CN105294521A - Organic metal sulfide compound and its preparation method and use - Google Patents
Organic metal sulfide compound and its preparation method and use Download PDFInfo
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- CPDDTGFHBQUITD-UHFFFAOYSA-L CC(C)(C)SNSCCNCCS[Zn]SC(C)(C)C Chemical compound CC(C)(C)SNSCCNCCS[Zn]SC(C)(C)C CPDDTGFHBQUITD-UHFFFAOYSA-L 0.000 description 1
Abstract
The invention provides an organic metal sulfide compound. The organic metal sulfide compound has a structure shown in the following description or a compound composed of repetitive units shown in the following description, wherein M represents Zn or Cu, R represents C2-C10 alkyl, C2-C10 alkenyl, straight chain or branched chain C6-C12 aryl, alicyclic hydrocarbon group, C3-C10 alkyl of which carbon atom is replaced by O, N or S, or C3-C10 alicyclic hydrocarbon group of which carbon atom is replaced by O, N or S. The organic metal sulfide compound has zinc content of 20-30% and effectively reduces sulfuration activator product weight so that tyre product weight is reduced. Tyre weight reduction reduces oil consumption, improves automobile acceleration performances, reduces a brake distance, improves turning flexibility, improves tyre uniformity, improves tyre high speed performances and control stability and realizes energy saving and emission reduction.
Description
Technical field
The invention belongs to organic compound field, be specifically related to a kind of organic compound and the Synthesis and applications thereof that contain sulphur and metal.
Background technology
Vulcanized rubber is the raw materials for production of tire, and its thermotolerance and ageing-resistant performance are the important factors affecting tire quality.The traditional method being used for now improving sizing material anti-reversion behaviour is that the consumption increasing promotor reduces sulfur consumption simultaneously, or add offset-type vulcanizing agent, in order to make up the loss of cross-link bond, keep the cross-linking density of sizing material, as DuralinkHTS (two hydration hexa-methylenes 1,6-bisthiosulfate disodium salt), Perkalink900 ((1,3-lemon imide methyl) benzene) etc.The structure of HTS is made up of two portions, and middle portion is six methylene radical, and two ends have the structure of two bunte salt.Sulphur sulfur bonds in Vulcanization Process of Rubber in bunte salt structure, middle portion and the rubber macromolecule of HTS are cross-linked by carbon-sulfur bond, so just reach and embed submissive hexamethylene group between sulphur sulfide linkage.But the part that effectively can participate in rubber macromolecule crosslinking reaction in HTS structure is only dithio hexa-methylene, this part only accounts for 38% of HTS molecular structure, all the other bunte salt structures of 62% are not keyed in cross-linked network structure, forming residue is present in cross-linked rubber, active constituent content thus in HTS is low, utilization ratio is lower, and residual material also may impact the mechanical property of vulcanized rubber.
For improving the utilization ratio of HTS, the bunte salt at HTS molecular structure two ends is replaced with other functional groups by many investigators, as silicane, to improve its service efficiency, reduce residue content, the functional group of access also can improve the processing characteristics, mechanical property etc. of rubber.Disclose the purposes of metal alkanedithiols as the linking agent of unsaturated rubber in China Patent Publication No. CN1727382A, be obtained by reacting metal alkanedithiols in a suitable solvent by corresponding metal-salt and 1,6-hexanedithiol.The method adopts noxious solvent methyl alcohol as reaction solvent, and 1,6-hexanedithiol has irritating smell, brings unsafe factor to production process.
Sulphur is unsaturated rubber, vulcanizing agent as the most frequently used in natural rubber (NR), cis-1,4-polybutadiene rubber (BR) and styrene-butadiene rubber(SBR) (SBR).Crosslinking reaction between natural rubber and sulphur be unable to do without the activation of zinc oxide, zinc oxide generates Zinic stearas with stearic acid generation chemical reaction in sulfuration early stage, coordinative activity presoma is formed with the sulfur-bearing of vulcanization accelerator or nitrogen-containing functional group, the insertion open loop of catalysis sulfur molecule, thus the reactive hydrogen atom dehydrogenation chemically crosslinked of the double bond caused in sulphur atom and unsaturated rubber molecular chain and allylic; Phase zinc oxide remains in rubber after curing, and comprehensive utilization, does not bring pollution to environment.Along with the arrival in low-carbon economy epoch, zinc pollution obtains more and more higher attention, and the substitute products of exploitation zinc oxide are subject to rubber processing aids field and more and more pay attention to.
