CN103755613B - The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc - Google Patents
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc Download PDFInfo
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- CN103755613B CN103755613B CN201410009894.0A CN201410009894A CN103755613B CN 103755613 B CN103755613 B CN 103755613B CN 201410009894 A CN201410009894 A CN 201410009894A CN 103755613 B CN103755613 B CN 103755613B
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- dibenzylamine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- SKLFNNLCTLZUOV-UHFFFAOYSA-N dibenzylcarbamodithioic acid;zinc Chemical compound [Zn].C=1C=CC=CC=1CN(C(=S)S)CC1=CC=CC=C1 SKLFNNLCTLZUOV-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000013040 rubber vulcanization Methods 0.000 title claims abstract description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000013543 active substance Substances 0.000 claims abstract description 12
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- AUMBZPPBWALQRO-UHFFFAOYSA-L zinc;n,n-dibenzylcarbamodithioate Chemical compound [Zn+2].C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1.C=1C=CC=CC=1CN(C(=S)[S-])CC1=CC=CC=C1 AUMBZPPBWALQRO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000008096 xylene Substances 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- -1 dibenzyl dithio zinc formate Chemical compound 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- YKVABMCSVUSETE-UHFFFAOYSA-N dibenzylcarbamodithioic acid;sodium Chemical compound [Na].C=1C=CC=CC=1CN(C(=S)S)CC1=CC=CC=C1 YKVABMCSVUSETE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 150000004005 nitrosamines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- MBBWTVUFIXOUBE-UHFFFAOYSA-L zinc;dicarbamodithioate Chemical compound [Zn+2].NC([S-])=S.NC([S-])=S MBBWTVUFIXOUBE-UHFFFAOYSA-L 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc.The method preparation process is as follows: the solution adding dibenzylamine, xylene mixture in container, add tensio-active agent simultaneously, add catalyzer and zinc oxide, when being raised to certain temperature, dithiocarbonic anhydride is added drop-wise in mixture, after the stirring reaction regular hour, from reaction mixture, filter out product zinc dibenzyldithiocarbamate; After filtering, product adds water and water component distillation again, obtained high purity product.Present method is simple to operate, compares with preparation method in the past, and reaction conditions is not harsh, and product purity is high, and recycled solvent is beneficial to environmental protection, and the most important thing is, adds catalyzer and substantially reduces the reaction times, reduces reaction time.
Description
(1) technical field:
The invention belongs to thiofide field, relate to a kind of preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc.
(2) technical background:
Zinc dibenzyldithiocarbamate can be abbreviated as: ZBEC, and its structural formula is:
This product is a kind of speed ultraaccelerator quickly, be applicable to natural gum and synthetical glue, this product is a kind of safe secondary amine dithiocarbamatetype accelerator, this product is used not release Carcinogenic Nitrosamines, in all zinc salt of dithiocarbamate class promotor, ZBEC has the longest scorching quality, has fabulous anti-early stage sulfo-effect in latex.Its sulfurate activity temperature is lower, operates safer, the uses such as alternative ZDBC, ZDEC, PZ, is the excellent promoting agent of thiazole accelerator.When using this product, the use level of zinc oxide and Sulfur is general, and lipid acid can be used can.It directly can add sizing material, also can make dispersion and add latex.The industrial general method for making of zinc dibenzyldithiocarbamate is: dibenzylamine, sodium hydroxide and dithiocarbonic anhydride react and generates dibenzyl aminodithioformic acid sodium solution, generate zinc dithiocarbamate in zinc sulfate or zinc oxide reaction again, the method produces a large amount of containing inorganic salt waste water.DE4102337 discloses a kind of preparation method of zinc dibenzyldithiocarbamate, though the method uses organic solution to drink zinc oxide, eliminates the generation of inorganic salt, reaction needed 24h, after steaming organic solution, washes product with water, produce a large amount of waste water.DE10017103 discloses a kind of preparation method of dibenzyl dithio zinc formate: dibenzylamine and zinc carbonate generate complex compound, then reacts with dithiocarbonic anhydride and sodium hydroxide, generates dibenzyl dithio zinc formate, still produces a large amount of brine waste.
(3) summary of the invention:
The present invention, for making up the deficiencies in the prior art, provides a kind of preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc.
