CN100366652C - Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber - Google Patents
Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber Download PDFInfo
- Publication number
- CN100366652C CN100366652C CNB2006100168173A CN200610016817A CN100366652C CN 100366652 C CN100366652 C CN 100366652C CN B2006100168173 A CNB2006100168173 A CN B2006100168173A CN 200610016817 A CN200610016817 A CN 200610016817A CN 100366652 C CN100366652 C CN 100366652C
- Authority
- CN
- China
- Prior art keywords
- tetraacetic acid
- ethylenediamine tetraacetic
- edta
- reaction
- weight percentage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a preparation method for a composite ferrum sodium salt activating agent prepared from styrene butadiene rubber (SBR). The preparation method comprises: ethylenediamine tetraacetic acid is stirred, and is added to a sodium hydroxide solution with the concentration of 15 to 30% at a temperature of 40 to 60 DEG C, wherein the weight proportion of the ethylenediamine tetraacetic acid to sodium hydroxide is 0.8:0.5 to 1.0:0.7; when the ethylenediamine tetraacetic acid is totally converted into ethylenediamine tetraacetic acid tetrasodium salts, a ferric trichloride solution with the concentration of 40 to 60% is dripped into the ethylenediamine tetraacetic acid tetrasodium salts during stirring the ethylenediamine tetraacetic acid tetrasodium salts, wherein the weight proportion of the ethylenediamine tetraacetic acid to ferric trichloride is 0.8:0.3 to 1.0:0.5, and a complex reaction temperature is from 50 to 80 DEG C; after the dripping of the ferric trichloride is stopped, the reaction is continued for 3 to 5 hours; a pH value of the system is maintained to 3 to 4 by a Na2CO3 water solution with the concentration of 2 to 5%; after the reaction ends, the materials are cooled; when a temperature of the materials is lower than 30 DEG C, stirring is stopped; after the materials are sedimentated for two days, mother liquor is drawn out for post treatment. A product is obtained, wherein a pH value of the product is from 6.6 to 7.6, the EDTA content is more than or equal to 74.0%, and the Fe content is more than or equal to 12%.
Description
Technical field
The present invention relates to used activation system in the styrene-butadiene rubber(SBR) production, relate in particular to and substitute in the styrene-butadiene rubber(SBR) production preparation method of the composite ferric sodium salt of the activation system that used tetrasodium salt of EDTA, ferrous sulfate constitute.
Background technology
Styrene-butadiene rubber(SBR) (SBR is as follows) device adopts tetrasodium salt of EDTA, ferrous sulfate (EDTA4Na-FeSO
4, as follows) and be activation system.This is the production technology that former Jiization organic synthesis factory (organic synthesis factory of existing Jilin Petrochemical branch office) the seventies is introduced from Japan.This production technique that falls behind has been brought activator preparation trouble, and polymerization rate is slow, shortcomings such as raw material consumption height.The SBR device that builds up after China's the eighties (Qilu Petrochemical rubber plant, Nantong rubber plant) all adopts iron edta sodium salt (EDTANaFe, as follows) activation system.EDTA4Na-FeSO
4In the activation system, EDTA exists in the system with the complexing ion state, and ferrous ion is maintained the optimum concn that can discharge radical under alkaline condition as iron in the complexing agent protection prescription; And EDTANaFe itself can make iron exist with the complexing ion form in emulsion, can guarantee concentration (State of Zhao's light, Jiization organic synthesis factory, national synthetic rubber annual meeting the tenth secondary annual meeting collected works: 349,1995) of spike all the time.Therefore, EDTANaFe is better than the EDTA4Na-FeSO activation system keeping on steadily the carrying out of polyreaction, and can simplify operational process of craft.But Jiization SBR device can not directly use with the EDTANaFe of market sale, and its major cause is that Jiization SBR device activator needs preparation separately and storage, and the activation system of domestic other rubber devices then adopts on-line mixing.Another kind of independently use or insert the commodity counterfeit prevention inquiry system that uses in arbitrary communication network system in China Mobile and the CHINAUNICOM, it is characterized in that: this system by gateway server, database server and on interface L, the internet that connects with wireless network and the joining short message servers of human consumer's mobile phone, by router and fireproof brickwork that SIM is housed dispose and form; Above-mentioned gateway server respectively with, SIM is housed realize wired the connection with wireless network and the joining short message servers of human consumer's mobile phone, database server, internet configuration; And database server is realized wired the connection by the interface L on it with the database of commodity production producer.