The domestic vulcanization activator product in order to alternative zinc oxide mainly contains nano zine oxide, organic zinc etc. at present.Nano zine oxide, due to nano zine oxide, to have the little and specific surface area of particle diameter large, Zn content increased, can play reduced training, but the reunion tendency of nano zine oxide in pure state and rubber must be solved could real its effect of performance.Organic zinc compound, as products such as two methylterephthalic acid two zinc, zinc acrylate resins, organic composition is introduced in structure, decrease Zn content in organic zinc compound (being down to 40%, 30%, 25% even 20% from original 80%), organic zinc is compared with common zinc oxide has Zn content and heavy metal content is low, density is low, the feature that anti ageing property is good.Organic zinc can improve the cross-linking density of sizing material, and the intensity of Reinforced Rubber, surely controls sulfidation, does not reduce rubber physical performance, also can improve its tensile strength and elongation at break, can increase substantially the heat aging property of rubber.Meanwhile, organic zinc shows better environment-friendly type, and the minimizing of zinc element can alleviate the pollution of heavy metal to environment.
Summary of the invention
For the deficiencies in the prior art part, the invention provides a kind of organic sulfide metallic compound.
Another object of the present invention is the preparation method proposing described organic sulfide metallic compound.
3rd object of the present invention is the application proposing described organic sulfide metallic compound.
The technical scheme realizing above-mentioned purpose of the present invention is:
A kind of organic sulfide metallic compound, to be structural formula be for it
compound, or by repeating unit
the compound formed,
Wherein, the aryl of the alkyl of M to be Zn or Cu, R be C2 ~ C10, the thiazolinyl of C2 ~ C10, C6 ~ 12 of straight or branched, alicyclic hydrocarbon radical, carbon atom by C3 ~ C10 alkyl of a kind of replacement in O, N or S, carbon atom by the one in C3 ~ C10 alicyclic hydrocarbon radical of a kind of replacement in O, N or S.
The preparation method of the organic sulfide metallic compound that the present invention proposes, comprises the following steps:
Step 1) thiocarbamide is joined in reaction vessel, add solvent, heated and stirred is dissolved, and described solvent is water or alcohol organic solvent, described alcohol organic solvent be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin one or more;
Step 2) drip halohydrocarbon, react 2 ~ 8h under reflux conditions;
Step 3) stop stirring, filter, obtain thiocarbamide salt with the oven dry of washing with alcohol solid;
Step 4) thiocarbamide salt is added in reaction vessel, under nitrogen or protection of inert gas, add the aqueous solution of alkali, stirring and dissolving;
Step 5) heating reflux reaction 1 ~ 4h, be then cooled to room temperature;
Step 6) in above-mentioned solution, drip the aqueous solution of soluble metallic salt, reaction 1 ~ 5h;
Step 7) suction filtration, washing, dries.
Wherein, described step 1) in, the mass ratio of thiocarbamide and solvent is 15 ~ 30:200.
Wherein, described step 2) in, the structural formula of halohydrocarbon is X-R-Y, and wherein, X is halogen, and Y is H or halogen; The mol ratio of described halohydrocarbon and thiocarbamide is 0.8:1 ~ 2.2:1.
Wherein, described step 4) in, the mass percentage concentration of the aqueous solution of alkali is 5 ~ 40%, and described alkali is one or both in sodium hydroxide, potassium hydroxide, sodium bicarbonate.
Preferably, described step 4) in, the mol ratio of thiocarbamide salt and alkali is 1:1 ~ 1:2.5.
Wherein, described step 6) in, soluble metallic salt is selected from the one in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, cupric chloride, neutralized verdigris, copper sulfate, cupric nitrate, and the mass percentage concentration of soluble metal salt brine solution is 10 ~ 60%.
Wherein, in step 6) reaction process in, the pH value controlling reaction mixture with the aqueous solution of alkali or buffered soln is 7 ~ 8, and described buffered soln is the one in boric acid-borax buffer solution, Glycine-NaOH buffered soln, borax-sodium hydroxide buffer solution, Sodium phosphate dibasic-sodium hydroxide buffer solution, sodium bicarbonate-sodium hydroxide buffer solution.
The organic sulfide metallic compound that the present invention proposes is as the application of vulcanization of rubber stablizer.
Particularly, the organic sulfide metallic compound that the present invention proposes and natural rubber, other auxiliary agents mix, and carry out the preparation of vulcanized rubber.The mass ratio of organic sulfide metallic compound and natural rubber can be 1 ~ 5:100.
Beneficial effect of the present invention is:
The organic sulfide metallic compound that the present invention proposes, in molecular structure, Zn content is 20 to 30%, effectively alleviates vulcanization activator product weight, makes final tire product also realize loss of weight.The loss of weight of tire can reduce oil consumption, improves automobile acceleration characteristics, reduces braking distance, increases the handiness turned to, can improve the homogeneity of tire, improves high speed performance and the control stability of tire, realizes energy-saving and emission-reduction.
