CN117658751A - Vulcanizing agent and preparation method and application thereof - Google Patents
Vulcanizing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN117658751A CN117658751A CN202211016748.1A CN202211016748A CN117658751A CN 117658751 A CN117658751 A CN 117658751A CN 202211016748 A CN202211016748 A CN 202211016748A CN 117658751 A CN117658751 A CN 117658751A
- Authority
- CN
- China
- Prior art keywords
- material system
- reaction
- organic
- vulcanizing agent
- sulfur
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 42
- 239000011593 sulfur Substances 0.000 claims abstract description 41
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 16
- -1 cyclic organic polysulfide Chemical class 0.000 claims abstract description 13
- 230000009471 action Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 92
- 239000007789 gas Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 42
- 229920006295 polythiol Polymers 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 17
- 150000008116 organic polysulfides Chemical group 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000012544 monitoring process Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000007530 organic bases Chemical class 0.000 claims description 8
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000010092 rubber production Methods 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 abstract description 4
- 239000005077 polysulfide Substances 0.000 abstract description 4
- 150000008117 polysulfides Polymers 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 32
- 239000000047 product Substances 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 9
- 238000004064 recycling Methods 0.000 description 9
- 230000000630 rising effect Effects 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a vulcanizing agent, a preparation method and application thereof, wherein the preparation method of the vulcanizing agent comprises the following steps: the low-carbon olefin and the sulfur source react under the action of organic alkali and/or inorganic alkali, the gas phase pressure of a reaction system is monitored in the reaction process, and when the gas phase pressure increase amplitude reaches 0.05-0.6Mpa/min, the reaction is stopped, preferably 0.1-0.4Mpa/min, and the vulcanizing agent is obtained by separation after cooling. The vulcanizing agent has the advantages of simple preparation method, easy control, high sulfur mass content, long sulfur chain containing cyclic organic polysulfide and high mass content of cyclic polysulfide.
Description
Technical Field
The invention relates to a vulcanizing agent and a preparation method and application thereof, in particular to an organic polysulfide vulcanizing agent and a preparation method and application thereof.
Background
The organic polythioether is a compound with a general formula of R-S x -R 1 X is between 2 and 20, R and R 1 The alkyl, alkylaryl, aryl or aralkyl functional groups, which may be the same or different, may be saturated or unsaturated hydrocarbons, may be linear, branched or cyclic hydrocarbons, and are commonly used in the presulfiding treatment of hydrogenation catalysts, both in-situ presulfiding and ex-situ presulfiding must be accomplished in the presence of a sulfiding agent.
The organic polythioether is synthesized by using mercaptan and elemental sulfur as raw materials, and the organic polythioether is prepared in the presence of a catalyst. The process has been developed in a direction which is mainly based on the improvement of the catalysts conventionally used, such as amines, alkylamines, alkanolamines, inorganic bases, mercaptides and alkoxides, for example, U.S. Pat. No. 3,182, using a catalyst having the general formula RSH.x (C m H 2m O). YMOH, US5068445 uses basic resin as catalyst, US6051739 uses conventional basic material and has the general formula R 2 O[CH 2 CH·(R 3 )O] n SO 3 The surface active substances of M are combined together to serve as a catalyst, so that the yield of synthetic reaction products is improved, and the catalyst is easy to separate from the products. US4937385, US6472354, US6544936 respectively provide a process for preparing organic polythioethers from olefins, sulfur and hydrogen sulfide in the presence of different catalysts. The reaction path is as follows: firstly, hydrogen sulfide reacts with olefin to generate an intermediate product alkyl mercaptan compound in the presence of elemental sulfur, then sulfur molecules are heated for ring opening, and a plurality of organic polythioethers with different sulfur atom contents are generated in the presence of an alkaline catalyst. The method uses mercaptan as a substrate or uses mercaptan as an intermediate in the reaction process, and most of the mercaptan is expensive and is a toxic and malodorous compound, so that the obtained organic polythioether has bad smell and poor stability due to the dissolution of hydrogen sulfide and unreacted mercaptan. US5135670. US5338468, US5849677 and CN200710098327.7 respectively disclose a method for preparing organic polysulfide containing polysulfide cross-linking bond by using olefin and elemental sulfur as raw materials under the action of different catalysts, the preparation process is simple, the raw materials are cheap and easily available, no halogen is introduced, but the obtained product has more impurities, bad smell and lower sulfur content. US4204969, US5410088 and CN1534019 respectively provide a method for preparing purer polythioether by dehalogenating, by using olefin and sulfur halide as raw materials, and by generating sulfured olefin containing halogen groups under the action of different catalysts. The synthetic route has higher sulfur content and milder conditions, but generates a large amount of wastewater and waste gas (HCl and H) in the reaction 2 S and other gases), waste residues (containing NaCl and sulfides), and the three wastes are difficult to treat.