Client's mobile phone connects with short message servers by wireless network.
The commodity counterfeit prevention inquiry system must set up goods in transit on their own with storage and prevent that the goods in transit database of false code connects realization work operation." SIM " by buying mobile telecommunication service company realized dock with the mobile telecommunication service network as the component of inserting in the short message servers, and the acquisition client inquires about the reception and the answer designated lane of news in brief." SIM " quantity depends on the needs.
The commodity counterfeit prevention inquiry system is according to commodity producers' actual needs, adopt dedicated system software (windows2000, the sql-server etc.) control of on-the-spot establishment, finish the retrieval authentication that client inquires about commercial product code, and in advance set two kinds of hommization response to query instructions of "Yes" or "No" (as Welcome my company's product, please relieved use.Or the commodity of purchasing are not that my company makes, and please require the dealer to change or the return of goods etc.) in, make unique correct selection, answer is made in client's inquiry.Also to and make the regressive while in the response to query instruction of selected "Yes", with the commercial product code of this inquiry from the above-mentioned composite ferric sodium salt main reaction formula of data:
Product the key technical indexes that the present invention makes and check and application result see Table 1
Table 1. product the key technical indexes and check and application result
| Project name | Index | Assay | |
| Test sample | The big product of producing | ||
| Outward appearance | Pale yellow powder | Pale yellow powder | Pale yellow powder |
| 1% aqueous solution state | Transparent | Transparent | Transparent |
| 1% aqueous solution pH | 6.6-7.6 | 7.1 | 7.0 |
| Loss on drying wt% | ≤11 | 2 | 2 |
| EDTA wt％ | ≥74.0 | 74.8 | 75.1 |
| Iron level wt% | ＞12 | 12 | 12 |
The iron edta sodium salt (EDTANaFe) that bright market sale has been levied in small test and big production application test can not substitute original EDTA4Na-FeSO on Ji SBR device
4Activation system.Test-results shows that the EDTANaFe of market sale slows down in late phase reaction speed, the activator muddiness, its reason is that commercially available ferrisodium salt brine solution is acidity, and the another kind of auxiliary agent Diao Bai piece of preparation activator is extremely unstable in acidic medium, produces toxic gases such as formaldehyde, hydrogen sulfide during decomposition.The present invention is exactly that the composite ferric sodium salt of the special use of developing according to the production characteristics of Ji SBR substitutes EDTA4Na-FeSO
4Activation system, thus former SBR activation system improved.We have designed complexing amount and the system pH of strict control iron on parent in reaction process for this reason.Through test and technology adjustment repeatedly, determined processing condition, develop the composite ferric sodium salt that satisfies Jiization SBR production technique.
During Jiization SBR produces, with composite ferric sodium salt of the present invention and former EDTA4Na-FeSO
4Activation system has carried out the contrast experiment:
After finishing synthetic and application test research of the present invention, at pilot plant, the qualified product of producing have in the first batch carried out big production application test on Ji SBR production line, and its application method and former big controlling of production process index are basic identical.SBR1500 in 10 days the process of the test
#, SBR1502
#Every index all meets top grade product specification.The polymerization rate and the activator storage case of different activation systems see Table 2.
The polymerization rate of the different activation systems of table 2. and activator storage case
| Activation system | Polymerization rate | The activator storage case | |||
| Time (h) | Transformation efficiency % | Time (h) | Outward appearance | Reducing power | |
| EDTA4Na-FeSO 4 | 4 | 27.26 | 4 | Transparent | 28.26 |
| 6 | 47.09 | 6 | Transparent | 28.35 | |
| 8 | 58.91 | 8 | Transparent | 27.22 | |
| During termination (8.5) | 60.13 | 12 | Transparent | 26.32 | |
| EDTANaFe | 4 | 29.72 | 4 | Transparent | 26.32 |
| 6 | 47.25 | 6 | Transparent | 25.26 | |
| 8 | 55.70 | 8 | Muddy | 21.09 | |
| During termination (9.0) | 59.02 | 10 | Muddy, the S flavor arranged | 26.32 | |
| Composite ferric sodium salt | 4 | 28.37 | 4 | Transparent | 29.03 |
| 6 | 48.21 | 6 | Transparent | 28.97 | |
| 8 | 59.33 | 8 | Transparent | 28.25 | |
| During termination (8.3) | 62.35 | 12 | Transparent | 27.20 | |
Illustrate: 1. 8.5 ± 0.5 hours polymerisation conversions of SBR production requirement reach 62 ± .0%;
2. the activator of configuration requires not decompose in 12 hours (clarification, no S flavor), reducing power＞25.
