KR20170051956A - manufacturing method of insoluble sulfur using diisopropenyl benzene - Google Patents

manufacturing method of insoluble sulfur using diisopropenyl benzene Download PDF

Info

Publication number
KR20170051956A
KR20170051956A KR1020150153707A KR20150153707A KR20170051956A KR 20170051956 A KR20170051956 A KR 20170051956A KR 1020150153707 A KR1020150153707 A KR 1020150153707A KR 20150153707 A KR20150153707 A KR 20150153707A KR 20170051956 A KR20170051956 A KR 20170051956A
Authority
KR
South Korea
Prior art keywords
sulfur
insoluble sulfur
polymer
insoluble
weight
Prior art date
Application number
KR1020150153707A
Other languages
Korean (ko)
Other versions
KR101833252B1 (en
Inventor
염용화
성대진
최현
최정민
문종박
Original Assignee
현대오일뱅크 주식회사
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 현대오일뱅크 주식회사 filed Critical 현대오일뱅크 주식회사
Priority to KR1020150153707A priority Critical patent/KR101833252B1/en
Publication of KR20170051956A publication Critical patent/KR20170051956A/en
Application granted granted Critical
Publication of KR101833252B1 publication Critical patent/KR101833252B1/en

Links

Images

Classifications

    • 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)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a method for producing insoluble sulfur using diisopropenylbenzene. The method for producing insoluble sulfur includes a step of producing an insoluble sulfur-based polymer by undergoing a bulk polymerization using diisopropenylbenzene (DIB) and ground sulfur acquired as a byproduct during a desulfurization process in an oil refinery, thereby increasing applicability of ground sulfur and reducing production costs for insoluble sulfur.

Description

[0001] The present invention relates to a method for producing insoluble sulfur using diisopropenylbenzene,

The present invention relates to insoluble sulfur as an additive for tires, and more particularly, to an insoluble sulfur polymer produced by adding diisopropenyl benzene (DIB) to a sulfur powder generated in a desulfurization process of an oil refinery, The present invention relates to a method for producing an insoluble sulfur by which an insoluble sulfur is produced by pulverizing, adding an additive and drying.

At the refinery, a desulfurization process is required in the process of refining the crude oil, where a large amount of liquid sulfur is produced. Such liquid sulfur can be used as sulfuric acid, fertilizer, etc. However, it is necessary to develop the application field by saturating the domestic market.

Another use of sulfur is insoluble sulfur, which is used to increase the strength and durability of rubber by adding sulfur to rubber raw materials when manufacturing tires. When sulfur is used, the sulfur molecular weight in the rubber is small so that it can move within the rubber. Resulting in a blooming phenomenon moving out of the rubber surface.

Such a blooming phenomenon lowers the adhesion of the rubber, which causes a problem in a portion to be bonded to the tire cord, which is a cause of deterioration of the physical properties of the rubber. There is a problem of deterioration of physical properties due to excessive addition of a pressure-sensitive adhesive used to overcome this problem, and a problem of lower productivity when the reaction rate is kept low by keeping a low temperature.

In order to solve such a blooming problem, insoluble sulfur using an insoluble sulfur polymer is applied to a specific portion such as rubber using a tire cord. This insoluble sulfur has no domestic producers and secures the technology in some overseas companies. As a result, it is relying on foreign imports in the form of oligopoly, and high prices are maintained.

In addition, a known conventional method for producing insoluble sulfur requires a process of vaporizing sulfur at a high temperature of 600 ° C or higher, and there is a risk of erosion and explosion of a manufacturing reactor due to operation technology, energy consumption, sulfur SO 3 conversion due to high temperature have. Furthermore, the reaction yield of the insoluble sulfur polymer is 30% in the liquid sulfur method, and 70% of the vaporized sulfur method, and requires the removal of unreacted sulfur and a solvent recycling process, where the solubility of the sulfur very high CS 2 Is used as a solvent. CS 2 is a toxic solvent that is not environmentally friendly and can cause personnel accidents. In addition, the vulcanization rate is generally determined by the vulcanization temperature of rubber and sulfur. Since the vulcanization speed directly affects the productivity, it is important to improve the speed, but commercial insoluble sulfur limits the vulcanization temperature due to the blooming problem .

