CN107381510B - 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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- CN107381510B CN107381510B CN201710779444.3A CN201710779444A CN107381510B CN 107381510 B CN107381510 B CN 107381510B CN 201710779444 A CN201710779444 A CN 201710779444A CN 107381510 B CN107381510 B CN 107381510B
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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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Abstract
The present invention provides a kind of production technologies of rubber high quality insoluble sulphur, the production technology is the following steps are included: (1) pre-grinding: turpentine oil being sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed, mixing fine powders are obtained；(2) it polymerize: mixing fine powders is poured into reactor, reactor internal pressure 0.14-0.16Mpa is made under inert environments；Preheating is warming up to 165-180 DEG C, keeps the temperature 20-30min, is warming up to 260-270 DEG C, keeps the temperature 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；It is filtered after extraction, is dry；(6) oil-filled: it pulverizes and sieves, and the compound stabilizer to 4- amino piperidine dihydrochloride, triphenyl phosphate is added, it is oil-filled；Raw material of the present invention is easy to get, and generates simple process, and dangerous small, low energy consumption, and insoluble sulfur content obtained by final production is high, dispersibility is high, stability is high, excellent combination property.
Description
Technical field
The present invention relates to the production fields of insoluble sulfur, and in particular to a kind of life of rubber high quality insoluble sulphur
Production. art.
Background technique
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 108 or more, 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, not reunited, and the incipient scorch tendency of rubber semi-finished product is reduced；No
The macromolecular chain of dissolubility sulphur is unstable, is heated and easily decomposes, can cause the vulcanization of rubber, and curingprocess rate under lower temperature
Fastly, 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, is easy to be depolymerized to usual endless macromolecular under high temperature.Present domestic production
Compared with foreign countries, content is low for insoluble sulfur, 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.
Summary of the invention
The purpose of the present invention is to provide a kind of production technology of rubber high quality insoluble sulphur, raw material is easy to get, raw
At simple process, dangerous small, low energy consumption, and insoluble sulfur content obtained by final production is high, dispersibility is high, stability is high, comprehensive
It has excellent performance.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of production technology of rubber high quality insoluble sulphur, comprising the following steps:
(1) pre-grinding: turpentine oil being sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, common sulphur mass ratio be 1-1.5:0.3-0.6:100.
(2) it polymerize: mixing fine powders is poured into reactor, then reactor is 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 reactor internal pressure
0.14-0.16Mpa；Mixing fine powders are preheated to 120-130 DEG C, then with the speed warming while stirring of 3-4 DEG C/min to 165-
180 DEG C, 20-30min is kept the temperature, then with the speed warming while stirring of 2-3 DEG C/min to 260-270 DEG C, keeps the temperature 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 being taken out, 4-5h is dried in vacuo at 60-65 DEG C, is crushed later simultaneously
100-140 mesh is crossed, insoluble sulfur crude powder is obtained；
(5) it extracts: insoluble sulfur crude powder being poured into extractant and is extracted, the extractant is four chlorinations
Carbon, tetrachloro-ethylene are mixed by certain mass ratio；It is filtered after extraction, is dry, obtaining insoluble sulfur fine work；
(6) oil-filled: insoluble sulfur fine work being crushed, crosses 200-240 mesh, and be added to two hydrochloric acid of 4- amino piperidine
The compound stabilizer of salt, triphenyl phosphate obtains oil-filled type insoluble sulfur through oil-filled after being uniformly mixed.Wherein filling oil is general
Common filling oil, such as naphthenic rubber oil or paraffinic base rubber oil, oil-filled quantity 10-30%.
Preferably, turpentine oil in the step (1), phosphorus pentachloride, common sulphur mass ratio be 1.2:0.5:100.
Preferably, the inert gas in the step (2) is nitrogen or argon gas.
Preferably, the four amylalcohol aqueous solution of season that chilling liquid is 0.2% in the step (3).
Preferably, extraction temperature is 70-75 DEG C, liquid-solid ratio 8-10:1, extraction time 15- in the step (5)
20min, the extractant is carbon tetrachloride, tetrachloro-ethylene 1:0.5-1.5 in mass ratio is mixed.
Preferably, 4- amino piperidine dihydrochloride in the step (6), triphenyl phosphate mass ratio be 1:1-8.
The beneficial effects of the present invention are:
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, and common sulphur surface is made to be coated with the mixed stability of one layer of turpentine oil and phosphorus pentachloride
Agent, good mixing effect.It in polymerization process, is heated up using staged, sulphur octatomic ring is broken and constantly aggregates into long chain macromolecule
Polymer effectively increases the content of insoluble sulfur by the way that heating rate, heating temperature, soaking time is rationally arranged.Wherein
Unsaturated sulphur atom of the free radical and chloride ion that the heated double bond of turpentine oil generates after being opened with insoluble sulfur both ends
Bonding, the two combine, and effectively enhance the stability quilt of insoluble sulfur, especially in the process set internal pressure to
0.14-0.16Mpa, can make bonding better effect, and the reinforcing effect of stability is good compared under condition of normal pressure.
