CN107381510A - A kind of production technology of rubber high quality insoluble sulphur - Google Patents
A kind of production technology of rubber high quality insoluble sulphur Download PDFInfo
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- CN107381510A CN107381510A CN201710779444.3A CN201710779444A CN107381510A CN 107381510 A CN107381510 A CN 107381510A CN 201710779444 A CN201710779444 A CN 201710779444A CN 107381510 A CN107381510 A CN 107381510A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/12—Insoluble sulfur (mu-sulfur)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a kind of production technology of rubber high quality insoluble sulphur, the production technology comprises the following steps：(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed, obtains mixing fine powders；(2) it polymerize：Mixing fine powders are poured into reactor, it is 0.14 0.16Mpa that reactor internal pressure is made under inert environments；Preheating, 165 180 DEG C are warming up to, are incubated 20 30min, be warming up to 260 270 DEG C, be incubated 60 80min；(3) chilling；(4) solidify：Vacuum drying, pulverizes and sieves；(5) extract：Extractant is carbon tetrachloride, tetrachloro-ethylene is mixed by certain mass ratio；Filter, dry after extraction；(6) it is oil-filled：Pulverize and sieve, and add to 4 amino piperidine dihydrochlorides, the compound stabilizer of triphenyl phosphate, it is oil-filled；Raw material of the present invention is easy to get, and generation technique is simple, and dangerous small, energy consumption is low, and insoluble sulfur content obtained by final production is high, dispersiveness is high, stability is high, excellent combination property.
Description
Technical field
The present invention relates to the production field of insoluble sulfur, and in particular to a kind of life of rubber high quality insoluble sulphur
Production. art.
Background technology
Insoluble sulfur is a kind of nontoxic, flammable yellow powder, is gained the name because it does not dissolve in carbon disulfide.It is through common
Sulphur thermal polymerization is made, and the number of sulfur atoms on strand is up to more than 108, there is the viscoplasticity and molecular weight distribution of high polymer, because
This is also referred to as elastic sulfur or polymerised sulphur, belongs to inorganic polymer industrial chemicals.
Insoluble sulfur is linear macromolecule, not easy to migrate insoluble in rubber, so bloom phenomenon can be reduced effectively
Generation；Insoluble sulfur can be uniformly dispersed in rubber, do not reunited, and reduce the incipient scorch tendency of rubber semi-finished product；No
The macromolecular chain of dissolubility sulphur is unstable, is heated and easily decomposes, and can triggers the vulcanization of rubber, and curingprocess rate under lower temperature
It hurry up, insoluble sulfur can also improve the tack of sizing material, improve the bonding between rubber semi-finished product, sizing material and all-steel cord
Degree.But insoluble sulfur linear macromolecule is unstable, usual endless macromolecular is easily depolymerized under high temperature.Present domestic production
For insoluble sulfur compared with foreign countries, content is low, bad dispersibility, poor high temperature stability.So production high content, high dispersive, Gao Wen
The problem of qualitative insoluble sulfur is urgent need to resolve.
The content of the invention
It is an object of the invention to provide a kind of production technology of rubber high quality insoluble sulphur, raw material is easy to get, raw
Simple into technique, dangerous small, energy consumption is low, and insoluble sulfur content obtained by final production is high, dispersiveness is high, stability is high, comprehensive
Excellent performance.
To realize object above, the present invention is achieved by the following technical programs：
A kind of production technology of rubber high quality insoluble sulphur, comprises the following steps：
(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1-1.5：0.3-0.6：100.
(2) it polymerize：Mixing fine powders are poured into reactor, then reactor vacuumized, and pour inert gas, so
3-5 times repeatedly, until the air in reactor is excluded completely, inert gas is finally poured again, and make the reactor internal pressure be
0.14-0.16Mpa；Mixing fine powders are preheated to 120-130 DEG C, then with 3-4 DEG C/min speed warming while stirring to 165-
180 DEG C, 20-30min is incubated, then with 2-3 DEG C/min speed warming while stirring to 260-270 DEG C, is incubated 60-80min；
(3) chilling：By the pressurized rear spray of above-mentioned liquid-state sulfur in chilling liquid, viscoplasticity insoluble sulfur crude product is obtained；
(4) solidify：Viscoplasticity insoluble sulfur crude product is taken out, 4-5h is dried in vacuo at 60-65 DEG C, is crushed afterwards simultaneously
100-140 mesh sieves are crossed, obtain insoluble sulfur crude powder；
(5) extract：Insoluble sulfur crude powder is poured into extractant and extracted, the extractant is four chlorinations
Carbon, tetrachloro-ethylene are mixed by certain mass ratio；Filter, dry after extraction, obtain insoluble sulfur fine work；
(6) it is oil-filled：Insoluble sulfur fine work is crushed, crosses 200-240 mesh sieves, and add to the hydrochloric acid of 4- amino piperidines two
The compound stabilizer of salt, triphenyl phosphate, oil-filled type insoluble sulfur is obtained through oil-filled after being well mixed.It is general wherein to fill oil
Conventional filling oil, such as naphthenic rubber oil or paraffinic base rubber oil, its oil-filled quantity are 10-30%.