This is because the conventional insoluble sulfur is produced by using sulfur only to produce a sulfur polymer, and because of the nature of sulfur, it decomposes from a polymer into a low molecule and eventually becomes a general sulfur. To prevent this, a stabilizer such as a radical scavenger is used. However, it is a key point of the technology to have a stabilizer which produces a stable insoluble sulfur with the limitation of the stabilizer in view of the nature of the material.

Conventionally, in order to secure the stability of the insoluble sulfur polymer, a lot of studies have been conducted to use co-polymerization using an organic material having a double bond such as dicyclopentadiene, but stability can not be obtained because a high molecular weight can not be obtained I can not.

It can be seen from Patent Document 1 and Non-Patent Document 1 that diisopropenyl benzene in an organic material can produce a sulfur polymer which is very stable according to the amount of organic matter in the production of sulfur and polymer.

In the above non-patent document 1, the sulfur polymer is very stable and is applied as a positive electrode material for a battery. In this case, the physical properties of a sulfur polymer having a DIB amount of 10 to 50% are focused.

PCT / US2012 / 050602)

NATURE CHEMISTRY, 5,518 (2013)

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a process for producing diisopropylacetate It is an object of the present invention to provide a method for producing insoluble sulfur using phenylene benzene.

It is another object of the present invention to provide a method for producing insoluble sulfur, which is capable of reducing the risk of explosion and energy consumption, increasing the yield, lowering the temperature at the time of producing insoluble sulfur, controlling the stability of the insoluble sulfur polymer, It is an object of the present invention to provide a sulfur production method.

It is an object of the present invention to provide a process for the production of sulfur-containing sulfur (DIB) by bulk polymerization of sulfur sulfur and diisopropenyl benzene obtained as a by- And a step of producing a polymer.

According to an aspect of the present invention, the method further comprises separating and recovering unreacted sulfur by using toluene in step a).

According to another aspect of the present invention, there is provided a method for producing an insoluble sulfur polymer, comprising the steps of: b) pulverizing an insoluble sulfur polymer; c) mixing the ground insoluble sulfur polymer with an additive; And d) drying the mixture obtained in step c).

According to another aspect of the present invention, it is preferable that the ratio of the sulfur powder to the diisopropenyl benzene in step a) is 1: 0.030 to 7.0.

According to another aspect of the present invention, in step a), the reaction temperature is 160 to 190 ° C, and the reaction time is preferably 5 to 60 minutes.

According to another aspect of the present invention, in step b), the insoluble sulfur polymer is preferably pulverized to a size of 10 to 35 mu m.

According to another aspect of the present invention, in step b), the insoluble sulfur polymer is pulverized and sorted through a wet process with a benzene-based solvent.

According to another aspect of the present invention, the additive in step c) comprises 10 to 30 parts by weight of a process oil, 0.5 to 2 parts by weight of a dispersant, and 0.5 to 2 parts by weight of a stabilizer, based on 100 parts by weight of the insoluble sulfur polymer .

According to the present invention, an insoluble sulfur polymer is prepared by adding diisopropenyl benzene to a sulfur powder which is a by-product generated in a desulfurization process of an oil refining plant. The insoluble sulfur polymer is pulverized, By manufacturing the sulfur, it is possible to increase the utilization value of the sulfur powder and lower the production cost of the insoluble sulfur.

Also, by lowering the reaction temperature of diisopropenyl benzene and sulfur powder, the present invention has the effect of reducing energy consumption, simplifying operating conditions, and reducing explosion risk.

In addition, since the stability of the insoluble sulfur polymer, which is an important characteristic of insoluble sulfur, can be controlled according to the amount of diisopropenylbenzene, the present invention has an effect that the polymer properties can be controlled as needed.

In addition, the yield is 30% of the conventional liquid sulfur production process and yield of the insoluble sulfur production process according to the present invention compared with a conventional vaporizing sulfur recipe of 70% is to obtain a high yield of 98% or more, by using the CS 2 Unlike the conventional method of removing unreacted sulfur, the use of toluene in the removal of unreacted sulfur has an advantage in that the toxic substances are not used and the stability is improved and the environment is harmless.

1 is a characteristic graph of torque according to vulcanization time.
2 is a graph of the tensile rate characteristics of the vulcanized rubber composition.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The method for producing insoluble emulsion using diisopropenyl benzene according to an embodiment of the present invention is a method for producing insoluble emulsion using diisopropenyl benzene by using sulfur sulfur obtained as a by-product in the desulfurization process of an oil refinery and high- Insoluble sulfur polymer is prepared by mixing diisopropenyl benzene used in the production.

