CN105566514B - Ternary integrated rubber emulsion condensation technique - Google Patents
Ternary integrated rubber emulsion condensation technique Download PDFInfo
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- CN105566514B CN105566514B CN201410528316.8A CN201410528316A CN105566514B CN 105566514 B CN105566514 B CN 105566514B CN 201410528316 A CN201410528316 A CN 201410528316A CN 105566514 B CN105566514 B CN 105566514B
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Abstract
The present invention relates to a kind of ternary integrated rubber emulsion condensation technique, belong to synthetic rubber technical field.Cohesion process of the present invention, it, with ternary integrated rubber latex as raw material, is cohesion mother liquor with ammonium sulfate solution with sulfuric acid as pH adjusting agent to be, the compound with poly-epoxychloropropane dimethylamine and cellulose derivative is as flocculating agent；Its step be to cohesion mother liquor in, first add flocculating agent, add raw material, be finally added thereto to pH adjusting agent and be condensed.The present invention uses compound flocculating agent, and the COD contents in production waste water can be reduced in the production of ternary integrated rubber；Compound flocculating agent is water-soluble preferably, can be applied in the range of pH wider；The particle of micelle is moderate after the completion of cohesion, and average grain diameter is 0.5 2cm, it is easy to dried；The present invention is cohesion mother liquor using the ammonium sulfate electrolyte of not metal ion, can prepare that metal ion content is low, the ternary integrated rubber small to metal protection.
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 ternary integrated rubber of emulsion polymerization is styrene, isoprene, three kinds of monomers of butadiene through free radical initiation
The polymer of emulsion copolymerization, the most important aspect of integrated rubber is that isoprene is incorporated into butadiene-styrene rubber, has it
There is the performance of part natural rubber.The cohesion process of ternary integrated rubber latex uses tradition cohesion in current emulsion polymerization
After the completion of technique, i.e. emulsion polymerization, the degassed unreacted raw material of removing, into cohesion unit, is added in condensing field
Flocculating agent is condensed, then, then through alkali cleaning, be dehydrated and dry after obtain ternary integrated rubber product.Cohesion process condition is：
50 DEG C -60 DEG C of condensation temperature, cohesion mother liquor is made with sodium-chloride water solution, and with sulfuric acid as pH adjusting agent, flocculating agent is polycyclic oxygen chlorine
Propane dimethylamine.
, there is following deficiency in the cohesion finishing process method of ternary integrated rubber emulsion of the prior art：
Coagel particle big (average grain diameter 2.5cm-4cm), drying is difficult, causes energy consumption, production cost to improve；Row
The COD (abbreviation COD) put in waste water is higher, and the integrated rubber of ternary prepared by cohesion mother liquor is made using sodium-chloride water solution
Glue metal ion content is high.
Patent CN103160056 discloses a kind of preparation of high performance butadiene-styrene-ispowder powder polymer
Method, including graft latex preparation and condensation powdering step, flocculant of the present invention be inorganic acid salt, flocculating agent is nothing
Machine acid.
Patent CN103724460 discloses a kind of cohesion process of nitrile rubber latex, and the invention is with Hydrin
Dimethylamine is flocculating agent, makees cohesion mother liquor with sodium-chloride water solution, with sulfuric acid as pH adjusting agent.
Patent CN103626924 discloses a kind of preparation method of liquid butadiene-acrylonitrrubber rubber with high nitrile content, including polymer system
Standby and emulsion condensation drying steps, add cellulose (methylcellulose or ethyl cellulose) in polymerization process.
Flocculant used or flocculating agent high, the perishable metal pattern that condenses the rubber-metal ion concentration in above patent
Tool.
From the point of view of current technical situation, the cohesion process for ternary integrated rubber latex is not disclosed in the prior art.
The content of the invention
It is an object of the invention to provide a kind of technique being condensed to ternary integrated rubber emulsion, micelle in flocculation process
Particle is moderate, and average grain diameter is 0.5-2cm, and drying time shortens, and reduces energy consumption, and it uses ammonium sulfate to do electrolyte, consumption
It is low and prepare the low ternary integrated rubber of metal ion content.
Ternary integrated rubber emulsion condensation technique of the present invention, is with ternary integrated rubber latex as raw material, with sulphur
Acid is pH adjusting agent, it is characterised in that：It is cohesion mother liquor with ammonium sulfate solution, with poly-epoxychloropropane dimethylamine and cellulose
The compound of derivative is flocculating agent；Its step be to cohesion mother liquor in, first add flocculating agent, add raw material, most it is backward its
Middle addition pH adjusting agent is condensed.
Described poly-epoxychloropropane dimethylamine and the compounding mass ratio of cellulose derivative are 90~98：10~2.
Described cellulose derivative is commercially available prod.It is preferred that lignin derivative, including acetyl lignin, methyl are wooden
Element, halogenation lignin, nitration of lignin etc..