Preferably, turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1.2 in the step (1)：0.5：100.
Preferably, the inert gas in the step (2) is nitrogen or argon gas.
Preferably, chilling liquid is the 0.2% amylalcohol aqueous solution of season four in the step (3).
Preferably, extraction temperature is 70-75 DEG C in the step (5), liquid-solid ratio 8-10：1, extraction time 15-
20min, the extractant are carbon tetrachloride, tetrachloro-ethylene in mass ratio 1：0.5-1.5 is mixed.
Preferably, 4- amino piperidines dihydrochloride, the mass ratio of triphenyl phosphate are 1 in the step (6)：1-8.
The beneficial effects of the invention are as follows：
The production technology of rubber high quality insoluble sulphur of the present invention, first using stabilizer turpentine oil, phosphorus pentachloride with
Common sulphur carries out mixed at high speed together, common sulphur Surface coating is had the mixed stability of one layer of turpentine oil and phosphorus pentachloride
Agent, good mixing effect.In polymerization process, heated up using staged, sulphur octatomic ring is broken and constantly aggregates into long chain macromolecule
Polymer, by rationally setting programming rate, heating-up temperature, soaking time, effectively increase the content of insoluble sulfur.Wherein
Unsaturated sulphur atom of the free radical and chlorion that the heated double bond of turpentine oil generates after being opened with insoluble sulfur both ends
Bonding, both are combined, and effectively enhance the stability quilt of insoluble sulfur, are particularly in the process arranged to internal pressure
0.14-0.16Mpa, bonding can be made better, the enhancing effect of stability is good compared with condition of normal pressure.
Further, the present invention in extraction process using the mixed liquor of carbon tetrachloride and tetrachloro-ethylene as extractant, can
Effectively improve the content of insoluble sulfur and strengthen its stability.In oil-filled preceding addition 4- amino piperidines dihydrochloride, tricresyl phosphate
The compound stabilizer of phenyl ester, both act synergistically, and the free electron of efficient coupling insoluble sulfur both-end free radical, prevent insoluble
Conversion of the property sulphur to soluble sulfur.
Raw material of the present invention is easy to get, and generation technique is simple, and dangerous small, energy consumption is low, insoluble sulfur content obtained by final production
High, dispersiveness height, stability are high, excellent combination property.In the vulcanization for using it for rubber, rubber can be effectively improved
Quality.High quality insoluble sulphur content >=96.5%, 105 DEG C/15min of the present invention high thermal stability >=90%, 120
DEG C/15min high thermal stability >=72%.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of production technology of rubber high quality insoluble sulphur, comprises the following steps：
(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1.2：0.5：100.
(2) it polymerize：Mixing fine powders are poured into reactor, then reactor vacuumized, and pour nitrogen, so repeatedly
5 times, until the air in reactor is excluded completely, nitrogen is finally poured again, and make reactor internal pressure be 0.16Mpa；Will be mixed
Close fine powder and be preheated to 130 DEG C, then with 3 DEG C/min speed warming while stirring to 180 DEG C, be incubated 25min, then with 3 DEG C/min
Speed warming while stirring to 265 DEG C, be incubated 80min；
(3) chilling：By above-mentioned liquid-state sulfur after pressurized spray in 0.2% season four in the amylalcohol aqueous solution, obtain viscoplasticity
Insoluble sulfur crude product；
(4) solidify：Viscoplasticity insoluble sulfur crude product is taken out, 4h is dried in vacuo at 65 DEG C, crushing afterwards and excessively 100
Mesh sieve, obtain insoluble sulfur crude powder；
(5) extract：Insoluble sulfur crude powder is poured into extractant and extracted, extraction temperature is 75 DEG C, and liquid is solid
Than for 10：1, extraction time 18min, extractant are carbon tetrachloride, tetrachloro-ethylene in mass ratio 1：1.5 mix；Extraction
Filter, dry afterwards, obtain insoluble sulfur fine work；
(6) it is oil-filled：Insoluble sulfur fine work is crushed, crosses 240 mesh sieves, and add to 4- amino piperidines dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester, 4- amino piperidines dihydrochloride, the mass ratio of triphenyl phosphate are 1：5；Passed through after well mixed
It is oil-filled to obtain oil-filled type insoluble sulfur.