CN103937540A and CN108097333A disclose a vulcanizing agent for hydrogenation catalysts and a preparation method thereof, wherein the sulfur content of the vulcanizing agent is 40-80 wt%, and the vulcanizing agent comprises linear polysulfide and cyclic sulfide. The method solves the problems of high toxicity, high production cost and the like of the existing vulcanizing agent. However, the ratio of the cyclic polythioether contained in the vulcanizing agent prepared by the method needs to be further improved, the length of a sulfur chain in the cyclic polythioether is generally below 2, and a 4A molecular sieve needs to be added in the preparation process.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a vulcanizing agent, and a preparation method and application thereof. The vulcanizing agent has the advantages of simple preparation method, easy control, high sulfur mass content, long sulfur chain containing cyclic organic polysulfide and high mass content of cyclic polysulfide.
A method of preparing a vulcanizing agent, the method comprising: the low-carbon olefin and the sulfur source react under the action of organic alkali and/or inorganic alkali, the gas phase pressure of a reaction system is monitored in the reaction process, and when the gas phase pressure increase amplitude reaches 0.05-0.6Mpa/min, the reaction is stopped, preferably 0.1-0.4Mpa/min, and the vulcanizing agent is obtained by separation after cooling.
According to the method of the invention, the sulfur source is sulfur, and the sulfurThe sulfonic acid is solid at normal temperature, S 8 Is present in the form of (c). The sulfur can be commercially available or prepared according to the prior art, the purity of the sulfur is not strictly limited, and the sulfur can contain a proper amount of impurities.
According to the method of the invention, the lower olefin is C 2 -C 5 Is an olefin of (a) a hydrocarbon of (b). The olefin can be pure olefin or mixed olefin, and the pure olefin can be any one of ethylene, propylene, 1-butene, 2-butene, isobutene, n-pentene and isoamylene; the mixed olefin may be any of the above pure olefins, or may be one or more of liquefied gas mainly containing the mixed olefin, carbon four before ether, and carbon four after ether.
According to the process of the invention, the organic base comprises methylamine, urea, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1, 3-propylenediamine, 1, 2-propylenediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine; preferably, one or more of dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1, 3-propylenediamine, 1, 2-propylenediamine, tripropylamine and triethanolamine are used.
According to the method of the invention, the inorganic base is one or more of potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water.
According to the method of the invention, the low-carbon olefin and the sulfur source react under the action of organic alkali and/or inorganic alkali, and the reaction temperature is controlled by the following modes: the material system containing the sulfur source is heated, the viscosity coefficient of the material system is monitored, when the viscosity coefficient of the material system is changed from gradual decrease to increase, the temperature of the material system is recorded as T, and the temperature of the material system is controlled to be higher than T0-15 ℃, preferably higher than 3-10 ℃.
According to the method of the invention, the organic base and/or inorganic base is added to the material system at least before the viscosity coefficient of the material system is changed from gradual decrease to increase, and can be added before the material system is heated or during the heating process of the material system.
According to the method of the invention, the low-carbon olefin compound can be added into the material system at one time or intermittently or continuously in the reaction process.
According to the method of the invention, the low-carbon olefin, the sulfur source, the organic base and/or the inorganic base are added into the reaction system at one time.
According to the process of the invention, the mass ratio of the organic base and/or inorganic base to the sulfur source is from 0.005 to 0.2, preferably from 0.01 to 0.1.
According to the method of the invention, the molar ratio of the low-carbon olefin to the elemental sulfur is 1:1-1:5, preferably 1:2-1:4.
According to the method of the invention, the specific viscosity measured when the viscosity coefficient of the material system is changed from gradually decreasing to increasing varies with the difference of the material system, and the viscosity is preferably 5 to 30 Pa.s when the viscosity is generally 3 to 40 Pa.s.