Composite ferric sodium salt and EDTA4Na-FeSO
4The finished product glue assay that system is produced sees Table 3:
Table 3. invention system and EDTA4Na-FeSO
4The finished product glue assay that system is produced
| Project | Index (top grade product) | EDTA4Na-FeSO 4System | Composite ferric sodium salt | |||
| May 3 | May 4 | May 9 | May 10 | May 11 | ||
| Volatile matter %≤ | 0.75 | 0.50 | 0.34 | 0.42 | 0.34 | 0.22 |
| Total percent of ash %≤ | 0.75 | 0.11 | 0.11 | 0.13 | 0.13 | 0.13 |
| Organic acid % | 4.50-6.75 | 6.13 | 6.16 | 6.02 | 6.02 | 5.89 |
| Soap %≤ | 0.50 | 0.01 | 0.02 | 0.01 | 0.01 | 0.01 |
| Combined styrene % | 22.5-24.5 | 23.1 | 22.8 | 23.4 | 23.4 | 23.4 |
| Mooney viscosity ML | 45-55 | 49 | 52 | 49 | 51 | 51 |
| Mixing Mooney ML≤ | 90 | 77 | 79 | 78 | 80 | 78 |
| Tensile strength Mpa (145 ℃ of X35min) | 23.7 | 26.7 | 25.1 | 25.1 | 25.9 | 26.9 |
| 145 ℃ * 35min of 300% stress at definite elongation MPa 25min 50mi n | 11.3-15.8 14.1-18.6 14.9-19.4 | 14.5 17.0 18.8 | 15.4 18.0 19.2 | 13.9 16.2 18.2 | 14.0 16.4 18.4 | 13.1 16.2 18.2 |
| Tensile yield % 〉=(145 ℃ of X35min) | 415 | 461 | 453 | 435 | 475 | 469 |
The present invention compared with prior art has significant technical progress and positive effect:
Same EDTA4Na-FeSO
4System is compared, and uses composite ferric sodium salt of the present invention to alleviate the labour intensity of shop floor worker widely, and easy technological operation has reduced activator level, has reduced production cost.Polymerization rate is obviously faster than EDTA4Na-FeSO
4System has reduced metal ion simultaneously and has entered polymerization system.
Calculate by producing 140000 tons of styrene-butadiene rubber(SBR) per year, can reduce about 1,420,000 yuan of raw materials cost every year;
Embodiment
Now by embodiment, the present invention is further described as follows:
Embodiment 1 (prior art)
Existing typical iron edta sodium salt (EDTANaFe is at present commercially available) synthesis technique:
Taking by weighing 56 gram disodium EDTAs, at room temperature is 15% aqueous sodium hydroxide solution neutralization with 85 gram weight percentage compositions, makes it to dissolve fully, and its pH value of solution value is controlled at 8～10.Again this solution is poured in 500 milliliters the there-necked flask that has whipping appts, be warming up to 60 ± 5 ℃, get weight percentage and be 45% ferric chloride aqueous solutions 85 grams, dropwise join in the above-mentioned there-necked flask with separating funnel, complex reaction begins, and along with the carrying out of reaction, the color of system is by the dark red yellow-green colour that progressively becomes, when pH was 1～2, solution began to occur crystallization.After iron trichloride drips, under above-mentioned temperature of reaction, continue reaction 3 hours; Behind the stopped reaction, again through settlement separate, wash to pH3～4, dehydration, after 100～120 ℃ of dryings, promptly obtain iron edta sodium salt product (yield 70%).Its product the key technical indexes is as shown in table 4 below:
The key technical indexes of the EDTANaFe of table 4. the present invention preparation
| Project name | Index | Assay |
| Outward appearance | Light yellow crystalline powder | Light yellow crystalline powder |
| 5% aqueous solution state | Transparent | Transparent |
| 5% aqueous solution pH | 4.0～5.0 | 4.1 |
| Loss on drying wt% | ≤11 | 7 |
| EDTAwt％ | ≥74.0 | 74.3 |
| Fewt％ | ≥14.7 | 14.9 |
Embodiment 2 (the present invention controls the complexing amount of iron in complex reaction)
Taking by weighing 49 gram ethylenediamine tetraacetic acid (EDTA)s, at room temperature is 25% aqueous sodium hydroxide solution 86 gram neutralizations with weight percentage, makes it to dissolve fully, and pH value of solution is controlled at 8～10.Solution is poured in 500 milliliters of there-necked flasks that have whipping appts, be warming up to 60 ± 5 ℃, get weight percentage and be 45% ferric chloride aqueous solutions 70 grams, dropwise join in the above-mentioned there-necked flask with separating funnel, complex reaction begins, along with the reaction carrying out, the color in the system by dark red progressively become pale red, when pH is 2, solution begins to occur crystallization, after iron trichloride drips, under above-mentioned temperature of reaction, continue reaction 3 hours.System pH value is 3% Na with heavy percentage composition