Ammonium sulfate, flocculating agent, the mass ratio of raw material are 50~100 in described cohesion mother liquor：0.8~2：100, raw material with
The weight meter 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：
The weight portion of ammonium sulfate 50~100 accurately is weighed, is dissolved in 20 weight portion desalinations, deoxygenated water, be made into cohesion mother liquor,
It is standby；
2. the preparation of coagulant solution：
After the mass parts of poly-epoxychloropropane dimethylamine 90~98 are mixed with the mass parts of cellulose derivative 10~2, with de-
Salt, deoxygenated water are diluted to the solution of solid content 10%, standby；Poly-epoxychloropropane dimethylamine, cellulose derivative totally 100 mass
Part；
3. the preparation of raw material：
The ternary integrated rubber latex that will be equivalent to 100 weight portion dry glues is preheated to 50~60 DEG C, removes unconverted monomer；
4. the preparation of pH adjusting agent：
The sulfuric acid solution that weight percent concentration is 20% is prepared, it is standby；
5. the cohesion of latex：
Cohesion mother liquor that 1. step is prepared is added in condensing field, starts stirring, add that 2. step prepare containing 0.8~
The coagulant solution of 2 weight portion flocculating agents；3. then step removed the ternary integrated rubber latex after unconverted monomer average
It is divided into 5 parts, divides 5 times and be added in cohesion mother liquor, the sulfuric acid solution 4. prepared using step adjusts pH value 4.0~6.0, is condensed to
Micelle particle is uniform, slurries it is limpid untill, the micelle for will be coagulated and crosses 40 mesh sieves, drying, obtain ternary integrated rubber product.
The present invention can be recycled to the unconverted monomer for removing.
Beneficial effects of the present invention are as follows：
The present invention is that poly-epoxychloropropane dimethylamine and cellulose derivative compound using compound flocculating agent, in three metasets
The COD contents in production waste water can be reduced into rubber production, COD contents are between 210-280mg/L；Compound flocculating agent
It is water-soluble preferable, can be applied in the scope wider of pH3~10；The particle of micelle is moderate after the completion of cohesion, and average grain diameter is
0.5-2cm, it is easy to dry；The present invention is cohesion mother liquor using the ammonium sulfate electrolyte of not metal ion, can prepare metal
Ion concentration is low, the ternary integrated rubber small to metal protection.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
Treatment is condensed to ternary integrated rubber latex according to following processing step：
1. the preparation of mother liquor is condensed：
50 grams of ammonium sulfate accurately is weighed, is dissolved in 20 weight portion desalinations, deoxygenated water, be made into cohesion mother liquor, it is standby；
2. the preparation of coagulant solution：
After the mass parts of commercially available poly-epoxychloropropane dimethylamine 98 are mixed with the mass parts of methyl lignin 2.0, with desalination, take off
Oxygen water is diluted to the solution of solid content 10%, standby；
3. the preparation of raw material：
500 grams of the ternary integrated rubber latex equivalent to 100 grams of dry glues, solid content 20% is preheated to 55 DEG C, it is standby；
4. the preparation of pH adjusting agent：
The sulfuric acid solution that weight percent concentration is 20% is prepared, it is standby；
5. the cohesion of latex：
The cohesion mother liquor that 1. step is prepared is added in condensing field, starts stirring, and what 2. addition step was prepared contains 2 weight
The coagulant solution of part flocculating agent；3. then step removed the ternary integrated rubber latex after unconverted monomer and is divided into 5
Part, dividing 5 times and be added in cohesion mother liquor, the sulfuric acid solution 4. prepared using step adjusts pH value 4.0~6.0, is condensed to micelle
Particle is uniform, slurries it is limpid untill, the micelle for will be coagulated and crosses 40 mesh sieves, drying, obtain ternary integrated rubber product.
Process conditions are as follows：
The technical indicator that cohesion process reaches is as follows：
COD contents mg/L 268 in waste water
Coagel mean particle size cm 1.2
Embodiment 2-6
The step of according to embodiment 1, is condensed treatment, raw material proportioning and agglomeration process work to ternary integrated rubber latex
The technical indicator that skill reaches is listed in table 1.