The invention is not limited to a method for preparing a vulcanizing agent, which comprises the following steps:
(1) Mixing a sulfur source, organic alkali and/or inorganic alkali, and then placing the mixture into a reaction kettle; then, the air is replaced by inert gas and then the required low-carbon olefin is directly filled, or the nitrogen is replaced by the low-carbon olefin and then the required low-carbon olefin is filled, and a material system containing a sulfur source, organic alkali and/or inorganic alkali and the low-carbon olefin is heated and heated to liquefy the sulfur element;
(2) Measuring the viscosity coefficient of a material system, when the viscosity coefficient of the material system is changed from gradual reduction to increase, recording the temperature of the material system as T, controlling the temperature of the material system to be higher than T0-15 ℃, preferably higher than 5-10 ℃, and continuously reacting for a period of time;
(3) Monitoring the gas phase pressure of the reaction system in the step (2), stopping the reaction when the gas phase pressure increasing amplitude reaches 0.05-0.6Mpa/min, preferably 0.1-0.4Mpa/min, and separating after cooling to obtain the vulcanizing agent.
A vulcanizing agent is an organic polysulfide, the sulfur content of the organic polysulfide is more than 45 percent, preferably 50 to 70 percent by weight, the vulcanizing agent contains linear organic polysulfide and cyclic organic polysulfide, and the mass content of the cyclic organic polysulfide in the organic polysulfide is more than 10 percent by weight, preferably 12 to 20 percent by weight based on the weight of the organic polysulfide
According to the present invention, the cyclic organic polysulfide comprises a cyclic trisulfide CnR 2 nS 3 Wherein R is any group which may be attached to a carbon atom, typically a hydrogen atom, an alkyl group (preferably methyl); further preferably C 3 H 6 S 3 。
According to the vulcanizing agent of the present invention, the cyclic trisulfide C contained in the cyclic organic polythioether n R 2n S 3 Accounting for 30 to 70 percent, preferably 40 to 60 percent of the total mass of the cyclic organic polythioether.
The vulcanizing agent can be used as vulcanizing agent of hydrogenation catalyst, vulcanizing agent in rubber production process and coke inhibitor in ethylene production process.
In the method of the invention, the length of the sulfur chain in the organic polysulfide vulcanizing agent is a key factor for determining the sulfur content and the property of the organic polysulfide, and the proportion of the linear organic polysulfide and the cyclic organic polysulfide in the organic polysulfide has an important influence on the vulcanizing property of the organic polysulfide. Taking as an example a vulcanizing agent for the hydrogenation catalyst, the continuous slow vulcanization of the catalyst can be achieved by utilizing the difference of the decomposition temperatures of the organic polythioether and the annular organic polythioether, and the adverse effect of concentrated vulcanization heat release on the active metal of the hydrogenation catalyst can be restrained. However, it is difficult to prepare organic polythioethers having long sulfur chains.
The inventors found on the basis of many years of intensive studies on the preparation of organic polythioethers that there are two main reasons for this: firstly, sulfur free radicals are generated in the reaction stage, and long-chain free radicals with more than 2 sulfur atoms are unstable and are easy to be further cracked, so that the content of the long-chain sulfur free radicals in a reaction system is low; secondly, the reaction balance is affected by the reaction temperature, the concentration of each material and other factors in the later stage of the reaction, and the generated long-chain organic polythioether is further decomposed. The inventor precisely controls the reaction process under the guidance of the theory, creatively proposes to avoid the decomposition of long-chain organic polythioether and monitor the viscosity of a material system to control the reaction temperature by controlling the end time of the content of the gas-phase pressure change, and the inventor surprisingly found that the concentration of more than three free radicals of sulfur promotes the formation of long-chain organic polythioether in the reaction process, by the control mode, the sulfur content in the organic polythioether is greatly improved, the proportion of the cyclic compound is obviously increased, and the cyclic trisulfide is found in the organic polythioether.
Detailed Description
The operation and effects of the method of the present invention are further described below with reference to examples and comparative examples, but the following examples do not limit the present invention. In the context of the present invention, the percentages are mass percentages unless otherwise indicated. The composition and sulfur content of the prepared organic polythioether were determined by GC-MAS in the method of the invention. The reaction equipment in the method is a reaction kettle, and a stirring device, a heat exchange device (heating or heat removing), a viscosity measuring device, a pressure measuring device, a temperature measuring device and the like are arranged according to requirements.