The reaction conditions in the method for producing an insoluble sulfur according to the embodiment of the present invention are as follows: the mixing ratio of sulfur powder to diisopropenylbenzene is 1: 0.030 to 0.070 by weight, the reaction temperature is 160 to 190 ° C, The reaction time is set to 5 minutes to 60 minutes.

More specifically, at a temperature of 160 ° C or higher, the rate at which the ring of sulfur S8 is ringed becomes very high, so that radicals are formed, self-polymers are produced, and the molecular weight is not high. In this case, using a powerful mechanical stirrer, stir at 450 rpm. When diisopropenylbenzene is added, a sulfur chain of a certain length is combined with diisopropenylbenzene to obtain an insoluble sulfur polymer suitable for insoluble sulfur have.

When diisopropenylbenzene is added to sulfur at 120-160 ° C, which is lower than the above-mentioned reaction temperature, the interval between sulfur and diisopropenylbenzene is small, so that the sulfur decomposed in the sulfur chain will be vulcanized in the future. The proportion is not correct and a large amount of diisopropenyl benzene is required.

In addition, when sulfur and diisopropenylbenzene are reacted at a temperature higher than the above reaction temperature of 190 ° C or higher, the sulfur decomposition rate is higher than the sulfur bonding rate, making it difficult to obtain a polymer condition having a high molecular weight.

The insoluble sulfur polymer thus prepared must be pulverized to an optimum size suitable for the insoluble sulfur. The optimum size of the insoluble sulfur polymer may be 35 탆 or less, preferably 10 to 35 탆.

As a method of pulverizing the insoluble sulfur polymer, for example, a wet method using a benzene-based solvent may be used. According to the wet method using the benzene-based solvent, a certain size of insoluble sulfur polymer particles can be obtained.

In this case, the additive is divided into processor oil, dispersant and stabilizer in order to have stable characteristics and to be well dispersed in rubber. In this case, the additive is added to the insoluble sulfur polymer 100 in an amount of 10 to 30 parts by weight, To 2 parts by weight, and a stabilizer in an amount of 0.5 to 2 parts by weight.

500 g of sulfur was stirred at 175 캜, and 25 g of diisopropenylbenzene was added thereto, and a polymer was obtained through a reaction for 30 minutes. At high temperature, decomposition proceeds at the same time, so it was cooled down in cold water and the reaction was terminated at room temperature.

The above polymer is a red opaque polymer, which is rigid. HTS (high thermal stability, when the sulfur polymer is applied for 15 minutes at 110 ° C, the sulfur polymer is changed from the polymer to the low molecule, which is the ratio of the low molecular weight to the total amount).

30 g of diisopropenylbenzene was added while stirring 500 g of sulfur at 175 DEG C, and the polymer was obtained through a reaction for 30 minutes. At high temperature, decomposition proceeds at the same time, so it was cooled down in cold water and the reaction was terminated at room temperature.

The above polymer becomes a transparent polymer of red color, and shows a characteristic of a rubbery rubber which is hard for a day. In the HTS test, a stable polymer can be obtained at 8.4%.

As a result of various experiments other than the above examples, it was found that the ratio of sulfur powder to diisopropenylbenzene was 1: 0.030 to 7.0, the reaction temperature was 160 to 190 ° C, and the reaction time was 5 to 60 minutes , And the insoluble sulfur polymer is pulverized to a size of 10 to 35 mu m. The additives are 10 to 30 parts by weight of the process oil, 0.5 to 2 parts by weight of the dispersing agent and 0.5 to 2 parts by weight of the stabilizer per 100 parts by weight of the insoluble sulfur polymer .