2CO
3Solution maintains 3～4, again after settlement separate, washing, dehydration, drying, promptly obtains the composite ferric sodium salt product behind the stopped reaction, and its yield is 85%.Product specification and assay see Table 5:
The technical specification of the composite ferric sodium salt that table 5. embodiment 2 makes and assay
| Project name | Index | Assay |
| Outward appearance | Light yellow crystalline powder | Light yellow crystalline powder |
| 1% aqueous solution state | Transparent | Transparent |
| 1% aqueous solution pH | 6.6-7.6 | 7.2 |
| Loss on drying wt% | ≤11 | 3 |
| EDTA wt％ | ≥74.0 | 75.3 |
| Fe wt％ | ＞12 | 12 |
Embodiment 3 (water consumption is to the influence of yield):
Taking by weighing 49 gram ethylenediamine tetraacetic acid (EDTA)s, at room temperature is 20% aqueous sodium hydroxide solution 105 gram neutralizations with heavy percentage composition, makes it to dissolve fully, and pH value of solution is controlled at 8-10.Solution is poured in 500 milliliters of there-necked flasks that have whipping appts, be warming up to 60 ± 5 ℃, get weight percentage and be 45% ferric chloride aqueous solutions 70 grams, dropwise join in the there-necked flask with separating funnel, complex reaction begins, along with the color of carrying out system of reaction progressively becomes pale redly by dark red, when pH was 2, solution began to occur crystallization.After iron trichloride drips, under above-mentioned temperature of reaction, continue reaction 3 hours.System's weight percentage is 3% Na
2CO
3Solution is kept pH3～4.Again after settlement separate, washing, dehydration, drying, promptly obtain product after stopping to stir, its yield is 78%.Product specification and assay see Table 6:
The product specification of the composite ferric sodium salt that table 6. embodiment 3 makes and assay
| Project name | Index | Assay |
| Outward appearance | Light yellow crystalline powder | Light yellow crystalline powder |
| 1% aqueous solution state | Transparent | Transparent |
| 1% aqueous solution pH | 6.6-7.6 | 7.2 |
| Loss on drying wt% | ≤11 | 3 |
| EDTA wt％ | ≥74.0 | 75.3 |
| Fe wt％ | ＞12 | 12 |
Claims (1)
1. styrene-butadiene rubber(SBR) production is characterized in that with the preparation method of composite ferric sodium salt:
With a certain amount of ethylenediamine tetraacetic acid (EDTA) under agitation, be added to weight percentage and be in 15～30% the sodium hydroxide solution and carry out neutralization reaction, temperature is controlled to be 40～60 ℃, and the weight ratio of ethylenediamine tetraacetic acid (EDTA) and sodium hydroxide is 0.8: 0.5～1.0: 0.7; After ethylenediamine tetraacetic acid (EDTA) all is converted into tetrasodium salt of EDTA, slow its weight percentage of dropping is 40～60% liquor ferri trichloridi under stirring, the weight ratio of ethylenediamine tetraacetic acid (EDTA) and iron trichloride is 0.8: 0.3～1.0: 0.5,50～80 ℃ of its complex reaction temperature, iron trichloride drips the back and continues reaction 3～5 hours, is 2～5%Na with weight percentage in above-mentioned reaction process
2CO
3The pH3 of aqueous solution regulation system～4, complex reaction finishes the back and feeds water coolant, when material be cooled to＜30 ℃ the time, stop to stir, it is put to settling bowl, sedimentation was extracted mother liquor out after 2 days, with wet stock after centrifuging, washing, drying, promptly obtaining the pH value is 6.6～7.6, ethylenediamine tetraacetic acid (EDTA) weight percentage 〉=74.0%, the product of Fe weight percentage 〉=12%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100168173A CN100366652C (en) | 2006-04-26 | 2006-04-26 | Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100168173A CN100366652C (en) | 2006-04-26 | 2006-04-26 | Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1837252A CN1837252A (en) | 2006-09-27 |