Example 1
Sequentially adding 300g of elemental sulfur and 3g of dimethylamine into a reaction kettle, then replacing air with nitrogen, directly charging propylene, wherein the molar ratio of propylene to elemental sulfur is 1:2, and heating a material system to raise the temperature to liquefy elemental sulfur; the temperature rising speed is 1 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 5 Pa.s (the viscosity coefficient is changed from a decreasing trend to an increasing critical point, and the same applies below), controlling the temperature of the material system to be not higher than 168 ℃ at the moment when the temperature of the reaction system is 158 ℃ and continuously reacting for a period of time; monitoring the gas phase pressure of the reaction system, stopping the reaction when the gas phase pressure increasing speed is 0.1Mpa/min, recycling the cooled gas phase material, and flashing the liquid phase material for 1.5h at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 2
Sequentially adding 300g of elemental sulfur, 15g of trimethylamine and 15g of diethylamine into a reaction kettle, then replacing air with nitrogen, directly filling isobutene, wherein the molar ratio of isobutene to elemental sulfur is 1:4, and heating a material system to raise the temperature to liquefy elemental sulfur; the temperature rising speed is 3 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 30 Pa.s, controlling the temperature of the material system to be not higher than 165 ℃ for continuous reaction for a period of time when the reaction temperature is 162 ℃; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.4Mpa/min, recycling the cooled gas phase material, and flashing the liquid phase material for 1.5h at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 3
Sequentially adding 300g of elemental sulfur, 7g of triethylamine and 8g of propylamine into a reaction kettle, then replacing air with nitrogen, directly charging 1-butene, wherein the molar ratio of the 1-butene to the elemental sulfur is 1:3, and heating a material system to raise the temperature to liquefy the elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 20 Pa.s, controlling the temperature of the material system to be 159 ℃ and controlling the temperature of the material system to be not higher than 166 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.2Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2h at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 4
300g of elemental sulfur, 8g of 1, 3-propylamine and 5g of 1, 2-propylamine are sequentially added into a reaction kettle, then air is replaced by nitrogen, 2-butene is directly filled into the reaction kettle, the molar ratio of the 2-butene to the elemental sulfur is 1:3, and a material system is heated to raise the temperature to liquefy the elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 20 Pa.s, controlling the temperature of the system to be 160 ℃ and controlling the temperature of the material system not to be higher than 167 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.15Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2 hours at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 5
Sequentially adding 300g of elemental sulfur, 5g of tripropylamine and 5g of triethanolamine into a reaction kettle, then replacing air with nitrogen, directly filling n-pentene, wherein the molar ratio of n-pentene to elemental sulfur is 1:3.2, and heating a material system to raise the temperature to liquefy elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 22 Pa.s, controlling the temperature of the system to be 162 ℃ and controlling the temperature of the material system not to be higher than 169 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.25Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2 hours at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 6
Sequentially adding 300g of elemental sulfur and 16g of sodium methoxide into a reaction kettle, then replacing air with nitrogen, directly filling isoamylene, wherein the molar ratio of the isoamylene to the elemental sulfur is 1:2, and heating a material system to raise the temperature to liquefy the elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 22 Pa.s, controlling the temperature of the system to be 159 ℃ and controlling the temperature of the material system not to be higher than 166 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.3Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2 hours at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 7
Sequentially adding 300g of elemental sulfur and 10g of sodium carbonate into a reaction kettle, then replacing air with nitrogen, directly charging a mixed gas of propylene and carbon four before ether (the volume ratio of the propylene to the carbon four before ether is 1:2), and heating a material system to raise the temperature to liquefy the elemental sulfur, wherein the molar ratio of the mixed gas to the elemental sulfur is 1:3; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 20 Pa.s, controlling the temperature of the system to be 165 ℃ and controlling the temperature of the material system not to be higher than 168 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.25Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2 hours at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 8
Sequentially adding 300g of elemental sulfur and 17g of potassium hydroxide into a reaction kettle, then replacing air with nitrogen, directly charging ethylene, wherein the molar ratio of ethylene to elemental sulfur is 1:4, and heating a material system to raise the temperature to liquefy elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 20 Pa.s, controlling the temperature of the material system to be 158 ℃ and controlling the temperature of the material system not to be higher than 165 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.2Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2h at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
Example 9
Sequentially adding 300g of elemental sulfur, 7g of sodium hydroxide and 5g of potassium ethoxide into a reaction kettle, then replacing air with nitrogen, directly filling ether with carbon four, wherein the molar ratio of the ether carbon four to the elemental sulfur is 1:3.3, and heating a material system to liquefy the elemental sulfur; the temperature rising speed is 2 ℃/min. Measuring the viscosity coefficient of a material system, and when the viscosity coefficient of the material system is 20 Pa.s, controlling the temperature of the system to be 160 ℃ and controlling the temperature of the material system not to be higher than 167 ℃ for continuous reaction for a period of time; monitoring the gas phase pressure of the reaction system in the step, stopping the reaction when the gas phase pressure increasing speed is 0.30Mpa/min, recycling the cooled gas phase material, and flash evaporating the liquid phase material for 2 hours at 50 ℃ and 10000 pa. The analysis results of the obtained vulcanizing agent product are shown in Table 1.