Embodiment 2：
A kind of production technology of rubber high quality insoluble sulphur, comprises the following steps：
(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1：0.6：100.
(2) it polymerize：Mixing fine powders are poured into reactor, then reactor vacuumized, and pour argon gas, so repeatedly
4 times, until the air in reactor is excluded completely, argon gas is finally poured again, and make reactor internal pressure be 0.14Mpa；Will be mixed
Close fine powder and be preheated to 125 DEG C, then with 4 DEG C/min speed warming while stirring to 165 DEG C, be incubated 30min, then with 2 DEG C/min
Speed warming while stirring to 260 DEG C, be incubated 70min；
(3) chilling：By above-mentioned liquid-state sulfur after pressurized spray in 0.2% season four in the amylalcohol aqueous solution, obtain viscoplasticity
Insoluble sulfur crude product；
(4) solidify：Viscoplasticity insoluble sulfur crude product is taken out, 5h is dried in vacuo at 60 DEG C, crushing afterwards and excessively 140
Mesh sieve, obtain insoluble sulfur crude powder；
(5) extract：Insoluble sulfur crude powder is poured into extractant and extracted, extraction temperature is 70 DEG C, and liquid is solid
Than for 8：1, extraction time 20min, extractant are carbon tetrachloride, tetrachloro-ethylene in mass ratio 1：0.5 mixes；After extraction
Filtering, dry, obtain insoluble sulfur fine work；
(6) it is oil-filled：Insoluble sulfur fine work is crushed, crosses 200 mesh sieves, and add to 4- amino piperidines dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester, 4- amino piperidines dihydrochloride, the mass ratio of triphenyl phosphate are 1：8；Passed through after well mixed
It is oil-filled to obtain oil-filled type insoluble sulfur.
Embodiment 3：
A kind of production technology of rubber high quality insoluble sulphur, comprises the following steps：
(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1.5：0.3：100.
(2) it polymerize：Mixing fine powders are poured into reactor, then reactor vacuumized, and pour nitrogen, so repeatedly
3 times, until the air in reactor is excluded completely, nitrogen is finally poured again, and make reactor internal pressure be 0.16Mpa；Will be mixed
Close fine powder and be preheated to 120 DEG C, then with 3 DEG C/min speed warming while stirring to 170 DEG C, be incubated 20min, then with 2 DEG C/min
Speed warming while stirring to 270 DEG C, be incubated 60min；
(3) chilling：By above-mentioned liquid-state sulfur after pressurized spray in 0.2% season four in the amylalcohol aqueous solution, obtain viscoplasticity
Insoluble sulfur crude product；
(4) solidify：Viscoplasticity insoluble sulfur crude product is taken out, 5h is dried in vacuo at 60 DEG C, crushing afterwards and excessively 120
Mesh sieve, obtain insoluble sulfur crude powder；
(5) extract：Insoluble sulfur crude powder is poured into extractant and extracted, extraction temperature is 70 DEG C, and liquid is solid
Than for 9：1, extraction time 15min, extractant are carbon tetrachloride, tetrachloro-ethylene in mass ratio 1：1 mixes；Mistake after extraction
Filter, dry, obtain insoluble sulfur fine work；
(6) it is oil-filled：Insoluble sulfur fine work is crushed, crosses 200-240 mesh sieves, and add to the hydrochloric acid of 4- amino piperidines two
The compound stabilizer of salt, triphenyl phosphate, 4- amino piperidines dihydrochloride, the mass ratio of triphenyl phosphate are 1：1；It is well mixed
Oil-filled type insoluble sulfur is obtained by oil-filled.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (6)
1. a kind of production technology of rubber high quality insoluble sulphur, it is characterised in that comprise the following steps：
(1) pre-grinding：Turpentine oil is sent into high-speed mixer after phosphorus pentachloride mixing together with common sulphur and mixed, is obtained mixed
Close fine powder；The turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1-1.5：0.3-0.6：100.