The present invention is achieved through the following technical solutions:
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc of the present invention, comprise the following steps: the solution adding dibenzylamine, xylene mixture in container, add tensio-active agent simultaneously, add catalyzer and zinc oxide, when being raised to certain temperature, dithiocarbonic anhydride is added drop-wise in mixture, after the stirring reaction regular hour, from reaction mixture, filter out product zinc dibenzyldithiocarbamate; After filtering, product adds water and water component distillation again, obtained high purity ZBEC product.
In reparation technology of the present invention, in the reaction times, temperature of reaction, adds the amount of dibenzylamine, dimethylbenzene, and the amount of catalyzer, zinc oxide all can affect the generation of product, according to optimum scheme choice of the present invention.
Mol ratio in the present invention: dibenzylamine: dithiocarbonic anhydride=1:0.9-1.2.
Dibenzylamine: zinc oxide=1:0.4-0.6.
In dibenzylamine in the present invention: the consumption of catalyzer is the 2-12% of dibenzylamine quality.
The amount of tensio-active agent is the 1-2% of dibenzylamine quality.
The amount of dimethylbenzene is 4-6 times of dibenzylamine quality.
Reaction times is 4-6 hour, and temperature of reaction is 25-60 DEG C.
Tensio-active agent is anionic surfactant sodium dodecylbenzene sulfonate.
Catalyzer is lower molecular weight lipid acid.
When after filtering, product adds water with water component distillation, the dimethylbenzene distilled out and Water Sproading utilize.
The invention has the beneficial effects as follows, simple to operate, compare with preparation method in the past, reaction conditions is not harsh, and product purity is high, and distillates solvent xylene and water can recycles, and non-wastewater discharge is beneficial to environmental protection.Use zinc oxide not produce inorganic salt, and the most important thing is, add catalyzer and substantially reduce the reaction times, reduce reaction time.
(4) embodiment:
Embodiment 1:
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc of the present invention, comprise the following steps: in the four-hole boiling flask of 500ml having thermometer, agitator, chuck and control temperature, add 200g dimethylbenzene, 50g dibenzylamine, 0.5g tensio-active agent, 17.4gCS
2, 8.3gZnO, 6g catalyzer, drips dithiocarbonic anhydride, stirring reaction 6h when being warming up to 25 DEG C.Then lower the temperature filtration, the filtration product azeotropic that adds water steams dimethylbenzene, and remained drying obtains product ZBEC.Product yield 98.1%, fusing point 183 DEG C, Zn content 10.17%.
Tensio-active agent is anionic surfactant sodium dodecylbenzene sulfonate.
Catalyzer is the one in formic acid, acetic acid, propionic acid.
When after filtering, product adds water with water component distillation, the dimethylbenzene distilled out and water recoverable.
Embodiment 2:
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc of the present invention, comprise the following steps: in the four-hole boiling flask of 500ml having thermometer, agitator, chuck and control temperature, add 240g dimethylbenzene, 50g dibenzylamine, 0.7g tensio-active agent, 21.0gCS
2, 10gZnO, 4g catalyzer, drips dithiocarbonic anhydride, stirring reaction 5h when being warming up to 40 DEG C.Then lower the temperature filtration, the filtration product azeotropic that adds water steams dimethylbenzene, and remained drying obtains product ZBEC.Product yield 97.9%, fusing point 183 DEG C, Zn content 10.87%.
All the other are identical with embodiment 1.
Embodiment 3:
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc of the present invention, comprise the following steps: in the four-hole boiling flask of 500ml having thermometer, agitator, chuck and control temperature, add 280g dimethylbenzene, 50g dibenzylamine, 0.8g tensio-active agent, 21.5gCS
2, 11.9gZnO, 2g catalyzer, drips dithiocarbonic anhydride, stirring reaction 5.5h when being warming up to 35 DEG C.Then lower the temperature filtration, the filtration product azeotropic that adds water steams dimethylbenzene, and remained drying obtains product ZBEC.Product yield 97.8%, fusing point 183 DEG C, Zn content 10.98%.
All the other are identical with embodiment 1.
Embodiment 4:
The preparation method of rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc of the present invention, comprise the following steps: in the four-hole boiling flask of 500ml having thermometer, agitator, chuck and control temperature, add 300g dimethylbenzene, 50g dibenzylamine, 1g tensio-active agent, 23gCS
2, 12.3gZnO, 1g catalyzer, drips dithiocarbonic anhydride, stirring reaction 4h when being warming up to 60 DEG C.Then lower the temperature filtration, the filtration product azeotropic that adds water steams dimethylbenzene, and remained drying obtains product ZBEC.Product yield 98.1%, fusing point 183 DEG C, Zn content 11.3%.