Further, the present invention in extraction process using the mixed liquor of carbon tetrachloride and tetrachloro-ethylene as extractant, can
It effectively improves the content of insoluble sulfur and enhances its stability.In oil-filled preceding addition 4- amino piperidine dihydrochloride, tricresyl phosphate
The compound stabilizer of phenyl ester, the two synergistic effect, 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 generates simple process, dangerous small, low energy consumption, insoluble sulfur content obtained by final production
High, dispersibility height, stability are high, excellent combination property.It is used in the vulcanization of rubber product, rubber product can be effectively improved
Quality.High thermal stability >=90%, 120 of high quality insoluble sulphur content >=96.5%, 105 DEG C/15min of the present invention
DEG C/high thermal stability >=72% of 15min.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A kind of production technology of rubber high quality insoluble sulphur, comprising the following steps:
(1) pre-grinding: turpentine oil being sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, common sulphur mass ratio be 1.2:0.5:100.
(2) it polymerize: mixing fine powders is poured into reactor, then reactor is vacuumized, and pour nitrogen, repeatedly
5 times, until the air in reactor is excluded completely, nitrogen is finally poured again, and make reactor internal pressure 0.16Mpa；It will mix
It closes fine powder and is preheated to 130 DEG C, then with the speed warming while stirring of 3 DEG C/min to 180 DEG C, keep the temperature 25min, then with 3 DEG C/min
Speed warming while stirring to 265 DEG C, keep the temperature 80min；
(3) chilling: by above-mentioned liquid-state sulfur after pressurized spray obtain viscoplasticity in 0.2% season in four amylalcohol aqueous solutions
Insoluble sulfur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product being taken out, 4h is dried in vacuo at 65 DEG C, crush later and cross 100
Mesh obtains insoluble sulfur crude powder；
(5) it extracts: insoluble sulfur crude powder being poured into extractant and is extracted, extraction temperature is 75 DEG C, and liquid is solid
Than for 10:1, extraction time 18min, extractant is that carbon tetrachloride, tetrachloro-ethylene 1:1.5 in mass ratio are mixed；Extraction
It filters afterwards, is dry, obtaining insoluble sulfur fine work；
(6) oil-filled: insoluble sulfur fine work being crushed, crosses 240 meshes, and be added to 4- amino piperidine dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester, 4- amino piperidine dihydrochloride, triphenyl phosphate mass ratio be 1:5；It is passed through after being uniformly 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, comprising the following steps:
(1) pre-grinding: turpentine oil being sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, common sulphur mass ratio be 1:0.6:100.
(2) it polymerize: mixing fine powders is poured into reactor, then reactor is vacuumized, and pour argon gas, repeatedly
4 times, until the air in reactor is excluded completely, argon gas is finally poured again, and make reactor internal pressure 0.14Mpa；It will mix
It closes fine powder and is preheated to 125 DEG C, then with the speed warming while stirring of 4 DEG C/min to 165 DEG C, keep the temperature 30min, then with 2 DEG C/min
Speed warming while stirring to 260 DEG C, keep the temperature 70min；
(3) chilling: by above-mentioned liquid-state sulfur after pressurized spray obtain viscoplasticity in 0.2% season in four amylalcohol aqueous solutions
Insoluble sulfur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product being taken out, 5h is dried in vacuo at 60 DEG C, crush later and cross 140
Mesh obtains insoluble sulfur crude powder；
(5) it extracts: insoluble sulfur crude powder being poured into extractant and is extracted, extraction temperature is 70 DEG C, and liquid is solid
Than for 8:1, extraction time 20min, extractant is that carbon tetrachloride, tetrachloro-ethylene 1:0.5 in mass ratio are mixed；After extraction
Filtering, drying, obtain insoluble sulfur fine work；
(6) oil-filled: insoluble sulfur fine work being crushed, crosses 200 meshes, and be added to 4- amino piperidine dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester, 4- amino piperidine dihydrochloride, triphenyl phosphate mass ratio be 1:8；It is passed through after being uniformly 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, comprising the following steps:
(1) pre-grinding: turpentine oil being sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed,
Obtain mixing fine powders；The turpentine oil, phosphorus pentachloride, common sulphur mass ratio be 1.5:0.3:100.
