CN106882770B - A kind of preparation method of modified high-grade insoluble sulfur - Google Patents
A kind of preparation method of modified high-grade insoluble sulfur Download PDFInfo
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- CN106882770B CN106882770B CN201710233876.4A CN201710233876A CN106882770B CN 106882770 B CN106882770 B CN 106882770B CN 201710233876 A CN201710233876 A CN 201710233876A CN 106882770 B CN106882770 B CN 106882770B
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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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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
Abstract
The present invention provides a kind of preparation methods of modified high-grade insoluble sulfur, comprising the following steps: (1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill and is ground together with common sulphur, obtains mixing fine powders；(2) it polymerize: mixing fine powders is poured into reactor, are warming up to 100-105 DEG C under inert gas protection, then be warming up to 230-240 DEG C with the speed of 2-3 DEG C/min, constant temperature 50-70min；(3) chilling: molten state sulphur is poured into chilling liquid；(4) solidify: solidifying 3-3.5h at 62-66 DEG C, grinder grinding is poured into together with calcium stearate；(5) it extracts: after extraction, filtering, is dry；(6) oil-filled: it crushes, sieving, the compound stabilizer of p-methylstyrene, triphenyl phosphate is added, it is oil-filled after mixing；The present invention keeps insoluble sulfur content obtained high, and high thermal stability and dispersibility are effectively improved by the technique in each stage in optimization preparation process.
Description
Technical field
The present invention relates to the production fields of sulphur, and in particular to a kind of preparation method of modified high-grade insoluble sulfur.
Background technique
Insoluble sulfur is formed by common sulphur ring-opening polymerisation, is linear big point of molecular weight between 4000-40000
Son does not dissolve in carbon disulfide.Insoluble sulfur is divided into oil-filled type and non-two class of oil-filled type.Oil-filled type insoluble sulfur refers to non-
It is filled with the special oil of 4-34% on the basis of oil-filled type product, is commonly used in rubber product, non-oil-filled type sulphur is mainly used
In chemical fibre industry.
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.These characteristics enable insoluble sulfur extensively in the production process for various rubber products.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of modified high-grade insoluble sulfur, are prepared by optimization
The technique in each stage in journey keeps insoluble sulfur content obtained high, and high thermal stability and dispersibility obtain effectively
It improves.
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of preparation method of modified high-grade insoluble sulfur, comprising the following steps:
(1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill together with common sulphur
2-3h is ground, mixing fine powders are obtained；
(2) it polymerize: mixing fine powders is poured into reactor, under inert gas protection warming while stirring to 100-105
DEG C, then it is warming up to 230-240 DEG C with the speed of 2-3 DEG C/min, constant temperature 50-70min；
(3) chilling: above-mentioned molten state sulphur is poured into chilling liquid, obtains viscoplasticity insoluble sulfur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product is solidified into 3-3.5h at 62-66 DEG C, will be cured after not
Dissolubility sulphur crude product is poured into grinder together with calcium stearate, grinds 1-2h under the protection of inert gas, is obtained insoluble
Sulphur crude product powder；
(5) it extracts: insoluble sulfur crude product powder being poured into extract liquor and is extracted, filtered, dry to obtain Gao Pin
Position insoluble sulfur；
(6) oil-filled: high-grade insoluble sulfur being crushed, crosses 200-240 mesh, and p-methylstyrene, phosphoric acid is added
The compound stabilizer of triphenylmethyl methacrylate obtains oil-filled type insoluble sulfur through oil-filled after being uniformly mixed.
Preferably, Chloropolystyrene in the step (1), methylene chloride, common sulphur mass ratio be 1-2:3-6:
300-350。
Preferably, the four amylalcohol aqueous solution of season that the chilling liquid is 0.3%.
Preferably, the calcium stearate in the step (4) is the 1-1.5% of insoluble sulfur crude product quality.
Preferably, the mass ratio of the insoluble sulfur crude product powder and extract liquor is 4-5:1.
Preferably, the extract liquor is that dimethylbenzene and n-butanol 1:0.5-1.5 in mass ratio are mixed.
Preferably, in the step (6), the additional amount of compound stabilizer is the 2- of high-grade insoluble sulfur quality
3.5%, p-methylstyrene, triphenyl phosphate mass ratio be 2-5:3-7.
Preferably, the inert gas is nitrogen or argon gas.
Beneficial effects of the present invention:
The present invention makes the stabilizer chlorine being previously added first by common sulphur and Chloropolystyrene, methylene chloride pre-grinding
Change polystyrene, methylene chloride are sufficiently mixed with common sulphur and contact, and in melt and dissolved polymerization process later, sulphur octatomic ring is disconnected
It splits and aggregates into long chain macromolecule polymer, by the way that heating rate and heating temperature is rationally arranged, effectively increase insoluble sulfur
Content.In quenching process later, the stabilizer being previously added can effectively prevent insoluble sulfur to soluble sulfur
Conversion.In the curing process, be added calcium stearate grind together, after through extraction, it is oil-filled obtain high-grade insoluble sulfur,
Before oil-filled, the compound stabilizer of p-methylstyrene and triphenyl phosphate is added, the content of insoluble sulfur can be effectively improved
And the thermal stability of enhancing insoluble sulfur.Preparation method of the present invention is simple, and dangerous small, used production equipment is simple,
Low energy consumption, advantageously reduces production cost, content >=97%, 105 DEG C × 15min of obtained high-grade insoluble sulfur
High thermal stability >=84%, 120 DEG C × 15min high thermal stability >=55%,
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 preparation method of modified high-grade insoluble sulfur, comprising the following steps:
(1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill together with common sulphur
3h is ground, mixing fine powders are obtained；Wherein Chloropolystyrene, methylene chloride, common sulphur mass ratio be 2:6:350；
(2) it polymerize: mixing fine powders is poured into reactor, warming while stirring is to 100 DEG C under nitrogen protection, then with 3
DEG C/speed of min is warming up to 235 DEG C, constant temperature 50min；
(3) chilling: above-mentioned molten state sulphur is poured into 0.3% season chilling in four amylalcohol aqueous solutions, it is insoluble to obtain viscoplasticity
Property sulphur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product is solidified into 3.5h at 62 DEG C, will be cured after insoluble sulfur
Sulphur crude product is poured into grinder together with the calcium stearate of insoluble sulfur crude product quality 1.2%, under the protection of nitrogen
1.5h is ground, insoluble sulfur crude product powder is obtained；
(5) it extracts: insoluble sulfur crude product powder being poured into the extract liquor of its 5 times amounts and extracted, extract liquor is
Dimethylbenzene and n-butanol 1:0.5 in mass ratio are mixed；It filtered after extraction, dry to obtain high-grade insoluble sulfur；
(6) oil-filled: high-grade insoluble sulfur being crushed, crosses 220 meshes, and be added by p-methylstyrene, tricresyl phosphate
The compound stabilizer that phenyl ester 5:7 in mass ratio is mixed, the additional amount of compound stabilizer are high-grade insoluble sulfur quality
2%, through oil-filled oil-filled type insoluble sulfur after being uniformly mixed.
Embodiment 2:
A kind of preparation method of modified high-grade insoluble sulfur, comprising the following steps:
(1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill together with common sulphur
2.5h is ground, mixing fine powders are obtained；Wherein Chloropolystyrene, methylene chloride, common sulphur mass ratio be 1.5:5:320；
(2) it polymerize: mixing fine powders is poured into reactor, warming while stirring is to 105 DEG C under protection of argon gas, then with
The speed of 2.5 DEG C/min is warming up to 230 DEG C, constant temperature 55min；
(3) chilling: above-mentioned molten state sulphur is poured into 0.3% season chilling in four amylalcohol aqueous solutions, it is insoluble to obtain viscoplasticity
Property sulphur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product is solidified into 3.5h at 65 DEG C, will be cured after insoluble sulfur
Sulphur crude product is poured into grinder together with the calcium stearate of insoluble sulfur crude product quality 1.5%, under the protection of argon gas
1h is ground, insoluble sulfur crude product powder is obtained；
(5) it extracts: insoluble sulfur crude product powder being poured into the extract liquor of its 4 times amounts and extracted, extract liquor is
Dimethylbenzene and n-butanol 1:1 in mass ratio are mixed；It filtered after extraction, dry to obtain high-grade insoluble sulfur；
(6) oil-filled: high-grade insoluble sulfur being crushed, crosses 200 meshes, and be added by p-methylstyrene, tricresyl phosphate
The compound stabilizer that phenyl ester 4:3 in mass ratio is mixed, the additional amount of compound stabilizer are high-grade insoluble sulfur quality
3.5%, through oil-filled oil-filled type insoluble sulfur after being uniformly mixed.
Embodiment 3:
A kind of preparation method of modified high-grade insoluble sulfur, comprising the following steps:
(1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill together with common sulphur
2h is ground, mixing fine powders are obtained；Wherein Chloropolystyrene, methylene chloride, common sulphur mass ratio be 1:3:300；
(2) it polymerize: mixing fine powders is poured into reactor, warming while stirring is to 105 DEG C under nitrogen protection, then with 2
DEG C/speed of min is warming up to 240 DEG C, constant temperature 70min；
(3) chilling: above-mentioned molten state sulphur is poured into 0.3% season chilling in four amylalcohol aqueous solutions, it is insoluble to obtain viscoplasticity
Property sulphur crude product；
(4) solidify: viscoplasticity insoluble sulfur crude product is solidified into 3h at 66 DEG C, will be cured after insoluble sulfur
Crude product is poured into grinder together with the calcium stearate of insoluble sulfur crude product quality 1.5%, is ground under the protection of nitrogen
2h is ground, insoluble sulfur crude product powder is obtained；
(5) it extracts: insoluble sulfur crude product powder being poured into the extract liquor of its 4 times amounts and extracted, extract liquor is
Dimethylbenzene and n-butanol 1:1.5 in mass ratio are mixed；It filtered after extraction, dry to obtain high-grade insoluble sulfur；
(6) oil-filled: high-grade insoluble sulfur being crushed, crosses 240 meshes, and be added by p-methylstyrene, tricresyl phosphate
The compound stabilizer that phenyl ester 2:5 in mass ratio is mixed, the additional amount of compound stabilizer are high-grade insoluble sulfur quality
3%, through oil-filled oil-filled type insoluble sulfur after being uniformly mixed.
