CN107055483A - Grade insoluble sulphur and preparation method thereof in a kind of high dispersive - Google Patents
Grade insoluble sulphur and preparation method thereof in a kind of high dispersive Download PDFInfo
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- CN107055483A CN107055483A CN201710233873.0A CN201710233873A CN107055483A CN 107055483 A CN107055483 A CN 107055483A CN 201710233873 A CN201710233873 A CN 201710233873A CN 107055483 A CN107055483 A CN 107055483A
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- high dispersive
- sulphur
- insoluble sulphur
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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
- 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
- C01B17/0221—Melting
Abstract
The present invention proposes grade insoluble sulphur in grade insoluble sulphur and preparation method thereof in a kind of high dispersive, the high dispersive and is made up of following mass fraction：100 110 parts of element sulfur raw material, 0.5 1.2 parts of compound stabilizer, 0.1 0.15 parts of activator, 0.05 0.5 parts of gas-phase silica, 13 parts of polystyrene, 0.5 1.5 parts of m-chloro epoxy benzoic acid, 0.05 0.1 parts of silicone acrylic emulsion, 0.1 1 parts of stearine, obtained middle grade insoluble sulphur has high content, polymolecularity and high thermal stability, compared to the yield that tradition preparation substantially increases insoluble sulfur.
Description
Technical field
The present invention relates to insoluble sulfur preparing technical field, and in particular in a kind of high dispersive grade insoluble sulphur and
Its preparation method.
Background technology
Insoluble sulfur (IS) is also known as polymerised sulphur, also known as μ types sulphur, refers to the sulphur insoluble in carbon disulfide, is the long-chain of sulphur
Polymer, with chemically and physically inertia, distributional stability is good in sizing material, and product vulcanization crosslinking point is uniform, with its vulcanization
Rubber has an optimal no blooming, and can effectively prevent sizing material occur early stage incipient scorch in process and promote rubber with
The bonding of steel wire or chemical fibre cord fabric thread, is the dedicated vulcanization agent of radial tyre production.It is right with the raising of tire meridian rate
The demand of high quality insoluble sulphur is also increased rapidly.It is external also there was only a few countries such as U.S., Germany, Russia, Japan etc.
It can produce.China will lean on a large amount of imports to meet demand every year.Therefore, the market prospects of domestic insoluble sulfur are seen very much
It is good.
The domestic and international method for preparing IS is divided from temperature mainly high temperature gasification and watery fusion method, from quenching medium again
Immersion method and solvent method can be divided into.The advantage that high temperature gasification prepares IS is that the content of IS in product is of a relatively high, is had the disadvantage
Whole course of reaction is under high-temperature and high-pressure conditions, and the requirement to consersion unit is harsher, and potential safety hazard is big in production process.
What the difference of watery fusion method and evaporating method was quenching is sulphur melt rather than overheat sulfur vapor, so with reaction temperature
Low, equipment corrosion is small, atmospheric operation, small investment, instant effect, operate it is comparatively safe the advantages of, but in product IS content it is relatively low,
Therefore develop a kind of rationally efficient stabilizer and preparation method is very necessary.
The content of the invention
For above-mentioned problem, the present invention proposes grade insoluble sulphur and its preparation side in a kind of high dispersive
Method, obtained middle grade insoluble sulphur has high content, polymolecularity and high thermal stability, is carried significantly compared to tradition preparation
The high yield of insoluble sulfur.
In order to realize above-mentioned purpose, the present invention uses following technical scheme：
Grade insoluble sulphur in a kind of high dispersive, is made up of following mass fraction：It is 100-110 parts of element sulfur raw material, compound
0.5-1.2 parts of stabilizer, 0.1-0.15 parts of activator, 0.05-0.5 parts of gas-phase silica, 1-3 parts of polystyrene, m-chloro epoxy
0.5-1.5 parts of benzoic acid, 0.05-0.1 parts of silicone acrylic emulsion, 0.1-1 parts of stearine.
It is preferred that, the compound stabilizer is mass ratio 1:3:15 hexamethylenetetramine, N- cyclohexyl -2-[4-morpholinodithio
The composition of sulfenamide and silicon tetrachloride.
It is preferred that, the activator is mass ratio 1:1:The composition of 4 nano zine oxides, zinc stearate and diethanol amine.
It is preferred that, the preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1-1.5h, compound stabilizer, activator, stearine then added under agitation, 210-215 DEG C is warming up to,
Melting stirring 2-3h, obtains molten state material；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
30-40min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse processing 20-25min obtains mixture two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 3-5h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding is produced
Grade insoluble sulphur in high dispersive.
It is preferred that, step 3) in it is ultrasonically treated be specially 25-28KHz.
It is preferred that, step 4) in chilling liquid be water, temperature be 8 DEG C.
It is preferred that, step 4) in after ball milling particle diameter be less than 70 μm.
