CN103937540A - Organic polythioether mixing vulcanizing agent and synthetic method thereof - Google Patents
Organic polythioether mixing vulcanizing agent and synthetic method thereof Download PDFInfo
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Abstract
The invention discloses an organic polythioether mixing vulcanizing agent and a synthetic method thereof. The general formula of the mixing vulcanizing agent is R-Sx-R, wherein R represents n-alkyl or iso-alkyl, x is selected from more than two of integers of 2-6, and the mass percentage of sulfur in the mixing vulcanizing agent is 50-70%. The synthetic method for the vulcanizing agent is environment-friendly by using easily available and harmless haloalkane as a raw material, the reaction conditions are mild, and the reaction time is relatively short; the synthetic product is high in sulfur content, wide in decomposition temperature range and good in oil solubility; when the vulcanizing agent is used for pre-vulcanizing treatment of a hydrogenation catalyst, the sulfur holding rate of the catalyst is high, and the pre-vulcanizing cost can be effectively reduced; moreover, the vulcanizing agent has a relatively large heat absorption effect in the process of introducing H2 to prepare H2S, and can counteract part of heat released in the subsequent vulcanizing process of the catalyst, thus realizing alleviated heat release in the pre-vulcanizing process of the hydrogenation catalyst, avoiding the phenomenon of centralized heat release during pre-vulcanizing treatment of the hydrogenation catalyst and achieving broad industrial application prospect.
Description
Technical field
The invention belongs to vulcanizing agent technical field, be specifically related to a kind of organic polythiaether mix sulphur agent and synthetic method thereof for catalytic hydrogenation catalyst prevulcanized.
Background technology
Quality and the environment of oil product are closely bound up, and the present general heaviness of crude oil, wherein contain relatively large nitrogen, sulphur, oxygen and metal, in addition the most oil product of China carrys out catalytic cracking, olefin(e) centent is higher, unavoidably can produce larger disadvantageous effect to environment, adopt catalytic hydrogenation process can effectively reduce these harm.Industry hydrogenation catalyst great majority are taking elements such as molybdenum, cobalt, nickel, tungsten as active ingredient, and they are attached on carrier with oxidation state, but not only active low but also poor stability, easy inactivation of the catalyzer of oxidation state.Research shows, the catalyzer of sulphided state not only active high, selectivity good and more stable, long service life, meanwhile, the activity of catalyzer increases along with the rising of sulphidity, so must carry out prevulcanized processing to hydrogenation catalyst.
No matter be prevulcanized or the outer prevulcanized of device in device, all must in the situation that vulcanizing agent exists, just can complete the activation of hydrogenation catalyst.The vulcanizing agent of industrial application mainly includes machine polythiaether if di-t-butyl polythiaether, dimethyl disulfide, dimethyl thioether, tertiary nonyl polythiaether and mercaptan are as normal-butyl mercaptan, ethanethio at present.The smell is awful mostly for mercaptan, toxicity is large and sulphur content is not high, and its industrial application is seriously limited.And organic polythiaether toxicity is lower, decomposition temperature a wider range, oil soluble is good, both can be applicable to prevulcanized in device, also can be widely used in the outer prevulcanized of device, is the main direction of current vulcanizing agent research.