 Recipe code Material F article Example 1 Example 2 NR 60 60 60 BR 20 20 20 SBR 20 20 20 Zinc oxide 3 3 3 Stearic acid One One One N660 50 50 50 Naphthenic oil 15 15 15 Tackifying resin 2 2 2 MBTS 1.0 1.0 1.0 DPG 0.25 0.25 0.25 Insolube sulfur 3.0 3.0 3.0 Total 175.25 177.25 178.25 Compound property (Unit) Measured value Mooney viscosity (ML1 + 4,100 < 0 > C) 47.3 47.8 47.7 M L (1 bf.in) * 0.093 0.080 0.083 M H (1bf.in) * 1.008 0.983 0.980 t 10 (min) * 1.88 2.15 2.19 t 90 (min) * 4.83 5.09 5.09 Vulcanization property (Unit) Measured vale Hardness (Shorea) 52-53 52-54 54-55 Shecific gravity 1.10 1.11 1.11 Tensile strength (kgf / ㎠) 195 198 180 Elongation (%) 585 620 560 Modulus at 100% (kgf / cm2) 18 17 19 Modulus at 300% (kgf / ㎠) 83 78 83 Tear strength (kgf / cm) 76 71 79 Akron abrasion (cc / 1000rev) 0.10 0.120 0.15 Compression set (%) *** 8 11 25

The data in Table 1 above are press molding at 155 DEG C, ODR (Oscillating Disk Rheometer) measurement, and 155 DEG C x t90.

As a result of the rubber vulcanization test, as shown in Table 1 above, Example 1 showed similar results to commercial products, but Example 2 shows that the results are off. The insoluble sulfur is a small part of the low molecular weight and is required to participate in vulcanization, but the vulcanization is less in Example 2 because the stability is higher than that of commercial products.

As a result of the above ODR test, it was confirmed that both t10 and t90 are slower than the commercial products as shown in Fig. Bin scotch is glass, but press time is 5% slower, but it can be seen that the amount of sulfur due to diisopropenylbenzene is relatively small compared to commercial products, so the amount of insoluble sulfur is increased It was confirmed that it was improved.

In the tensile strength test, as shown in FIG. 2, Example 1 exhibited similar characteristics to those of the conventional article. In Example 2, however, the tensile strength and elongation at the point of breakage were found to be different from those of the article.

[Comparative Example 1]

35 g of diisopropenyl benzene was added while stirring 500 g of sulfur at 175 DEG C, and the polymer was obtained through a reaction for 30 minutes. At high temperature, decomposition proceeds at the same time, so it was cooled down in cold water and the reaction was terminated at room temperature.

The above polymer is a red transparent polymer and has a rigid property. It is not suitable for insoluble sulfur because it can not be vulcanized to 0% in HTS test.

[Comparative Example 2]

15 g of diisopropenylbenzene was added to 500 g of sulfur while stirring at 175 DEG C, and a polymer was obtained through a reaction for 30 minutes. At high temperature, decomposition proceeds at the same time, so it was cooled down in cold water and the reaction was terminated at room temperature.

The above polymer was a bright red opaque polymer and showed a rigid property. In the HTS test, it was found that the application of insoluble sulfur at 42% resulted in excessive vulcanization and blooming phenomenon.

The present invention relates to a process for producing an insoluble sulfur polymer by adding diisopropenyl benzene to a sulfur powder which is a by-product generated in a desulfurization process of an oil refining plant. The insoluble sulfur polymer is pulverized, By manufacturing, it is possible to supply a product that increases the utilization value of sulfur powder and reduces the manufacturing cost of insoluble sulfur.

Claims (9)

(a) Bulk polymerization of sulfur sulfur and diisopropenyl benzene (DIB) obtained as a by-product in a desulfurization process at an oil refinery to produce an insoluble sulfur polymer , A method for producing insoluble sulfur. The method of claim 1,
Further comprising the step of separating and recovering the unreacted sulfur by using toluene in the step a). 3. The method according to claim 1 or 2,
b) pulverizing the insoluble sulfur polymer;
c) mixing the pulverized insoluble sulfur polymer with an additive; And
d) drying the mixture obtained in step c);
≪ / RTI > The method according to claim 1,
Wherein the ratio of the sulfur powder to the diisopropenylbenzene in the step (a) is 1: 0.030 to 7.0 in weight ratio. The method according to claim 1,
Wherein the reaction temperature in step a) is 160 to 190 占 폚 and the reaction time is 5 to 60 minutes. The method of claim 3,
Wherein in step b), the insoluble sulfur polymer is ground to a size of 10 to 35 mu m. The method of claim 3,
Wherein the insoluble sulfur polymer is pulverized and selected through a wet process using a benzene-based solvent in the step b). The method according to claim 1,
Wherein the additive in step c) comprises 10 to 30 parts by weight of a process oil, 0.5 to 2 parts by weight of a dispersant, and 0.5 to 2 parts by weight of a stabilizer, based on 100 parts by weight of the insoluble sulfur polymer. Way. An insoluble sulfur produced by the process of any one of claims 1 to 8.
KR1020150153707A 2015-11-03 2015-11-03 manufacturing method of insoluble sulfur using diisopropenyl benzene KR101833252B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020150153707A KR101833252B1 (en) 2015-11-03 2015-11-03 manufacturing method of insoluble sulfur using diisopropenyl benzene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020150153707A KR101833252B1 (en) 2015-11-03 2015-11-03 manufacturing method of insoluble sulfur using diisopropenyl benzene