| CN100366652C true CN100366652C (en) | 2008-02-06 |
Family
ID=37014774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100168173A Expired - Fee Related CN100366652C (en) | 2006-04-26 | 2006-04-26 | Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100366652C (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015408A (en) * | 1988-03-19 | 1991-05-14 | Reckitt Gmbh | Denture cleaning tablet containing a bleach activator and an organic phosphonic acid stabilizer |
-
2006
- 2006-04-26 CN CNB2006100168173A patent/CN100366652C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015408A (en) * | 1988-03-19 | 1991-05-14 | Reckitt Gmbh | Denture cleaning tablet containing a bleach activator and an organic phosphonic acid stabilizer |
Non-Patent Citations (2)
| Title |
|---|
| 丁苯橡胶合成用活化剂乙二胺四乙酸盐溶液比热容的测定. 赵小明，刘志刚，陈钟颀.应用化学，第12卷第1期. 1995 * |
| 脂肪酸钠对丁苯橡胶聚合反应的影响分析. 柴树花，郝玉东.工业技术，第32卷第3期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1837252A (en) | 2006-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100534917C (en) | Composite emulsion breaking scavenging agnet and preparation method thereof | |
| CN105293661B (en) | Without chlorion organic phosphine chelating agent and preparation method thereof | |
| CN104117435A (en) | Preparation method for titanic iron ore floatation collecting agent | |
| CN104355336A (en) | Method of utilizing ferrous sulfate waste residue to prepare polymeric ferric sulfate | |
| CN100366652C (en) | Process for preparing composite ferric sodium salt for preparation of styrene butadiene rubber | |
| CN101671285A (en) | Preparation method of BBI | |
| CN102139246A (en) | Method for preparing feldspar iron removal floatation collecting agent | |
| CN111056760B (en) | Aliphatic water reducer prepared from aminobenzenesulfonic acid wastewater and synthesis process thereof | |
| CN104445281A (en) | Waste residue comprehensive utilization method for trichlorosilane leaching system | |
| CN103011362B (en) | Preparation method for high-efficiency dye decolorizing agent | |
| CN103496871A (en) | Method for preparing environment-friendly low-cost sulfamate superplasticizer | |
| CN104829504A (en) | New solvent sulfonation technology of G acid | |
| CN110857280B (en) | Preparation method of 2-acrylamide-2-methylpropanesulfonate | |
| CN112759454B (en) | Preparation method for preparing amino acid liquid surface fertilizer raw material from tanning chromium-containing leather scraps | |
| CN113072150B (en) | Method for preparing iron-titanium-vanadium ternary inorganic polymeric flocculant based on sulfuric acid acidolysis vanadium-titanium magnetite two-step method | |
| CN102198968B (en) | Heavy metal and arsenic ion complexing agent and preparation method and using method thereof | |
| CN113044946A (en) | Method for treating chromium in tanning dyeing and finishing wastewater | |
| CN102718632B (en) | Method for preparing terpin hydrate by virtue of continuous hydration | |
| CN102002739B (en) | Compounded main brightener for preparing zinc-plating brightener | |
| CN102502932A (en) | High-effective composite flocculant for treating low-turbidity water and preparation method of high-effective composite flocculant | |
| CN101708880A (en) | Novel environment friendly water treatment flocculant and preparation method thereof | |
| CN102978051B (en) | Preparation method for disproportionated rosin potassium soap with solid content of 25% | |
| CN104556697B (en) | A kind of golden yellow crystal bead blank and preparation method thereof | |
| CN102671640B (en) | Hydrated titanium dioxide-persimmon tannin acrylic resin compound sorbent, preparation method thereof and application thereof | |
| CN109160846B (en) | Phosphorus compound fertilizer coating coloring agent and preparation method thereof, and phosphorus compound fertilizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080206 Termination date: 20110426 |