Organic polythiaether is that a class general formula is R-S
x-R
1material, x between 2～20, R and R
1for alkyl, alkaryl, aryl or aralkyl functional group, both can be the same or different, it can be saturated or unsaturated hydro carbons, also can be straight chain, side chain or cycloalkane, it synthesizes multiple route, both at home and abroad the normal method using is taking mercaptan and elemental sulfur as raw material, prepares organic polythiaether under catalyzer existence condition.The developing direction of this method is mainly that tradition catalyzer used is improved as amine, alkylamine, alkanolamine, mineral alkali, thiolate and alcoholate, is RSHx (C as US4876389 adopts a kind of general formula
mh
2mo) composition catalyst of yMOH, US5068445 adopt basic resin to make catalyzer, US6051739 to utilize traditional alkaline matter and general formula be R
2o[CH
2cH (R
3) O]
nsO
3the surfactant of M is combined and is made catalyzer, and building-up reactions product yield improves, and catalyzer is easy and product separation.It is a kind of taking alkene, sulphur and hydrogen sulfide as raw material that US4937385, US6472354, US6544936 provide respectively, prepares the method for organic polythiaether under different catalysts existence condition.Its response path is: under the condition first existing at elemental sulfur, hydrogen sulfide and olefine reaction generate intermediate product alkyl sulfhydryl compounds, the then sulfur molecule open loop of being heated generates organic polythiaether of multiple different sulphur atom content under basic catalyst existence condition.Aforesaid method or use mercaptan are as substrate, or in reaction process, have mercaptan to produce as intermediate, because most of mercaptan prices are more expensive, and be poisonous, accompany cacodorous compound, therefore the organic polythiaether of gained is because of dissolved hydrogen sulfide and unreacted mercaptan, the smell is awful, less stable.
US5135670, US5338468, US5849677, CN200710098327.7 disclose respectively a kind of taking alkene and elemental sulfur as raw material, the method of organic polythiaether that preparation contains polysulfide crosslink bond under different catalysts effect, this method preparation technology is simple, cost of material is cheaply easy to get, do not introduce halogen, but its products obtained therefrom impurity is more, the smell is awful and products therefrom sulphur content is lower.US4204969, US5410088, CN1534019 provide respectively a kind of taking alkene with halogenation sulphur as raw material, under different catalysts effect, first generate the olefine sulfide of halogen-containing group, after prepare the method for purer polythiaether through dehalogenate.This synthetic route products therefrom sulphur content is higher, and condition is gentleer, but produces a large amount of waste water, waste gas (HCl, H in reaction
2the gases such as S), waste residue (containing NaCl and sulfide), process three wastes difficulty.Also have scholar taking alkylating reagent and sulphur or thiocarbamide as raw material, synthetic symmetrical alkyl disulfide under different catalysts effect, this method reaction conditions gentleness, resultant productive rate is high, good reaction selectivity, but prepared sulfide is mostly single disulphide.
Summary of the invention
A technical problem to be solved by this invention is to overcome the problems such as existing organic polythiaether class vulcanizing agent toxicity is large, production cost is high, security is low, transport is difficult, sulphur content is low, provides that a kind of sulphur content is high, decomposition temperature wide ranges, organic polythiaether mix sulphur agent that oil soluble is good.
Another technical problem to be solved by this invention is as above-mentioned organic polythiaether mix sulphur agent provides a kind of environmental friendliness, reacts and takes shorter and mild condition, and mix products can directly apply to the synthetic method of the prevulcanized processing of hydrogenation catalyst.
Solving the problems of the technologies described above adopted technical scheme is: the general formula of this mix sulphur agent is R-S
x-R, in formula, R represents C
2～C
6positive structure or isomery alkyl, x represents the number of S atom, and it gets two or more in 2～6 integer, and in mix sulphur agent, the massfraction of sulphur is 50%～70%.
The synthetic method of above-mentioned organic polythiaether mix sulphur agent is made up of following step:
1, strong alkaline substance and sulphur are dissolved in distilled water than for 1:2～1:10 by amount of substance, normal temperature～80 DEG C reaction 5～60 minutes, isolates unreacted sulphur, obtains the intermediate containing sodium polysulphide.
What 2, obtain to step 1 adds halogenated alkane and phase-transfer catalyst containing in the intermediate of sodium polysulphide, the add-on of halogenated alkane is 1～10 times of strong alkaline substance amount of substance, the add-on of phase-transfer catalyst is 0.5%～10% of strong alkaline substance amount of substance, normal-temperature reaction 0.5～2 hour, naturally be down to normal temperature, standing separation, obtains organic polythiaether mix sulphur agent.