(2) it polymerize: mixing fine powders is poured into reactor, then reactor is vacuumized, and pour nitrogen, repeatedly
3 times, until the air in reactor is excluded completely, nitrogen is finally poured again, and make reactor internal pressure 0.16Mpa；It will mix
It closes fine powder and is preheated to 120 DEG C, then with the speed warming while stirring of 3 DEG C/min to 170 DEG C, keep the temperature 20min, then with 2 DEG C/min
Speed warming while stirring to 270 DEG C, keep the temperature 60min；
(3) chilling: by above-mentioned liquid-state sulfur after pressurized spray obtain viscoplasticity in 0.2% season in four amylalcohol aqueous solutions
Insoluble sulfur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product being taken out, 5h is dried in vacuo at 60 DEG C, crush later and cross 120
Mesh obtains insoluble sulfur crude powder；
(5) it extracts: insoluble sulfur crude powder being poured into extractant and is extracted, extraction temperature is 70 DEG C, and liquid is solid
Than for 9:1, extraction time 15min, extractant is that carbon tetrachloride, tetrachloro-ethylene 1:1 in mass ratio are mixed；Mistake after extraction
Filter, drying, obtain insoluble sulfur fine work；
(6) oil-filled: insoluble sulfur fine work being crushed, crosses 200-240 mesh, and be added to two hydrochloric acid of 4- amino piperidine
The compound stabilizer of salt, triphenyl phosphate, 4- amino piperidine dihydrochloride, triphenyl phosphate mass ratio be 1:1；It is uniformly 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
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of production technology of rubber high quality insoluble sulphur, which comprises the following steps:
(1) pre-grinding: turpentine oil is sent into high-speed mixer together with common sulphur after phosphorus pentachloride mixing and is mixed, is obtained mixed
Close fine powder；The turpentine oil, phosphorus pentachloride, common sulphur mass ratio be 1-1.5:0.3-0.6:100；
(2) it polymerize: mixing fine powders is poured into reactor, then reactor is vacuumized, and pour inert gas, repeatedly
3-5 times, until the air in reactor is excluded completely, inert gas is finally poured again, and make reactor internal pressure 0.14-
0.16MPa；Mixing fine powders are preheated to 120-130 DEG C, then with the speed warming while stirring of 3-4 DEG C/min to 165-180 DEG C,
20-30min is kept the temperature, then with the speed warming while stirring of 2-3 DEG C/min to 260-270 DEG C, keeps the temperature 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 being taken out, 4-5h is dried in vacuo at 60-65 DEG C, later crushing and mistake
100-140 mesh obtains insoluble sulfur crude powder；
(5) it extracts: insoluble sulfur crude powder being poured into extractant and is extracted, the extractant is carbon tetrachloride, four
Vinyl chloride is mixed by certain mass ratio；It is filtered after extraction, is dry, obtaining insoluble sulfur fine work；
(6) oil-filled: insoluble sulfur fine work being crushed, crosses 200-240 mesh, and be added to 4- amino piperidine dihydrochloride, phosphorus
The compound stabilizer of triphenyl phosphate ester obtains oil-filled type insoluble sulfur through oil-filled after being uniformly mixed.
2. the production technology of rubber high quality insoluble sulphur according to claim 1, which is characterized in that the step
(1) turpentine oil in, phosphorus pentachloride, common sulphur mass ratio be 1.2:0.5:100.
3. the production technology of rubber high quality insoluble sulphur according to claim 1, which is characterized 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, which is characterized in that the step
(3) the pentaerythrite aqueous solution that chilling liquid is 0.2% in.
5. the production technology of rubber high quality insoluble sulphur according to claim 1, which is characterized in that the step
(5) extraction temperature is 70-75 DEG C, liquid-solid ratio 8-10:1, extraction time 15-20min in, and the extractant is four chlorinations
Carbon, tetrachloro-ethylene 1:0.5-1.5 in mass ratio are mixed.
6. the production technology of rubber high quality insoluble sulphur according to claim 1, which is characterized in that the step
(6) 4- amino piperidine dihydrochloride in, triphenyl phosphate mass ratio be 1:1-8.
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| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689227A (en) * | 1971-11-12 | 1972-09-05 | Union Oil Co | Method for producing insoluble sulfur |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100488870C (en) * | 2007-03-20 | 2009-05-20 | 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 |
| CN106995206B (en) * | 2017-04-11 | 2019-02-12 | 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 |
| CN106882770B (en) * | 2017-04-11 | 2019-02-22 | 上海京海（安徽）化工有限公司 | A kind of preparation method of modified high-grade insoluble sulfur |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3689227A (en) * | 1971-11-12 | 1972-09-05 | Union Oil Co | Method for producing insoluble sulfur |
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