mother liquor, adopt the sulphuric acid soln adjust ph 4.0 ~ 6.0 that 4. step is prepared, be condensed to micelle uniform particles, slurries limpid till, crossing 40 mesh sieves, drying by coagulating the micelle, obtaining ternary integrated rubber product.
The present invention can recycle the unconverted monomer removed.
Beneficial effect of the present invention is as follows:
The present invention uses compound flocculation agent and poly-epoxychloropropane dimethylamine and derivatived cellulose composite, and can reduce the COD content in factory effluent in ternary integrated rubber is produced, COD content is between 210-280mg/L; Compound flocculation agent is better water-soluble, can apply in the scope that pH3 ~ 10 are wider; The particle having condensed rear micelle is moderate, and median size is 0.5-2cm, is easy to dry; The present invention uses the ammonium sulfate ionogen of not metal ion for cohesion mother liquor, can prepare metal ion content low, the ternary integrated rubber little to metal protection.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
According to following processing step, agglomeration process is carried out to ternary integrated rubber latex:
1. the preparation of mother liquor is condensed:
Accurately take 50 grams, ammonium sulfate, be dissolved in 20 weight part desalinations, de-oxygenised water, be made into cohesion mother liquor, for subsequent use;
2. the preparation of coagulant solution:
After commercially available poly-epoxychloropropane dimethylamine 98 mass parts being mixed with methyl xylogen 2.0 mass parts, be diluted to the solution of solid content 10% with desalination, de-oxygenised water, for subsequent use;
3. the preparation of raw material:
Being equivalent to 100 grams of dry glue, 500 grams, the ternary integrated rubber latex of solid content 20% is preheated to 55 DEG C, for subsequent use;
4. the preparation of pH adjusting agent:
Preparation weight percent concentration is the sulphuric acid soln of 20%, for subsequent use;
5. the cohesion of latex:
Cohesion mother liquor step 1. prepared adds in condensing field, starts and stirs, and adds the coagulant solution containing 2 weight part flocculation agent that 2. step is prepared; Then 3. step is removed the ternary integrated rubber latex after unconverted monomer and be divided into 5 parts, divide and join for 5 times in cohesion mother liquor, adopt the sulphuric acid soln adjust ph 4.0 ~ 6.0 that 4. step is prepared, be condensed to micelle uniform particles, slurries limpid till, crossing 40 mesh sieves, drying by coagulating the micelle, obtaining ternary integrated rubber product.
Processing condition are as follows:
The technical indicator that cohesion process reaches is as follows:
COD content mg/L268 in waste water
Coagel mean particle size cm1.2
Embodiment 2-6
Carry out agglomeration process according to the step of embodiment 1 to ternary integrated rubber latex, the technical indicator that proportioning raw materials and agglomeration process technique reach lists in table 1.
Table 1 embodiment 2-6 proportioning raw materials and technical target of the product table
| Project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Latex solid content, % | 20 | 21 | 22 | 23 | 24 |
| Ammonium sulfate, g | 60 | 70 | 80 | 90 | 100 |
| Coagulant solution is containing flocculation agent weight part | 1.5 | 1.2 | 1.0 | 0.9 | 0.8 |
| COD content in waste water, mg/L | 265 | 220 | 270 | 242 | 257 |
| Coagel mean particle size, cm | 0.8 | 1.0 | 1.5 | 1.3 | 1.8 |
Comparative example 1
According to following processing step, ternary integrated rubber latex is condensed:
1. the preparation of mother liquor is condensed:
Accurately take 200 grams, sodium-chlor, be dissolved in 20 weight part desalinations, de-oxygenised water, be made into cohesion mother liquor, for subsequent use;
2. the preparation of flocculation agent:
By poly-epoxychloropropane dimethylamine, be diluted to the coagulant solution of solid content 10% with desalination, de-oxygenised water, for subsequent use;
3. the preparation of raw material:
Being equivalent to 100 grams of dry glue, 500 grams, the ternary integrated rubber latex of solid content 20% is preheated to 55 DEG C, for subsequent use;
4. the preparation of pH adjusting agent:
Preparation weight percent concentration is the sulphuric acid soln of 20%, for subsequent use;
5. the cohesion of latex
Cohesion mother liquor step 1. prepared adds in condensing field, starts and stirs, add the coagulant solution 20ml that 2. step is prepared; Then by step 3. the ternary integrated rubber latex of preheating divide 5 times according to cohesion situation to add, add the sulphuric acid soln adjust ph that 4. step is prepared in good time, in right amount simultaneously, control flocculating result, crossing 40 mesh sieves, drying by coagulating the micelle, obtaining product ternary integrated rubber.
Processing condition are as follows:
The technical indicator that agglomeration process technique reaches is as follows:
COD content mg/L357 in waste water
Coagel mean particle size mm3.0
Comparative example 2-4
Carry out agglomeration process according to the step of comparative example 1 to ternary integrated rubber latex, the technical indicator that proportioning raw materials and agglomeration process technique reach lists in table 2:
Table 2 comparative example 2-4 proportioning raw materials and technical target of the product table
Claims (5)
1. a ternary integrated rubber emulsion condensation technique, with ternary integrated rubber latex for raw material, be pH adjusting agent with sulfuric acid, it is characterized in that: take ammonium sulfate solution as cohesion mother liquor, with the compound of poly-epoxychloropropane dimethylamine and derivatived cellulose for flocculation agent; Its step is in cohesion mother liquor, first adds flocculation agent, then adds raw material, finally add pH adjusting agent wherein and condense.