The embodiment 2-6 raw material proportionings of table 1 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 weight portion containing flocculating agent | 1.5 | 1.2 | 1.0 | 0.9 | 0.8 |
| COD contents 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
Ternary integrated rubber latex is condensed according to following processing step：
1. the preparation of mother liquor is condensed：
200 grams of sodium chloride accurately is weighed, is dissolved in 20 weight portion desalinations, deoxygenated water, be made into cohesion mother liquor, it is standby；
2. the preparation of flocculating agent：
By poly-epoxychloropropane dimethylamine, the coagulant solution of solid content 10% is diluted to desalination, deoxygenated water, it is standby；
3. the preparation of raw material：
500 grams of the ternary integrated rubber latex equivalent to 100 grams of dry glues, solid content 20% is preheated to 55 DEG C, it is standby；
4. the preparation of pH adjusting agent：
The sulfuric acid solution that weight percent concentration is 20% is prepared, it is standby；
5. the cohesion of latex
The cohesion mother liquor that 1. step is prepared is added in condensing field, starts stirring, and the flocculating agent for adding step 2. to prepare is molten
Liquid 20ml；Then the ternary integrated rubber latex for 3. step being preheated is added for 5 times according to cohesion situation point, while in good time, in right amount
The sulfuric acid solution regulation pH value that 4. step is prepared is added, flocculating result is controlled, the micelle for will be coagulated and crossed 40 mesh sieves, drying, obtained
Product ternary integrated rubber.
Process conditions are as follows：
The technical indicator that agglomeration process technique reaches is as follows：
COD contents mg/L 357 in waste water
Coagel mean particle size mm 3.0
Comparative example 2-4
The step of according to comparative example 1, is condensed treatment, raw material proportioning and agglomeration process work to ternary integrated rubber latex
The technical indicator that skill reaches is listed in table 2：
The comparative example 2-4 raw material proportionings of table 2 and technical target of the product table
Claims (3)
1. a kind of ternary integrated rubber emulsion condensation technique, with ternary integrated rubber latex as raw material, with sulfuric acid as pH adjusting agent,
It is characterized in that：It is cohesion mother liquor with ammonium sulfate solution, with poly-epoxychloropropane dimethylamine and the compounding of cellulose derivative
Thing is flocculating agent；Its step be to cohesion mother liquor in, first add flocculating agent, add raw material, be finally added thereto to pH regulation
Agent is condensed；
The compounding mass ratio of poly-epoxychloropropane dimethylamine and cellulose derivative is 90~98：10~2；
Ammonium sulfate, flocculating agent, the mass ratio of raw material are 50~100 in cohesion mother liquor：0.8~2：100, raw material is with the integrated rubber of ternary
The weight meter of the dry glue of glue latex.
2. ternary integrated rubber emulsion condensation technique according to claim 1, it is characterised in that：Comprise the following steps：
1. the preparation of mother liquor is condensed：
The weight portion of ammonium sulfate 50~100 accurately is weighed, is dissolved in 20 weight portion desalinations, deoxygenated water, be made into cohesion mother liquor, it is standby
With；
2. the preparation of coagulant solution：
After the mass parts of poly-epoxychloropropane dimethylamine 90~98 are mixed with the mass parts of cellulose derivative 10~2, with desalination, take off
Oxygen water is diluted to the solution of solid content 10%, standby；Poly-epoxychloropropane dimethylamine, cellulose derivative totally 100 mass parts；
3. the preparation of raw material：
The ternary integrated rubber latex that will be equivalent to 100 weight portion dry glues is preheated to 50~60 DEG C, removes unconverted monomer；
4. the preparation of pH adjusting agent：
The sulfuric acid solution that weight percent concentration is 20% is prepared, it is standby；
5. the cohesion of latex：
The cohesion mother liquor that 1. step is prepared is added in condensing field, starts stirring, and what 2. addition step was prepared contains 0.8~2 weight
Measure the coagulant solution of part flocculating agent；3. then step removed the ternary integrated rubber latex after unconverted monomer to be divided into
5 parts, divide 5 times and be added in cohesion mother liquor, the sulfuric acid solution 4. prepared using step adjusts pH value 4.0~6.0, is condensed to micelle
Particle is uniform, slurries it is limpid untill, the micelle for will be coagulated and crosses 40 mesh sieves, drying, obtain ternary integrated rubber product.
3. ternary integrated rubber emulsion condensation technique according to claim 2, it is characterised in that：To the unpolymerized of removing
Monomer is recycled.
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| 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 |
| CN110431172B (en) * | 2017-03-28 | 2022-03-25 | 日本瑞翁株式会社 | Method for producing carboxyl group-containing nitrile rubber |
| 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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| US4001486A (en) * | 1975-06-11 | 1977-01-04 | Nalco Chemical Company | Latex coagulant for emulsion breakers |
| WO2006092898A1 (en) * | 2005-02-28 | 2006-09-08 | Kaneka Corporation | Process for producing coagulated latex particle |
| CN103539912B (en) * | 2012-07-12 | 2016-03-09 | 中国石油天然气股份有限公司 | A kind of preparation method of high-performance butadiene-styrene liquid rubber |
| CN103724460B (en) * | 2012-10-15 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of cohesion process of paracril latex |
| CN103319632B (en) * | 2013-06-27 | 2015-03-11 | 中昊晨光化工研究院有限公司 | Preparation method of powder rubber |
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