All the other are identical with embodiment 1.
Claims (1)
1. the preparation method of a rubber vulcanization accelerator dibenzyl aminodithioformic acid zinc, it is characterized in that: comprise the following steps: the solution adding dibenzylamine, xylene mixture in container, add tensio-active agent simultaneously, add catalyzer and zinc oxide, when being raised to certain temperature, dithiocarbonic anhydride is added drop-wise in mixture, after the stirring reaction regular hour, from reaction mixture, filter out product zinc dibenzyldithiocarbamate; After filtering, product adds water and water component distillation again, obtained high purity product; Mol ratio is, dibenzylamine: dithiocarbonic anhydride=1:0.9-1.2; Dibenzylamine: zinc oxide=1:0.4-0.6; Catalyzer is the 2-12% of dibenzylamine quality; Tensio-active agent is the 1-2% of dibenzylamine quality; Dimethylbenzene is 4-6 times of dibenzylamine quality; Reaction times is 4-6 hour, and temperature of reaction is 25-60 DEG C; When after filtering, product adds water with water component distillation, the dimethylbenzene distilled out and Water Sproading utilize;
Tensio-active agent is anionic surfactant sodium dodecylbenzene sulfonate;
Catalyzer is the one in formic acid, acetic acid, propionic acid.
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FR3023289B1 (en) * | 2014-07-03 | 2016-07-15 | Mlpc Int | PROCESS FOR THE PREPARATION OF METAL DITHIOCARBAMATES |
FR3028855B1 (en) | 2014-11-25 | 2018-01-12 | Mlpc International | PROCESS FOR THE PREPARATION OF METAL DITHIOCARBAMATES |
CN106588726B (en) * | 2016-12-12 | 2018-09-11 | 江苏连连化学股份有限公司 | The method that one-step method prepares thiofide N- ethyl, N-phenyl zinc dithiocarbamates |
CN106588727B (en) * | 2016-12-12 | 2018-09-11 | 江苏连连化学股份有限公司 | The method that one-step method prepares thiofide N- ethyl, N-phenyl zinc dithiocarbamates |
CN108147985B (en) * | 2017-12-20 | 2020-06-12 | 蔚林新材料科技股份有限公司 | Preparation method of zinc dibutyl dithiocarbamate |
CN114213297A (en) * | 2021-12-01 | 2022-03-22 | 蔚林新材料科技股份有限公司 | Method for continuously synthesizing rubber vulcanization accelerator EZ |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4859787A (en) * | 1987-04-30 | 1989-08-22 | C. F. Spiess & Sohn Gmbh & Co. | Process for the preparation of dialkyldithiocarbamates of multivalent metals |
DE4102337A1 (en) * | 1991-01-26 | 1992-07-30 | Metallgesellschaft Ag | Zinc bis-di:benzyl:thiocarbamate prodn. - by direct reaction of di:benzylamine with carbon di:sulphide and zinc oxide in azeotrope-forming solvent, in presence of anionic emulsifier |
CN101955452A (en) * | 2010-04-29 | 2011-01-26 | 濮阳蔚林化工股份有限公司 | Method for preparing zinc dibenzyl dithiocarbamate (ZBDC) thiofide |
CN102276509A (en) * | 2011-06-03 | 2011-12-14 | 鹤壁联昊化工有限公司 | One-step method for preparing rubber promoter zinc dibenzyl dithiocarbamate |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4859787A (en) * | 1987-04-30 | 1989-08-22 | C. F. Spiess & Sohn Gmbh & Co. | Process for the preparation of dialkyldithiocarbamates of multivalent metals |
DE4102337A1 (en) * | 1991-01-26 | 1992-07-30 | Metallgesellschaft Ag | Zinc bis-di:benzyl:thiocarbamate prodn. - by direct reaction of di:benzylamine with carbon di:sulphide and zinc oxide in azeotrope-forming solvent, in presence of anionic emulsifier |
CN101955452A (en) * | 2010-04-29 | 2011-01-26 | 濮阳蔚林化工股份有限公司 | Method for preparing zinc dibenzyl dithiocarbamate (ZBDC) thiofide |
CN102276509A (en) * | 2011-06-03 | 2011-12-14 | 鹤壁联昊化工有限公司 | One-step method for preparing rubber promoter zinc dibenzyl dithiocarbamate |
Non-Patent Citations (1)
Title |
---|
橡胶硫化促进剂Pz的合成;杨鑫莉等;《广西化工》;19981231;第27卷(第4期);第30-33页 * |
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