It is preferred that, step 4) in insoluble sulfur content is more than 60% in grade insoluble sulphur in high dispersive.
Due to using above-mentioned technical scheme, the beneficial effects of the invention are as follows：The present invention is prepared insoluble using fusion method
Sulphur, gas-phase silica, activator, stearine are added with raw material jointly, are coordinated compound stabilizer, are effectively increased
The heat endurance of insoluble sulfur, and reverse reduction is effectively prevented during the long chain extension of high temperature, improve insoluble sulfur
Conversion ratio, insoluble sulfur content is up to more than 60%.It is cross-linking modified using polystyrene, m-chloro epoxy benzoic acid, coordinate silicon
Acrylic emulsion effectively increases the stability of insoluble type sulphur end group, and has certain protection effect to insoluble type sulphur powder surface
Really, combination property is improved, period of validity is extended.Middle grade insoluble sulphur produced by the present invention has high content, high score
Property and high thermal stability are dissipated, compared to the yield that tradition preparation substantially increases insoluble sulfur.
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.Based on embodiments of the invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
Embodiment 1：
Grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 100
Part, 0.7 part of compound stabilizer, 0.1 part of activator, 0.06 part of gas-phase silica, 3 parts of polystyrene, m-chloro epoxy benzoic acid 0.7
Part, 0.05 part of silicone acrylic emulsion, 0.6 part of stearine.
The preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1.5h, compound stabilizer, activator, stearine are then added under agitation, 215 DEG C are warming up to, melting is stirred
2.5h is mixed, molten state material is obtained；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
35min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse handles 20min under the conditions of 26KHz, must mix
Thing two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 3h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding produces height
Insoluble sulfur content is 62% in grade insoluble sulphur in grade insoluble sulphur in scattered, high dispersive.
Embodiment 2：
Grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 105
Part, 0.5 part of compound stabilizer, 0.15 part of activator, 0.3 part of gas-phase silica, 2 parts of polystyrene, m-chloro epoxy benzoic acid 1.2
Part, 0.08 part of silicone acrylic emulsion, 0.1 part of stearine.
The preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1.5h, compound stabilizer, activator, stearine are then added under agitation, 210 DEG C are warming up to, melting is stirred
2h is mixed, molten state material is obtained；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
40min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse handles 25min under the conditions of 28KHz, must mix
Thing two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 4h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding produces height
Insoluble sulfur content is 65% in grade insoluble sulphur in grade insoluble sulphur in scattered, high dispersive.
Embodiment 3：
Grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 110
Part, 1 part of compound stabilizer, 0.12 part of activator, 0.5 part of gas-phase silica, 2 parts of polystyrene, m-chloro epoxy benzoic acid 1.5
Part, 0.08 part of silicone acrylic emulsion, 0.6 part of stearine.
The preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1h, compound stabilizer, activator, stearine are then added under agitation, be warming up to 215 DEG C, melting stirring
3h, obtains molten state material；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
40min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse handles 25min under the conditions of 28KHz, must mix
Thing two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 4h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding produces height
Insoluble sulfur content is 63% in grade insoluble sulphur in grade insoluble sulphur in scattered, high dispersive.
Embodiment 4：
Grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 105
Part, 1.5 parts of compound stabilizer, 0.1 part of activator, 0.05 part of gas-phase silica, 3 parts of polystyrene, m-chloro epoxy benzoic acid 1
Part, 0.06 part of silicone acrylic emulsion, 0.8 part of stearine.
The preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1.2h, compound stabilizer, activator, stearine are then added under agitation, 210 DEG C are warming up to, melting is stirred
2.5h is mixed, molten state material is obtained；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
30min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse handles 20min under the conditions of 25KHz, must mix
Thing two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 3.5h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding is produced
Insoluble sulfur content is 64% in grade insoluble sulphur in grade insoluble sulphur in high dispersive, high dispersive.
Embodiment 5：
Grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 100
Part, 1.2 parts of compound stabilizer, 0.12 part of activator, 0.4 part of gas-phase silica, 1 part of polystyrene, m-chloro epoxy benzoic acid 0.5
Part, 0.1 part of silicone acrylic emulsion, 1 part of stearine.
The preparation method of grade insoluble sulphur in high dispersive, step is as follows：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of fritting
Melt 1h, compound stabilizer, activator, stearine are then added under agitation, be warming up to 215 DEG C, melting stirring
2.5h, obtains molten state material；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirrings
35min is reacted, 40 DEG C is then cooled to and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse handles 20min under the conditions of 26.5KHz, obtains mixed
Compound two；
4) mixture two is added into chilling night high speed stirring 8-10min, molten state material is then poured into chilling liquid again
In, insoluble sulfur crude product must be solidified, 5h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding produces height
Insoluble sulfur content is 63% in grade insoluble sulphur in grade insoluble sulphur in scattered, high dispersive.