In above-mentioned step 1, preferably strong alkaline substance and sulphur are dissolved in distilled water than for 1:3～1:6 by amount of substance, 50～60 DEG C are reacted 30～60 minutes, isolate unreacted sulphur, obtain the intermediate containing sodium polysulphide.
In above-mentioned step 2, what preferably obtain to step 1 adds halogenated alkane and phase-transfer catalyst containing in the intermediate of sodium polysulphide, the add-on of halogenated alkane is 2 times of strong alkaline substance amount of substance, the add-on of phase-transfer catalyst is 2%～5% of strong alkaline substance amount of substance, normal-temperature reaction 0.5～1.5 hour, naturally be down to normal temperature, standing separation, obtains organic polythiaether mix sulphur agent.
Above-mentioned halogenated alkane is C
2～C
6halogenated alkane; Strong alkaline substance is inorganic sulphide soluble in water, as nine water cure sodium or anhydrous potassium sulphide; Phase-transfer catalyst is any one in polyalcohols, quaternary ammonium salt, cyclic crown ether, tertiary amine, season phosphonium salt, can be specifically any one in Macrogol 200, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, didecyl Dimethy brometo de amonio.
Advantage of the present invention is as follows:
1, high, the decomposition temperature wide ranges of organic polythiaether mix sulphur agent sulphur content of the present invention, oil soluble are good, its synthetic method is selected non-mercaptan, is easy to get, harmless halogenated alkane is raw material, environmental friendliness, and reaction conditions gentleness, take shortlyer, mix products can directly apply in the device of hydrogenation catalyst or the outer prevulcanized processing of device.
2, organic polythiaether mix sulphur agent of the present invention is at logical H
2h processed
2in S process, there is larger endothermic effect, can offset the part heat that subsequent catalyst sulfidation is emitted, be conducive to realize the mitigation heat release of hydrogenation catalyst presulfurizing process, the generation of concentrating exothermic phenomenon while avoiding hydrogenation catalyst presulfurizing to process.
3, organic polythiaether mix sulphur agent of the present invention is for hydrogenation catalyst presulfurizing processing, and catalyzer hold sulphur rate is high, effectively reduces prevulcanized cost, and prospects for commercial application is wide.
Brief description of the drawings
Fig. 1 is diethyl polythiaether mix sulphur agent total ions chromatogram prepared by embodiment 1.
Fig. 2 is the mass spectrum of the diethyl polythiaether mix sulphur agent main ingredient diethyl disulfide prepared of embodiment 1.
Fig. 3 is the mass spectrum of the diethyl polythiaether mix sulphur agent main ingredient diethyl trithioether prepared of embodiment 1.
Fig. 4 is the mass spectrum of the diethyl polythiaether mix sulphur agent main ingredient diethyl tetrasulfide ether prepared of embodiment 1.
Fig. 5 is diethyl polythiaether mix sulphur agent heat decomposition curve prepared by embodiment 1.
Fig. 6 is diethyl polythiaether mix sulphur agent DSC curve prepared by embodiment 1.
Fig. 7 is the XRD spectra that adopts organic polythiaether mix sulphur agent prevulcanized front and back catalyzer of embodiment 1～3 preparation.
Embodiment
The sulphur content of vulcanizing agent is the important indicator of evaluation vulcanizing agent performance quality, below taking vulcanizing agent sulphur massfraction as target value, the present invention is described in more detail in conjunction with the accompanying drawings and embodiments, but protection scope of the present invention is not limited only to these embodiment.
Embodiment 1
To synthesize diethyl polythiaether mix sulphur agent as example, its synthetic method is as follows:
1, by 18g(0.075mol) nine water cure sodium, 9.6g(0.3mol) sulphur, 90mL distilled water adds in 250mL flask and mixes, be placed in the water-bath of magnetic force heating stirrer, at 50 DEG C, react 30 minutes, then naturally near normal temperature, filter, isolate unreacted sulphur, obtain the intermediate containing sodium polysulphide.
What 2, obtain to step 1 adds 16.5g(0.15mol containing in the intermediate of sodium polysulphide) monobromethane and 1.0g(0.003mol) Tetrabutyl amonium bromide, normal-temperature reaction 2 hours, then reaction solution is moved into standing separatory in separating funnel, take off the faint yellow bright organic layer of layer, obtain diethyl polythiaether mix sulphur agent.
Products therefrom adopts gas phase chromatogram-ion trap GC-MS to carry out compositional analysis, the results are shown in Figure 1～4.As seen from the figure, products therefrom is the mixture of diethyl disulfide, diethyl trithioether and diethyl tetrasulfide ether, and its structural formula is respectively:
Its flash-point (cup of remaining silent) is 83.5 DEG C, and the sulphur massfraction that adopts tube furnace high-temp combustion-neutralization titration to measure product is 65.52%.
Products therefrom is respectively at N
2atmosphere and H
2heat decomposition curve in atmosphere is shown in Fig. 5, and DSC curve is shown in Fig. 6.As seen from Figure 5, products therefrom is at H
2in atmosphere, there is wider decomposition temperature scope (50～235 DEG C), be better than being widely used at present and evaluating the decomposition temperature (200～250 DEG C) of good dimethyl disulfide, the generation of concentrating exothermic phenomenon can effectively avoid hydrogenation catalyst presulfurizing to process time., be it can also be seen that by Fig. 6, products therefrom is at logical H meanwhile
2h processed
2in S process, there is larger endothermic effect, can offset the part heat that subsequent catalyst sulfidation is emitted, be conducive to realize the mitigation heat release of hydrogenation catalyst presulfurizing process.
Embodiment 2
To synthesize diisobutyl polythiaether mix sulphur agent as example, its synthetic method is as follows:
In embodiment 1, the chloro-iso-butane of the amount of substances such as monobromethane use used is replaced, other steps are identical with embodiment 1, obtain the mix sulphur agent of diisobutyl disulfide, diisobutyl trithioether, diisobutyl tetrasulfide ether, diisobutyl five thioethers, wherein sulphur massfraction is 55.46%, and its decomposition temperature scope is 55～250 DEG C.
Embodiment 3
To synthesize dihexyl polythiaether mix sulphur agent as example, its synthetic method is as follows:
In embodiment 1, the bromo normal hexane of the amount of substances such as monobromethane use used is replaced, other steps are identical with embodiment 1, obtain the mix sulphur agent of dihexyl disulfide, dihexyl trithioether, dihexyl four thioethers, dihexyl five thioethers, dihexyl six thioethers, wherein sulphur massfraction is 50.19%, and its decomposition temperature scope is 60～260 DEG C.
Embodiment 4
In the present embodiment, the add-on of Tetrabutyl amonium bromide changes 0.5% of nine water cure sodium amount of substances into, and other steps are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 55.09%.
Embodiment 5
In the present embodiment, the add-on of Tetrabutyl amonium bromide changes 2% of nine water cure sodium amount of substances into, and other steps are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 62.50%.
Embodiment 6
In the present embodiment, the add-on of Tetrabutyl amonium bromide changes 5% of nine water cure sodium amount of substances into, and other steps are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 64.25%.
Embodiment 7
In the present embodiment, the add-on of Tetrabutyl amonium bromide changes 10% of nine water cure sodium amount of substances into, and other steps are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 64.33%.
Embodiment 8
In the step 1 of embodiment 1, temperature of reaction is down to normal temperature, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 60.70%.
Embodiment 9
In the step 1 of embodiment 1, temperature of reaction is increased to 60 DEG C, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 63.27%.
Embodiment 10
In the step 1 of embodiment 1, temperature of reaction is increased to 80 DEG C, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 63.05%.
Embodiment 11
In the step 1 of embodiment 1, it is original 1/2 that the consumption of sulphur changes into, and other conditions are identical with embodiment 1, obtain diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 50.53%.