(2) it polymerize：Mixing fine powders are poured into reactor, then reactor vacuumized, and pour inert gas, so repeatedly
3-5 times, until the air in reactor is excluded completely, inert gas is finally poured again, and make reactor internal pressure be 0.14-
0.16Mpa；Mixing fine powders are preheated to 120-130 DEG C, then with 3-4 DEG C/min speed warming while stirring to 165-180 DEG C,
20-30min is incubated, then with 2-3 DEG C/min speed warming while stirring to 260-270 DEG C, is incubated 60-80min；
(3) chilling：By the pressurized rear spray of above-mentioned liquid-state sulfur in chilling liquid, viscoplasticity insoluble sulfur crude product is obtained；
(4) solidify：Viscoplasticity insoluble sulfur crude product is taken out, 4-5h is dried in vacuo at 60-65 DEG C, afterwards crushing and mistake
100-140 mesh sieves, obtain insoluble sulfur crude powder；
(5) extract：Insoluble sulfur crude powder is poured into extractant and extracted, the extractant is carbon tetrachloride, four
Vinyl chloride is mixed by certain mass ratio；Filter, dry after extraction, obtain insoluble sulfur fine work；
(6) it is oil-filled：Insoluble sulfur fine work is crushed, crosses 200-240 mesh sieves, and add to 4- amino piperidines dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester, oil-filled type insoluble sulfur is obtained through oil-filled after being well mixed.
2. the production technology of rubber high quality insoluble sulphur according to claim 1, it is characterised in that the step
(1) turpentine oil, phosphorus pentachloride, the mass ratio of common sulphur are 1.2 in：0.5：100.
3. the production technology of rubber high quality insoluble sulphur according to claim 1, it is characterised in that the step
(2) inert gas in is nitrogen or argon gas.
4. the production technology of rubber high quality insoluble sulphur according to claim 1, it is characterised in that the step
(3) chilling liquid is the 0.2% amylalcohol aqueous solution of season four in.
5. the production technology of rubber high quality insoluble sulphur according to claim 1, it is characterised in that the step
(5) extraction temperature is 70-75 DEG C in, liquid-solid ratio 8-10：1, extraction time 15-20min, the extractant are four chlorinations
Carbon, tetrachloro-ethylene in mass ratio 1：0.5-1.5 is mixed.
6. the production technology of rubber high quality insoluble sulphur according to claim 1, it is characterised in that the step
(6) 4- amino piperidines dihydrochloride, the mass ratio of triphenyl phosphate are 1 in：1-8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368599A (en) * | 2018-11-02 | 2019-02-22 | 山东阳谷华泰化工股份有限公司 | A kind of preparation method of insoluble sulfur and its anti-stabilizer that reverts used |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689227A (en) * | 1971-11-12 | 1972-09-05 | Union Oil Co | Method for producing insoluble sulfur |
| CN101037191A (en) * | 2007-03-20 | 2007-09-19 | 南京工业大学 | Preparation method of oil-filled insoluble sulphur |
| CN103204479A (en) * | 2013-03-22 | 2013-07-17 | 上海京海（安徽）化工有限公司 | Production method for high-content insoluble sulfur |
| CN106882770A (en) * | 2017-04-11 | 2017-06-23 | 上海京海（安徽）化工有限公司 | A kind of preparation method of modified high-grade insoluble sulfur |
| CN106995206A (en) * | 2017-04-11 | 2017-08-01 | 上海京海（安徽）化工有限公司 | A kind of production technology of rubber high-content high-stability insoluble sulfur |
-
2017
- 2017-09-01 CN CN201710779444.3A patent/CN107381510B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689227A (en) * | 1971-11-12 | 1972-09-05 | Union Oil Co | Method for producing insoluble sulfur |
| CN101037191A (en) * | 2007-03-20 | 2007-09-19 | 南京工业大学 | Preparation method of oil-filled insoluble sulphur |
| CN103204479A (en) * | 2013-03-22 | 2013-07-17 | 上海京海（安徽）化工有限公司 | Production method for high-content insoluble sulfur |
| CN106882770A (en) * | 2017-04-11 | 2017-06-23 | 上海京海（安徽）化工有限公司 | A kind of preparation method of modified high-grade insoluble sulfur |
| CN106995206A (en) * | 2017-04-11 | 2017-08-01 | 上海京海（安徽）化工有限公司 | A kind of production technology of rubber high-content high-stability insoluble sulfur |
Non-Patent Citations (1)
| Title |
|---|
| 张利民 等: "《江苏省环境科学研究院科技论文集》", 30 November 2005 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109368599A (en) * | 2018-11-02 | 2019-02-22 | 山东阳谷华泰化工股份有限公司 | A kind of preparation method of insoluble sulfur and its anti-stabilizer that reverts used |
| CN109368599B (en) * | 2018-11-02 | 2022-03-15 | 山东阳谷华泰化工股份有限公司 | Preparation method of insoluble sulfur and anti-reversion stabilizer used by same |
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| CN107381510B (en) | 2019-11-22 |
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