Product made from the embodiment of the present invention is subjected to performance test, obtained：
3h is heated at 95 DEG C, insoluble sulfur changes of contents rate is less than 1.5%；15min, insoluble sulfur are heated at 105 DEG C
Sulphur changes of contents rate is less than 4%；15min is heated at 110 DEG C, insoluble sulfur changes of contents rate is less than 7.5%；Add at 115 DEG C
Hot 15min, insoluble sulfur changes of contents rate is less than 21.5%.
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 (8)
1. grade insoluble sulphur in a kind of high dispersive, it is characterised in that be made up of following mass fraction：Element sulfur raw material 100-
110 parts, 0.5-1.2 parts of compound stabilizer, 0.1-0.15 parts of activator, 0.05-0.5 parts of gas-phase silica, polystyrene 1-3
Part, 0.5-1.5 parts of m-chloro epoxy benzoic acid, 0.05-0.1 parts of silicone acrylic emulsion, 0.1-1 parts of stearine.
2. grade insoluble sulphur in high dispersive according to claim 1, it is characterised in that：The compound stabilizer is matter
Amount compares 1:3:The composition of 15 hexamethylenetetramine, N cyclohexyl 2 benzothiazole sulfenamide and silicon tetrachloride.
3. grade insoluble sulphur in high dispersive according to claim 1, it is characterised in that：The activator is mass ratio
1:1:The composition of 4 nano zine oxides, zinc stearate and diethanol amine.
4. the preparation method of grade insoluble sulphur in high dispersive according to claim 1, it is characterised in that step is such as
Under：
1) added after element sulfur raw material is well mixed with gas-phase silica in pyroreaction kettle, be first warming up to 142 DEG C of pre-fusion 1-
1.5h, then adds compound stabilizer, activator, stearine under agitation, is warming up to 210-215 DEG C, melting
2-3h is stirred, molten state material is obtained；
2) polystyrene is dissolved in carbon tetrachloride, be then added thereto m-chloro epoxy benzoic acid, be warming up to 70 DEG C of stirring reactions
30-40min, is then cooled to 40 DEG C and stands insulation 1h, obtain mixture one；
3) silicone acrylic emulsion is slowly added in mixture one, ultrasonic disperse processing 20-25min obtains mixture two；
4) mixture two is added into chilling night high speed stirring 8-10min, then molten state material is poured into chilling liquid again, obtained
Solidify insoluble sulfur crude product, 3-5h is dried in vacuo under the conditions of 55 DEG C after filtering, washing, then ball mill grinding produces high dispersive
Middle grade insoluble sulphur.
5. grade insoluble sulphur in high dispersive according to claim 4, it is characterised in that：Step 3) in ultrasonically treated tool
Body is 25-28KHz.
6. grade insoluble sulphur in high dispersive according to claim 4, it is characterised in that：Step 4) in chilling liquid be
Water, temperature is 8 DEG C.
7. grade insoluble sulphur in high dispersive according to claim 4, it is characterised in that：Step 4) in particle diameter after ball milling
Less than 70 μm.
8. grade insoluble sulphur in high dispersive according to claim 4, it is characterised in that：Step 4) in product in high dispersive
Insoluble sulfur content is more than 60% in the insoluble sulfur of position.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324290A (en) * | 2017-09-01 | 2017-11-07 | 上海京海（安徽）化工有限公司 | A kind of high-grade insoluble sulfur extraction process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2076843C1 (en) * | 1996-05-28 | 1997-04-10 | Смирнов Александр Витальевич | Method of producing polymer sulfur |
| JP3697248B2 (en) * | 2003-04-21 | 2005-09-21 | 四国化成工業株式会社 | Insoluble sulfur composition |
| CN104724681A (en) * | 2015-03-18 | 2015-06-24 | 无锡华盛橡胶新材料科技股份有限公司 | Highly dispersed high-stability insoluble sulfur and preparation method thereof |
| 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 |
| CN106395757A (en) * | 2016-03-02 | 2017-02-15 | 赵水斌 | Fully-automatic continuous production method for insoluble sulfur |
-
2017
- 2017-04-11 CN CN201710233873.0A patent/CN107055483B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2076843C1 (en) * | 1996-05-28 | 1997-04-10 | Смирнов Александр Витальевич | Method of producing polymer sulfur |
| JP3697248B2 (en) * | 2003-04-21 | 2005-09-21 | 四国化成工業株式会社 | Insoluble sulfur composition |
| CN104724681A (en) * | 2015-03-18 | 2015-06-24 | 无锡华盛橡胶新材料科技股份有限公司 | Highly dispersed high-stability insoluble sulfur and preparation method thereof |
| 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 |
| CN106395757A (en) * | 2016-03-02 | 2017-02-15 | 赵水斌 | Fully-automatic continuous production method for insoluble sulfur |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107324290A (en) * | 2017-09-01 | 2017-11-07 | 上海京海（安徽）化工有限公司 | A kind of high-grade insoluble sulfur extraction process |
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