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 (4)
1. a kind of preparation method of modified high-grade insoluble sulfur, it is characterised in that: the following steps are included:
(1) pre-grinding: Chloropolystyrene is dissolved in methylene chloride, is then poured into ball mill and is ground together with common sulphur
2-3h obtains mixing fine powders；The Chloropolystyrene, methylene chloride, common sulphur mass ratio be 1-2:3-6:300-350；
(2) it polymerize: mixing fine powders is poured into reactor, warming while stirring is to 100-105 DEG C under inert gas protection, then
It is warming up to 230-240 DEG C with the speed of 2-3 DEG C/min, constant temperature 50-70min；
(3) chilling: above-mentioned molten state sulphur is poured into chilling liquid, obtains viscoplasticity insoluble sulfur crude product；The chilling liquid
For 0.3% four amylalcohol aqueous solution of season；
(4) solidify: viscoplasticity insoluble sulfur crude product is solidified into 3-3.5h at 62-66 DEG C, will be cured after it is insoluble
Sulphur crude product is poured into grinder together with calcium stearate, is ground 1-2h under the protection of inert gas, is obtained insoluble sulfur
Crude product powder；
(5) extract: insoluble sulfur crude product powder is poured into extract liquor and is extracted, filtered, dry high-grade not
Dissolubility sulphur；The extract liquor is that dimethylbenzene and n-butanol 1:0.5-1.5 in mass ratio are mixed；
(6) oil-filled: high-grade insoluble sulfur being crushed, crosses 200-240 mesh, and p-methylstyrene, phosphoric acid triphen is added
The compound stabilizer of ester obtains oil-filled type insoluble sulfur through oil-filled after being uniformly mixed；The additional amount of the compound stabilizer is height
The 2-3.5% of grade insoluble sulphur quality, p-methylstyrene, triphenyl phosphate mass ratio be 2-5:3-7.
2. the preparation method of modified high-grade insoluble sulfur according to claim 1, it is characterised in that: the step
(4) calcium stearate in is the 1-1.5% of insoluble sulfur crude product quality.
3. the preparation method of modified high-grade insoluble sulfur according to claim 1, it is characterised in that: described insoluble
The mass ratio of sulphur crude product powder and extract liquor is 4-5:1.
4. the preparation method of modified high-grade insoluble sulfur according to claim 1, it is characterised in that: the indifferent gas
Body is nitrogen or argon gas.
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| CN107381510B (en) * | 2017-09-01 | 2019-11-22 | 上海京海（安徽）化工有限公司 | A kind of production technology of rubber high quality insoluble sulphur |
| CN109650839A (en) * | 2019-02-26 | 2019-04-19 | 中国人民解放军陆军勤务学院 | A kind of sulphur concrete and preparation method thereof of anti-distillation corrosion |
| CN114348969A (en) * | 2022-01-12 | 2022-04-15 | 嘉兴学院 | Preparation method of insoluble sulfur |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037191A (en) * | 2007-03-20 | 2007-09-19 | 南京工业大学 | Preparation method of oil-filled insoluble sulphur |
| CN105645361A (en) * | 2016-01-22 | 2016-06-08 | 上海京海（安徽）化工有限公司 | Liquid phase method for producing insoluble sulfur |
| CN105694096A (en) * | 2016-01-29 | 2016-06-22 | 常州达奥新材料科技有限公司 | Environment-friendly preparation method of high-dispersity insoluble sulfur |
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| CN105936500A (en) * | 2016-06-27 | 2016-09-14 | 董晓 | Preparation method of insoluble sulfur |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037191A (en) * | 2007-03-20 | 2007-09-19 | 南京工业大学 | Preparation method of oil-filled insoluble sulphur |
| CN105645361A (en) * | 2016-01-22 | 2016-06-08 | 上海京海（安徽）化工有限公司 | Liquid phase method for producing insoluble sulfur |
| CN105694096A (en) * | 2016-01-29 | 2016-06-22 | 常州达奥新材料科技有限公司 | Environment-friendly preparation method of high-dispersity insoluble sulfur |
Non-Patent Citations (1)
| Title |
|---|
| 不溶性硫磺的合成、改性及其对橡胶性能的影响;李文灿;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;中国学术期刊（光盘版）电子杂志社;20150415;第3-18,23-24,43-44,55页 |
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