The organic sulfide metallic compound that the present invention proposes, promoter action is played to the vulcanization crosslinking reaction process of rubber, participates in vulcanization of rubber reaction simultaneously, form cross-linked network, enhance the thermostability of vulcanized rubber cross-link bond, improve the anti-reversion behaviour of cross-linked rubber.
Compared with prior art, preparation method's technique provided by the invention is simple, raw material is easy to get, energy consumption is low, without harmful reagent in reaction process, both the security of reaction process had been improved, free from environmental pollution again, reproducible, meet the developing direction of safety, green, environmental protection, there is great development prospect.
Embodiment
Following examples for illustration of the present invention, but should not be used for limiting the scope of the invention.
Embodiment 1:
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 15.2g thiocarbamide, join in four-hole boiling flask, then add 200g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip 33.0g bromohexane, stirred at reflux condition reaction 5h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add the above-mentioned thiocarbamide salt of 28.8g, after nitrogen purging, add the NaOH aqueous solution that 20.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then add 44.0g zinc acetate (this zinc acetate be mixed with mass percentage concentration be 25% the aqueous solution add), under reflux conditions react, the pH value of the NaOH solution control reaction solution by dropping 20% in reaction process remains between 7 ~ 8, after back flow reaction 4h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the alkyl zinc sulfide compounds structural formula obtained is as follows:
Embodiment 2
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, to take 17.4g thiocarbamide, join in four-hole boiling flask, then 200g ethanol is added, after heated and stirred makes thiocarbamide dissolve completely, drip the bromo-2-butylene of 24.4g trans-Isosorbide-5-Nitrae-two, stirred at reflux condition reaction 5h, stop stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add the above-mentioned thiocarbamide salt of 21.9g, after nitrogen purging, add the NaOH aqueous solution that 20.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then add 44.0g zinc acetate (be mixed with mass percentage concentration be 25% zinc acetate aqueous solution add), under reflux conditions react, the pH value of the NaOH solution control reaction solution by dropping 20% in reaction process remains between 7 ~ 8, after back flow reaction 3h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the unsaturated alkyl zinc sulfide compounds obtained, its structure is made up of following repeating unit:
Embodiment 3
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 15.2g thiocarbamide, join in four-hole boiling flask, then add 150g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip 24.6g2-N-PROPYLE BROMIDE, stirred at reflux condition reaction 3h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add 23.8g thiocarbamide salt, after nitrogen purging, add the NaOH aqueous solution that 20.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then 20.5g zinc chloride (being mixed with the solder(ing)acid that mass percentage concentration is 40.0%) is added, under reflux conditions react, sodium bicarbonate-the sodium hydroxide buffer solution being 11.0 by dropping pH value in reaction process (takes 0.42g sodium bicarbonate and 0.18g sodium hydroxide, add 110mL water, being mixed with sodium bicarbonate-sodium hydroxide buffer solution that pH value is 11.0) pH value that controls reaction solution remains between 7 ~ 8, heating reflux reaction 2h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the branched-chain alkyl zinc sulfide compounds structural formula obtained is as follows
Embodiment 4
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 16.0g thiocarbamide, join in four-hole boiling flask, then add 200g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip two (2-bromotrifluoromethane) ether of 23.2g, stirred at reflux condition reaction 6h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add 16.8g thiocarbamide salt, after nitrogen purging, add the NaOH aqueous solution that 40.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then 22.0g zinc sulfate (being made into the zinc sulfate solution that mass percentage concentration is 50.0%) is added, under reflux conditions react, the pH value of the NaOH solution control reaction solution by dropping 20% in reaction process remains between 7 ~ 8, heating reflux reaction 4h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the alkyl oxide zinc sulfide compounds obtained, its structure is made up of following repeating unit:
Embodiment 5
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 22.8g thiocarbamide, join in four-hole boiling flask, then add 200g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip 27.4g epoxy bromopropane, stirred at reflux condition reaction 6h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add 19.1g thiocarbamide salt, after nitrogen purging, add the NaOH aqueous solution that 40.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then the zinc acetate aqueous solution that 40.0g mass percentage concentration is 15.0% is added, under reflux conditions react, SODIUM PHOSPHATE, MONOBASIC-the sodium hydroxide buffer solution being 12.0 by dropping pH value in reaction process (takes 0.82g bis-hypophosphite monohydrate sodium dihydrogen and 0.20g sodium hydroxide, add 100mL water, being mixed with SODIUM PHOSPHATE, MONOBASIC-sodium hydroxide buffer solution that pH value is 12.0) pH value that controls reaction solution remains between 7 ~ 8, heating reflux reaction 3h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the cycloalkyl zinc sulfide compounds structural formula obtained is as follows
Embodiment 6
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 20.5g thiocarbamide, join in four-hole boiling flask, then add 200g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip 15.4g cylite, stirred at reflux condition reaction 2h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add 29.5g thiocarbamide salt, after nitrogen purging, add the NaOH aqueous solution that 20.0g mass percentage concentration is 10%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 4h under heated reflux condition, be cooled to room temperature, then 40.0g zinc acetate (being made into the zinc acetate aqueous solution that mass percentage concentration is 27.5%) is added, under reflux conditions react, the pH value of the NaOH solution control reaction solution by dropping 10% in reaction process remains between 7 ~ 8, heating reflux reaction 5h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the aryl zinc sulfide compounds structural formula obtained is as follows
Embodiment 7
To be equipped with the 500mL four-hole boiling flask of temperature regulating device, whipping appts and reflux condensate device as reaction vessel, take 15.2g thiocarbamide, join in four-hole boiling flask, then add 200g ethanol, after heated and stirred makes thiocarbamide dissolve completely, drip 33.0g bromohexane, stirred at reflux condition reaction 5h, stops stirring, be cooled to suction filtration reaction solution after room temperature, and use washing with alcohol solid, be dried to constant weight, obtain thiocarbamide salt.
To with temperature control unit, in the 250mL four-hole boiling flask of whipping appts and reflux condensate device, add the above-mentioned thiocarbamide salt of 28.8g, after nitrogen purging, add the NaOH aqueous solution that 20.0g mass percentage concentration is 20%, stirring under nitrogen protection condition makes thiocarbamide salt dissolve, after reacting 2h under heated reflux condition, be cooled to room temperature, then the neutralized verdigris aqueous solution that 40.0g mass percentage concentration is 30% is added, under reflux conditions react, the pH value of the sodium hydrogen carbonate solution control reaction solution by dropping 20% in reaction process remains between 7 ~ 8, after back flow reaction 6h, be cooled to room temperature, suction filtration, washing, be dried to constant weight, the alkyl sulfuration copper compound structural formula obtained is as follows:
Experimental example
The curability of organic sulfide metallic compound in natural rubber formulations prepared by testing example 1 ~ 7 and anti-reversion behaviour, and contrast with HTS, test formulations is as follows:
Basal component and each Parts by Ingredients consumption as follows: natural rubber 100.0, carbon black N33045.0, stearic acid 2.0, ZnO4.5, anti-aging agent RD 1.0, antioxidant 4020 1.0, accelerator NS 1.0, sulphur 2.0, only adds mentioned component in blank, the compound that formula 1 ~ 8 adds HTS respectively, prepared by embodiment 1 ~ 7, consumption is 3.0.
Its performance test is as follows:
The tensile stress-strain performance measurement that fracture tensile strength specifies according to GB/T528-2009, the fracture tensile strength of formula 1# is set to 100, and fracture tensile strength is with the exponential representation in equation below.
Fracture tensile strength index=(values of tensile strength at break of each composition)/(values of tensile strength at break of formula 1#) × 100
The tensile stress-strain performance measurement that elongation at break specifies according to GB/T528-2009, the elongation at break of formula 1# is set to 100, and elongation at break is with the exponential representation in equation below.
Elongation at break index=(elongation at break values of each composition)/(elongation at break values of formula 1#) × 100
The tensile stress-strain performance measurement that stress at definite elongation specifies according to GB/T528-2009, the stress at definite elongation of formula 1# is set to 100, and stress at definite elongation is with the exponential representation in equation below.
Stress at definite elongation index=(the stress at definite elongation value of each composition)/(the stress at definite elongation value of formula 1#) × 100
The mensuration of the rubber unvulcanizate vulcanization characteristics that reversion percentage specifies according to GB/T16584-1996, wherein: SMax is the torque capacity reached at the appointed time, S30min is the torque value when 30min.
Reversion percentage index=(the reversion percentage value of each composition)/(the reversion percentage value of formula 1#) × 100
The performance comparison of table 1. test formulations
As seen from the results in Table 1, add the compound of HTS or embodiment 1 ~ 7 preparation, the anti-reversion behaviour of formula significantly improves, and fill a prescription and 2 ~ 8 be compared to formula 1, without aging condition, quite or slightly poor, but after 100 DEG C of * 24h are aging, its Performance Ratio formula 1 will be got well for both tensile properties.In addition, by reversion percentage, formula 2 ~ 8 also has better anti-recovery effect than formula 1.
Those skilled in the art in the art will be appreciated that, above-described embodiment is only used to the present invention is described, and be not used as limitation of the invention, as long as in spirit of the present invention, the conversion of above-described embodiment, modification all will be dropped in the scope of the claims in the present invention.
Claims (9)
1. an organic sulfide metallic compound, is characterized in that, being structural formula is
compound, or by repeating unit
the compound formed,
Wherein, M is Zn or Cu, R is the one in the alkyl of C2 ~ C10, the thiazolinyl of C2 ~ C10, the aryl of C6 ~ 12 of straight or branched, alicyclic hydrocarbon radical, or carbon atom by C3 ~ C10 alkyl of a kind of replacement in O, N or S, carbon atom by the one in C3 ~ C10 alicyclic hydrocarbon radical of a kind of replacement in O, N or S.
2. the preparation method of organic sulfide metallic compound described in claim 1, is characterized in that, comprise the following steps:
Step 1) thiocarbamide is joined in reaction vessel, add solvent, heated and stirred is dissolved, and described solvent is water or alcohol organic solvent, described alcohol organic solvent be selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, the trimethyl carbinol, hexalin one or more;
Step 2) drip halohydrocarbon, react 2 ~ 8h under reflux conditions;
Step 3) stop stirring, filter, use washing with alcohol solid, dry and obtain thiocarbamide salt;
Step 4) thiocarbamide salt is added in reaction vessel, under nitrogen or protection of inert gas, add the aqueous solution of alkali, stirring and dissolving;
Step 5) heating reflux reaction 1 ~ 4h, be then cooled to room temperature;
Step 6) in above-mentioned solution, drip the aqueous solution of soluble metallic salt, reaction 1 ~ 5h;
Step 7) suction filtration, washing, dries.
3. preparation method according to claim 2, is characterized in that, described step 1) in, the mass ratio of thiocarbamide and solvent is 15 ~ 30:200.
4. preparation method according to claim 2, is characterized in that, described step 2) in, the structural formula of halohydrocarbon is X-R-Y, and wherein, X is halogen, and Y is H or halogen; The mol ratio of described halohydrocarbon and thiocarbamide is 0.8:1 ~ 2.2:1.
5. preparation method according to claim 2, is characterized in that, described step 4) in, the mass percentage concentration of the aqueous solution of alkali is 5 ~ 40%, and described alkali is one or both in sodium hydroxide, potassium hydroxide, sodium bicarbonate.
6., according to the arbitrary described preparation method of claim 2 ~ 5, it is characterized in that, described step 4) in, the mol ratio of thiocarbamide salt and alkali is 1:1 ~ 1:2.5.
7. according to the arbitrary described preparation method of claim 2 ~ 5, it is characterized in that, described step 6) in, soluble metallic salt is selected from the one in zinc chloride, zinc sulfate, zinc nitrate, zinc acetate, cupric chloride, neutralized verdigris, copper sulfate, cupric nitrate, and the mass percentage concentration of soluble metal salt brine solution is 10 ~ 60%.
8. according to the arbitrary described preparation method of claim 2 ~ 5, it is characterized in that, in step 6) reaction process in, the pH value controlling reaction mixture with the aqueous solution of alkali or buffered soln is 7 ~ 8, and described buffered soln is the one in boric acid-borax buffer solution, Glycine-NaOH buffered soln, borax-sodium hydroxide buffer solution, Sodium phosphate dibasic-sodium hydroxide buffer solution, sodium bicarbonate-sodium hydroxide buffer solution.
9. organic sulfide metallic compound according to claim 1 is as the application of vulcanization of rubber stablizer.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727382A (en) * | 2004-05-05 | 2006-02-01 | 兰爱克谢斯德国有限责任公司 | Use of metal alkanedithiols as crosslinking agents for unsaturated rubbers |
| CN104370784A (en) * | 2014-12-11 | 2015-02-25 | 北京彤程创展科技有限公司 | Naphthenic-base zinc sulfide compound and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1727382A (en) * | 2004-05-05 | 2006-02-01 | 兰爱克谢斯德国有限责任公司 | Use of metal alkanedithiols as crosslinking agents for unsaturated rubbers |
| CN104370784A (en) * | 2014-12-11 | 2015-02-25 | 北京彤程创展科技有限公司 | Naphthenic-base zinc sulfide compound and preparation method thereof |
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| COLUMBUS,OHIO,US: "Registry[Online]", 《STN INTERNATIONAL》 * |
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Application publication date: 20160203 |