Publications (2)

Publication Number Publication Date
KR20170051956A true KR20170051956A (en) 2017-05-12
KR101833252B1 KR101833252B1 (en) 2018-03-02

Family

ID=58740161

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020150153707A KR101833252B1 (en) 2015-11-03 2015-11-03 manufacturing method of insoluble sulfur using diisopropenyl benzene

Country Status (1)

Country Link
KR (1) KR101833252B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210156002A (en) * 2020-06-17 2021-12-24 주식회사 엔티시스템 Manufacturing method of insoluble sulfur
CN114348969A (en) * 2022-01-12 2022-04-15 嘉兴学院 Preparation method of insoluble sulfur

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101491969B1 (en) * 2013-09-16 2015-02-11 에이치설퍼 주식회사 Process for production of high quality insoluble sulfur

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20210156002A (en) * 2020-06-17 2021-12-24 주식회사 엔티시스템 Manufacturing method of insoluble sulfur
CN114348969A (en) * 2022-01-12 2022-04-15 嘉兴学院 Preparation method of insoluble sulfur

Also Published As

Publication number Publication date
KR101833252B1 (en) 2018-03-02

Similar Documents

Publication Publication Date Title
CN106062019B (en) Ethylene/alpha-olefin/unconjugated polyene copolymer, its manufacturing method and purposes
KR101577651B1 (en) Novel cardanol based organic vulcanizing agent, manufacturing method of the same and rubber composition for tire using the same
CN1934182A (en) Rubber composition and pneumatic tire using same
CN102341451A (en) Vibration-damping rubber composition
KR101833252B1 (en) manufacturing method of insoluble sulfur using diisopropenyl benzene
CN107531942A (en) Crosslinkable rubber composition
CN103923351A (en) Preparation method of lignocellulose/montmorillonite rubber reinforcing agent and rubber reinforcing method
EP2488587B1 (en) Crumb rubber modified asphalt with improved stability
CN104262976A (en) Air tightness improver as well as preparation method and application thereof
CN1324079C (en) Mfg. process olefine series thermoplastics elastomer compsn.
CN103382270A (en) Anti-corrosion rubber composition and anti-corrosion rubber lining
CN102585294A (en) Compound rubber bonding promoting agent and preparation method thereof
US20220403056A1 (en) Cured rubber network with covalent and hydrogen-bonded crosslinks
CN101173063A (en) Multifunctional rubber chemicals and method for producing the same
TWI225876B (en) In situ preparation of A bis-(benzothiazolesulfen) amide in a polymeric matrix
CN1286860C (en) Synthesis and use of chain-coupled polymeric sulfide compounds in rubber formulations
JP5731321B2 (en) Rubber composition for tire and pneumatic tire
JP2013155305A (en) Rubber composition for tire, production method thereof, and pneumatic tire
CN101659827A (en) Long-afterglow luminescent paint
KR20040056562A (en) Acrylonitrile butadiene rubber resin composition for oil seal
CN111073085A (en) Wear-resistant rubber material and preparation method thereof
KR102037271B1 (en) Organic vulcanizing agent for rubber compounding, preparation method of the same, and rubber compounding composition containing the same
CN109401083A (en) A kind of sealing ring modified EPT rubber and preparation method thereof
KR100454284B1 (en) Preparation of a rubber composition having a high elongation
CN108034150A (en) A kind of wear-resisting type nano-composite rubber

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
AMND Amendment
E902 Notification of reason for refusal
AMND Amendment
E601 Decision to refuse application
AMND Amendment
X701 Decision to grant (after re-examination)
GRNT Written decision to grant