Embodiment 12
In the step 1 of embodiment 1, it is original 3/4 that the consumption of sulphur changes into, and other conditions are identical with embodiment 1, obtain diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 57.48%.
Embodiment 13
In the step 1 of embodiment 1, the consumption of sulphur changes original 1.5 times into, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 65.19%.
Embodiment 14
In the step 1 of embodiment 1, the reaction times foreshortens to 5 minutes, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 59.52%.
Embodiment 15
In the step 1 of embodiment 1, the reaction times extends to 60 minutes, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 65.86%.
Embodiment 16
In the step 2 of embodiment 1, the reaction times foreshortens to 0.5 hour, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 60.10%.
Embodiment 17
In the step 2 of embodiment 1, the reaction times foreshortens to 1.5 hours, and other conditions are identical with embodiment 1, obtains diethyl polythiaether mix sulphur agent, and wherein sulphur massfraction is 63.78%.
Embodiment 18
In embodiment 1～17, Tetrabutyl amonium bromide use used waits the Macrogol 200 of amount of substance to replace, and other steps are identical with corresponding embodiment, obtain organic polythiaether mix sulphur agent.
The Macrogol 200 of the present embodiment also can be with any one replacement waiting in the tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, didecyl Dimethy brometo de amonio of amount of substance.
In order to prove beneficial effect of the present invention, contriver adopts organic polythiaether mix sulphur agent (hereinafter to be referred as vulcanizing agent of the present invention) of embodiment 1～3 preparation for the prevulcanized of catalyzer, and concrete test situation is as follows:
Catalyst sample is industrial goods, and it consists of: w (WO
3) ≈ 20.5%, w (NiO) ≈ 6.1%, carrier is the γ-Al of a small amount of molecular sieve of doping
2o
3.The prevulcanized of catalyzer is carried out in micro fixed-bed reactor (internal diameter 6mm), and loaded catalyst is 10mL.First under nitrogen protection, system is rapidly heated to 130 DEG C, keeps 3 hours with dry catalyst, removes moisture, maintains system pressure and is always 2.0MPa; Then be warming up to 200 DEG C with the speed of 50 DEG C/h, pass into H
2with the straight run oil (sulphur massfraction is about 2%) of vulcanizing agent of the present invention, constant temperature sulfuration 4 hours; Regulate again reactor inlet temperature to be warming up to 280 DEG C with the speed of 15 DEG C/h, constant temperature sulfuration 4 hours; Finally regulate reactor inlet temperature to be warming up to 340 DEG C with the speed of 10 DEG C/h, keep 1 hour, be naturally cooled to room temperature.Catalyzer after sulfuration becomes Dark grey from yellow-green colour.Adopt Xray fluorescence spectrometer to analyze principal element before and after catalyst vulcanization and mass content thereof, the results are shown in Table 1, adopt x-ray powder diffraction instrument to carry out the thing identification of phases to before and after catalyst vulcanization, the results are shown in Figure 7.
Principal element and content thereof before and after table 1 catalyst vulcanization
Note *: theoretical sulphur content is pressed WS
2, Ni
3s
2calculate, blank sample refers to unvulcanized catalyzer.
From table 1 and Fig. 7, catalyzer is after prevulcanized, and metal active constituent is converted into sulphided state by oxidation state, and catalyzer hold sulphur rate is high, can reach more than 90%.
Claims (6)
1. an organic polythiaether mix sulphur agent, is characterized in that: the general formula of this mix sulphur agent is R-S
x-R, in formula, R represents C
2～C
6positive structure or isomery alkyl, x gets two or more in 2～6 integer, and in mix sulphur agent, the massfraction of sulphur is 50%～70%.