TABLE 1
Claims (19)
1. A preparation method of a vulcanizing agent is characterized by comprising the following steps: the method comprises the following steps: the low-carbon olefin and the sulfur source react under the action of organic alkali and/or inorganic alkali, the gas phase pressure of a reaction system is monitored in the reaction process, the reaction is stopped when the gas phase pressure increase amplitude reaches 0.05-0.6MPa/min, and the vulcanizing agent is obtained by separation after cooling.
2. The method according to claim 1, characterized in that: monitoring the gas phase pressure of the reaction system in the reaction process, stopping the reaction when the gas phase pressure increasing amplitude reaches 0.1-0.4MPa/min, and separating after cooling to obtain the vulcanizing agent.
3. The method according to claim 1, characterized in that: the sulfur source is sulfur, which is prepared by adopting commercial products or according to the prior art.
4. The method according to claim 1, characterized in that: the lower olefin is C 2 -C 5 Preferably propylene and/or isobutylene.
5. The method according to claim 1, characterized in that: the olefin is pure olefin or mixed olefin or one or more of liquefied gas containing mixed olefin, carbon four before ether and carbon four after ether.
6. The method according to claim 1, characterized in that: the organic base comprises methylamine, urea, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1, 3-propylenediamine, 1, 2-propylenediamine, tripropylamine, triethanolamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine; preferably, one or more of dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, 1, 3-propylenediamine, 1, 2-propylenediamine, tripropylamine and triethanolamine are used.
7. The method according to claim 1, characterized in that: the inorganic base is one or more of potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water.
8. The method according to claim 1, characterized in that: the reaction of the low-carbon olefin and the sulfur source is carried out under the action of organic alkali and/or inorganic alkali, and the reaction temperature is controlled by the following modes: the material system containing the sulfur source is heated, the viscosity coefficient of the material system is monitored, when the viscosity coefficient of the material system is changed from gradual decrease to increase, the temperature of the material system is recorded as T, and the temperature of the material system is controlled to be higher than T0-15 ℃, preferably higher than 3-10 ℃.
9. The method according to claim 1, characterized in that: the organic base and/or the inorganic base is/are added to the material system at least before the viscosity coefficient of the material system is changed from gradual decrease to increase, in particular before the material system is heated or during the heating process of the material system.
10. The method according to claim 1, characterized in that: the low-carbon olefin compound is added into the material system at one time or intermittently or continuously in the reaction process.
11. The method according to claim 1, characterized in that: the low-carbon olefin, the sulfur source, the organic base and/or the inorganic base are added into the reaction system at one time.
12. The method according to claim 1, characterized in that: the mass ratio of the organic base and/or inorganic base to the sulfur source is 0.005-0.2, preferably 0.01-0.1.
13. The method according to claim 1, characterized in that: the molar ratio of the low-carbon olefin to the sulfur simple substance is 1:1-1:5, preferably 1:2-1:4.
14. The method according to claim 1, characterized in that: the viscosity coefficient of the material system is preferably 5-30 Pa.s when the viscosity is 3-40 Pa.s when the viscosity is gradually reduced to be increased.