2. ternary integrated rubber emulsion condensation technique according to claim 1, is characterized in that: the composite mass ratio of poly-epoxychloropropane dimethylamine and derivatived cellulose is 90 ~ 98:10 ~ 2.
3. ternary integrated rubber emulsion condensation technique according to claim 1, is characterized in that: in cohesion mother liquor, the mass ratio of ammonium sulfate, flocculation agent, raw material is 50 ~ 100:0.8 ~ 2:100, and raw material is with the weighing scale of the dry glue of ternary integrated rubber latex.
4., according to the arbitrary described ternary integrated rubber emulsion condensation technique of claim 1-3, it is characterized in that: comprise the following steps:
1. the preparation of mother liquor is condensed:
Accurately take ammonium sulfate 50 ~ 100 weight part, be dissolved in 20 weight part desalinations, de-oxygenised water, be made into cohesion mother liquor, for subsequent use;
2. the preparation of coagulant solution:
After poly-epoxychloropropane dimethylamine 90 ~ 98 mass parts being mixed with derivatived cellulose 10 ~ 2 mass parts, be diluted to the solution of solid content 10% with desalination, de-oxygenised water, for subsequent use; Poly-epoxychloropropane dimethylamine, derivatived cellulose be totally 100 mass parts;
3. the preparation of raw material:
The ternary integrated rubber latex being equivalent to the dry glue of 100 weight part is preheated to 50 ~ 60 DEG C, removes unconverted monomer;
4. the preparation of pH adjusting agent:
Preparation weight percent concentration is the sulphuric acid soln of 20%, for subsequent use;
5. the cohesion of latex:
Cohesion mother liquor step 1. prepared adds in condensing field, starts and stirs, and adds the coagulant solution containing 0.8 ~ 2 weight part flocculation agent that 2. step is prepared; Then 3. step is removed the ternary integrated rubber latex after unconverted monomer and be divided into 5 parts, divide and join for 5 times in cohesion mother liquor, adopt the sulphuric acid soln adjust ph 4.0 ~ 6.0 that 4. step is prepared, be condensed to micelle uniform particles, slurries limpid till, crossing 40 mesh sieves, drying by coagulating the micelle, obtaining ternary integrated rubber product.
5. ternary integrated rubber emulsion condensation technique according to claim 4, is characterized in that: recycle the unconverted monomer removed.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459687A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of wide temperature zone high damping nano-rubber composite and preparation method thereof |
| CN107973385A (en) * | 2017-11-27 | 2018-05-01 | 吉林市正凡工贸有限公司 | Environment-friendly type flocculant and preparation method thereof |
| CN110431172A (en) * | 2017-03-28 | 2019-11-08 | 日本瑞翁株式会社 | The manufacturing method of the nitrile rubber containing carboxyl |
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| US4001486A (en) * | 1975-06-11 | 1977-01-04 | Nalco Chemical Company | Latex coagulant for emulsion breakers |
| CN101128517A (en) * | 2005-02-28 | 2008-02-20 | 株式会社钟化 | Process for producing coagulated latex particle |
| CN103319632A (en) * | 2013-06-27 | 2013-09-25 | 中昊晨光化工研究院有限公司 | Preparation method of powder rubber |
| CN103539912A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Preparation method of high-performance butadiene-styrene liquid rubber |
| CN103724460A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Nitrile butadiene rubber latex coagulation technology |
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2014
- 2014-10-09 CN CN201410528316.8A patent/CN105566514B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001486A (en) * | 1975-06-11 | 1977-01-04 | Nalco Chemical Company | Latex coagulant for emulsion breakers |
| CN101128517A (en) * | 2005-02-28 | 2008-02-20 | 株式会社钟化 | Process for producing coagulated latex particle |
| CN103539912A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Preparation method of high-performance butadiene-styrene liquid rubber |
| CN103724460A (en) * | 2012-10-15 | 2014-04-16 | 中国石油化工股份有限公司 | Nitrile butadiene rubber latex coagulation technology |
| CN103319632A (en) * | 2013-06-27 | 2013-09-25 | 中昊晨光化工研究院有限公司 | Preparation method of powder rubber |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459687A (en) * | 2016-06-06 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of wide temperature zone high damping nano-rubber composite and preparation method thereof |
| CN107459687B (en) * | 2016-06-06 | 2020-04-14 | 中国石油化工股份有限公司 | Wide-temperature-range high-damping nano rubber composite material and preparation method thereof |
| CN110431172A (en) * | 2017-03-28 | 2019-11-08 | 日本瑞翁株式会社 | The manufacturing method of the nitrile rubber containing carboxyl |
| EP3604397A4 (en) * | 2017-03-28 | 2020-11-18 | Zeon Corporation | Method for producing carboxyl-group-containing nitrile rubber |
| CN110431172B (en) * | 2017-03-28 | 2022-03-25 | 日本瑞翁株式会社 | Method for producing carboxyl group-containing nitrile rubber |
| CN107973385A (en) * | 2017-11-27 | 2018-05-01 | 吉林市正凡工贸有限公司 | Environment-friendly type flocculant and preparation method thereof |
| CN107973385B (en) * | 2017-11-27 | 2020-12-29 | 吉林市正凡工贸有限公司 | Environment-friendly flocculating agent and preparation method thereof |
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