2. a synthetic method for organic polythiaether mix sulphur agent of claim 1, is characterized in that it is made up of following step:
(1) strong alkaline substance and sulphur are dissolved in distilled water than for 1:2～1:10 by amount of substance, normal temperature～80 DEG C reaction 5～60 minutes, isolates unreacted sulphur, obtains the intermediate containing sodium polysulphide;
(2) what obtain to step (1) adds halogenated alkane and phase-transfer catalyst containing in the intermediate of sodium polysulphide, the add-on of halogenated alkane is 1～10 times of strong alkaline substance amount of substance, the add-on of phase-transfer catalyst is 0.5%～10% of strong alkaline substance amount of substance, normal-temperature reaction 0.5～2 hour, naturally be down to normal temperature, standing separation, obtains organic polythiaether mix sulphur agent;
Above-mentioned halogenated alkane is C
2～C
6halogenated alkane, strong alkaline substance is inorganic sulphide soluble in water, phase-transfer catalyst is any one in polyalcohols, quaternary ammonium salt, cyclic crown ether, tertiary amine, season phosphonium salt.
3. the synthetic method of organic polythiaether mix sulphur agent according to claim 2, it is characterized in that: in described step (1), strong alkaline substance and sulphur are dissolved in distilled water than for 1:3～1:6 by amount of substance, 50～60 DEG C are reacted 30～60 minutes, isolate unreacted sulphur, obtain the intermediate containing sodium polysulphide.
4. the synthetic method of organic polythiaether mix sulphur agent according to claim 2, it is characterized in that: in described step (2), what obtain to step (1) adds halogenated alkane and phase-transfer catalyst containing in the intermediate of sodium polysulphide, the add-on of halogenated alkane is 2 times of strong alkaline substance amount of substance, the add-on of phase-transfer catalyst is 2%～5% of strong alkaline substance amount of substance, normal-temperature reaction 0.5～1.5 hour, naturally be down to normal temperature, standing separation, obtains organic polythiaether mix sulphur agent.
5. the synthetic method of organic polythiaether mix sulphur agent according to claim 4, is characterized in that: described phase-transfer catalyst is any one in Macrogol 200, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, didecyl Dimethy brometo de amonio.
6. according to the synthetic method of the organic polythiaether mix sulphur agent described in claim 2～4 any one, it is characterized in that: described strong alkaline substance is nine water cure sodium or anhydrous potassium sulphide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104841492A (en) * | 2015-04-16 | 2015-08-19 | 江苏科创石化有限公司 | Vulcanizing agent preparing and deodorizing method for hydrogenation catalyst ex-situ pre-vulcanizing |
| CN107954814A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of phenylacetylene selection hydrogenation in eight fraction of carbon |
| CN114105904A (en) * | 2021-11-25 | 2022-03-01 | 蔚林新材料科技股份有限公司 | Preparation method of rubber organic polysulfide |
| CN114920674A (en) * | 2022-06-28 | 2022-08-19 | 山东京博石油化工有限公司 | Method for preparing organic pre-vulcanizing agent at low cost |
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| CN1216860C (en) * | 2003-03-28 | 2005-08-31 | 中国石油化工股份有限公司 | Preparation method of olefine sulfide |
| CN100509777C (en) * | 2007-04-20 | 2009-07-08 | 大庆石油学院 | Synthesis of organic polysulfide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1216860C (en) * | 2003-03-28 | 2005-08-31 | 中国石油化工股份有限公司 | Preparation method of olefine sulfide |
| CN100509777C (en) * | 2007-04-20 | 2009-07-08 | 大庆石油学院 | Synthesis of organic polysulfide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841492A (en) * | 2015-04-16 | 2015-08-19 | 江苏科创石化有限公司 | Vulcanizing agent preparing and deodorizing method for hydrogenation catalyst ex-situ pre-vulcanizing |
| CN107954814A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of phenylacetylene selection hydrogenation in eight fraction of carbon |
| CN114105904A (en) * | 2021-11-25 | 2022-03-01 | 蔚林新材料科技股份有限公司 | Preparation method of rubber organic polysulfide |
| CN114920674A (en) * | 2022-06-28 | 2022-08-19 | 山东京博石油化工有限公司 | Method for preparing organic pre-vulcanizing agent at low cost |
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