15. The method according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) Mixing a sulfur source, organic alkali and/or inorganic alkali, and then placing the mixture into a reaction kettle; then, the air is replaced by inert gas and then the required low-carbon olefin is directly filled, or the nitrogen is replaced by the low-carbon olefin and then the required low-carbon olefin is filled, and a material system containing a sulfur source, organic alkali and/or inorganic alkali and the low-carbon olefin is heated and heated to liquefy the sulfur element;
(2) Measuring the viscosity coefficient of a material system, when the viscosity coefficient of the material system is changed from gradual reduction to increase, recording the temperature of the material system as T, controlling the temperature of the material system to be higher than T0-15 ℃, preferably higher than 5-10 ℃, and continuously reacting for a period of time;
(3) Monitoring the gas phase pressure of the reaction system in the step (2), stopping the reaction when the gas phase pressure increasing amplitude reaches 0.05-0.6MPa/min, preferably 0.1-0.4MPa/min, and separating after cooling to obtain the vulcanizing agent.
16. A vulcanising agent prepared according to any of the claims 1 to 15, characterised in that: the vulcanizing agent is organic polysulfide, the sulfur content of the organic polysulfide is more than 45%, preferably 50-70%, the vulcanizing agent contains linear organic polysulfide and cyclic organic polysulfide, and the mass content of the cyclic organic polysulfide in the organic polysulfide is more than 10%, preferably 12-20%, based on the weight of the organic polysulfide.
17. The vulcanizing agent of claim 16, wherein: the cyclic organic polythioether contains cyclic trisulfide CnR 2 nS 3 Wherein R is any group attached to a carbon atom, and the cyclic trisulfide is preferably C 3 H 6 S 3 。
18. The vulcanizing agent of claim 16, wherein: a cyclic trisulfide C contained in the cyclic organic polythioether n R 2n S 3 Accounting for 30 to 70 percent, preferably 40 to 60 percent of the total mass of the cyclic organic polythioether.
19. A sulfiding agent for hydrogenation catalysts, sulfiding agent for rubber production process, scorch retarder for ethylene production process according to any one of claims 16 to 18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211016748.1A CN117658751A (en) | 2022-08-24 | 2022-08-24 | Vulcanizing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211016748.1A CN117658751A (en) | 2022-08-24 | 2022-08-24 | Vulcanizing agent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117658751A true CN117658751A (en) | 2024-03-08 |
Family
ID=90068488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211016748.1A Pending CN117658751A (en) | 2022-08-24 | 2022-08-24 | Vulcanizing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117658751A (en) |
-
2022
- 2022-08-24 CN CN202211016748.1A patent/CN117658751A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4211676A (en) | Process for reclaiming scrap vulcanized rubber | |
| JPH0351700B2 (en) | ||
| CN108101815B (en) | Vulcanizing agent for hydrogenation catalyst and preparation process thereof | |
| CN117658751A (en) | Vulcanizing agent and preparation method and application thereof | |
| CN117654646A (en) | Organic sulfur complexing agent, preparation method thereof and application of organic sulfur complexing agent as vulcanizing agent | |
| CN117658978A (en) | Organic polythioether and preparation method and application thereof | |
| CN117654645A (en) | Hydrogenation catalyst vulcanizing agent and preparation method and application thereof | |
| CN1059204C (en) | Process for preparing dimethyl thio-ether and methylthio-alcohol | |
| CN107074736A (en) | The method for making fluosulfonic acid ester compounds be coupled with amines | |
| JP7160827B2 (en) | Method for producing methyl methacrylate or methacrylic acid | |
| CN106432799A (en) | Reclaimed rubber activation agent, preparation method and application | |
| CN108097333B (en) | Vulcanizing agent for hydrogenation catalyst and preparation method thereof | |
| CN110845440B (en) | Method for preparing 2-mercaptobenzothiazole | |
| JPS622584B2 (en) | ||
| JPS63159362A (en) | Production of methyleneimine compound | |
| US6242652B1 (en) | Process for producing organic trisulfides | |
| CN108409713B (en) | Method for synthesizing sulfurized isobutylene | |
| US2985692A (en) | Manufacture of alkyl magnesium compounds | |
| US2511961A (en) | Beta-nitroalkyi | |
| JP4873944B2 (en) | Use of an H2S-containing offgas stream to prepare a sulfur-containing product | |
| EP0308462B1 (en) | Protic solvent in a dehydrohalogenation process | |
| US3801662A (en) | Production of anthracene from 2-methyl diphenyl methanes in presence of sulfur | |
| WO2022264852A1 (en) | METHOD FOR PRODUCING α-OLEFIN | |
| Mori et al. | Curing reaction of elastomers with triazine thiols and sulfen amides | |
| US2426648A (en) | Manufacture of sulfur compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |