CN102408367A - Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide - Google Patents
Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide Download PDFInfo
- Publication number
- CN102408367A CN102408367A CN2011102987315A CN201110298731A CN102408367A CN 102408367 A CN102408367 A CN 102408367A CN 2011102987315 A CN2011102987315 A CN 2011102987315A CN 201110298731 A CN201110298731 A CN 201110298731A CN 102408367 A CN102408367 A CN 102408367A
- Authority
- CN
- China
- Prior art keywords
- preparation
- thiuram disulfide
- thiofide
- methylphenylamine
- ammoniacal liquor
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000013040 rubber vulcanization Methods 0.000 title abstract 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims abstract description 20
- CGTGVSBVWWZIDT-UHFFFAOYSA-N isoquinolin-6-yl(trimethyl)stannane Chemical compound C1=NC=CC2=CC([Sn](C)(C)C)=CC=C21 CGTGVSBVWWZIDT-UHFFFAOYSA-N 0.000 claims abstract description 19
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 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 claims description 15
- 150000002978 peroxides Chemical class 0.000 claims description 8
- UMRSVAKGZBVPKD-UHFFFAOYSA-N acetic acid;copper Chemical compound [Cu].CC(O)=O UMRSVAKGZBVPKD-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000010446 mirabilite Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010057 rubber processing Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- HCAHMRPMYBVHGU-UHFFFAOYSA-N 1,2-dimethyl-3-phenylbenzene Chemical compound CC1=CC=CC(C=2C=CC=CC=2)=C1C HCAHMRPMYBVHGU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide. In the preparation method, N-methylaniline, ammonia water with the concentration of 10-18% and carbon disulfide are taken as reactants for reacting in the presence of a catalyst-copper acetate so as to generate the dimethyl-diphenyl thiuram disulfide under the action of an oxidant, wherein, the mole ratio of the N-methylaniline to the ammonia water with the concentration of 15% to the carbon disulfide is 1: (1.05-1.3): (1.1-1.5), the catalyst accounts for 0.03-0.08% of the total mass of the N-methylaniline, and the oxidant is a mixed solution of hydrogen peroxide and sulfuric acid. The preparation method provided by the invention has the advantages that the hydrogen peroxide is taken as the oxidant, and less waste water is generated so that the preparation process is more environmentally-friendly, and in addition, a reaction can be performed at normal pressure so as to save energy; the ammonia water is taken as a solvent so as to prevent generation of waste mirabilite; the copper acetate is taken as the catalyst so as to shorten condensation reaction time; and the process flow is short, the production cost is low, and the product competitiveness can be enhanced.
Description
Technical field
The invention belongs to the rubber ingredients technical field, be specifically related to a kind of preparation method of thiofide dimethyldiphenyl thiuram disulfide.
Background technology
In recent years, along with the fast development of Rubber processing industry, the fast development of domestic automobile industry, communication industry drives the Rubber processing industry and increases fast, unprecedented good opportunity is provided for the development of Rubber Chemicals Industries.Since the entry to WTO, though the production of China's rubber accelerator product oneself be improved largely, still have the space of developing on a large scale very much at aspects such as product inner quality and " green " green technologies.
Thiuram is one type of promotor that activity is bigger, and its disulphide and polysulfide also are the vulcanizing agents of sulphur-free vulcanization system.Use at present more thiuram accelerator and be tetramethyl-and thiuramsulfides; The low-sulfur of being made up of it and the cross-linked rubber of sulphur-free vulcanization system have good resistance toheat, impart tear and less compression set characteristics; Its main drawback is that the scorching quality of sizing material is poor; Short in the curing temperature current downflow time, process safety is poor, cross-linked rubber surface bloom.The thiofide dimethyldiphenyl thiuram disulfide is a kind of green environmental protection thiofide, can be used for high low-sulfur or does not have vulcanization systems such as sulphur, both can do promotor, can make vulcanizing agent again.It has good plateau cure curve, and vulcanization rate is fast, and aftereffect property is strong.Ageing-resistant, low temperature resistant, anti-sticking wet goods aspect all is superior to tetramethyl-thiuram disulfide.And still do not have report so far about the preparation method of dimethyldiphenyl thiuram disulfide.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of dimethyldiphenyl thiuram disulfide.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
The preparation method of thiofide dimethyldiphenyl thiuram disulfide of the present invention is following; With methylphenylamine, 10-18% ammoniacal liquor and dithiocarbonic anhydride is reactant; With neutralized verdigris as catalyzer; Reaction generates dimethyldiphenyl thiuram disulfide under the oxygenant effect; The mol ratio of described methylphenylamine, 15% ammoniacal liquor and dithiocarbonic anhydride is 1:1.05-1.3:1.1-1.5, and catalyst levels is the 0.03-0.08% of methylphenylamine quality, and said oxygenant is ydrogen peroxide 50 and sulfuric acid mixture liquid.
The preparation method of thiofide dimethyldiphenyl thiuram disulfide of the present invention is undertaken by following step: drop into methylphenylamine, 15% ammoniacal liquor respectively in the condensation still (1); After mixing, add catalyst acetic acid copper, under 120 rev/mins of rotating speeds, mixed 20-30 minute; Air-tight state slowly drips dithiocarbonic anhydride down; Temperature remains between 25-40 ℃, reacts after 2-3 hour, continues to stir 20-30 minute; (2) slow dropping oxidizing agent between temperature 30-40 ℃, the amount of splashing into is 1.15 times of theoretical molar amount; Maintain the temperature at and continue reaction between 30-40 ℃ after 2-3 hour, get finished product thiofide dimethyldiphenyl thiuram disulfide after separation, the drying then.
Described methylphenylamine, 15% ammoniacal liquor (in the molar weight of ammonia) are 1:1.1:1.15 with the mol ratio of dithiocarbonic anhydride.
Ydrogen peroxide 50 and vitriolic mol ratio are 1:1-1.2 in the said oxygenant.
The present invention is a raw material with methylphenylamine, dithiocarbonic anhydride, ammoniacal liquor, and neutralized verdigris is the catalyst compounded of master, and ydrogen peroxide 50 is an oxygenant synthesization of dimethyl phenylbenzene thiuram-disulfide, and technological operation is simple, is prone to realize suitability for industrialized production, and facility investment is few.With hydrogen peroxide as oxidant, the waste water growing amount is few, makes this technology have more the feature of environmental protection; In addition, adopt hydrogen peroxide as oxidant, can react save energy under the normal temperature.Make solvent with ammoniacal liquor, avoided the generation of waste saltcake; Adopt neutralized verdigris as catalyzer, shortened condensation reaction time.Technical process is short, and production cost is low, has increased competitiveness of product.
Embodiment
Through embodiment the present invention is elaborated below, but and do not limit the present invention in any way.
Embodiment 1
(1) 1071.5gN-monomethylaniline, 1246.7g15% ammoniacal liquor are dropped into respectively in the condensation still; After mixing, add 0.54g catalyst acetic acid copper, under 120 rev/mins of rotating speeds, mixed 25 minutes; Air-tight state slowly drips 875.6g dithiocarbonic anhydride down; Temperature remains between 30-35 ℃, reacts after 2.5 hours, continues to stir 25 minutes.
(2) slow dropping oxidizing agent between temperature 35-38 ℃, the amount of splashing into is 1.15 times of methylphenylamine molar weight; Said oxygenant is 170g ydrogen peroxide 50 and 490g vitriolic mixture.Maintain the temperature at and continue reaction between 38-40 ℃ after 2.5 hours, get finished product thiofide dimethyldiphenyl thiuram disulfide after separation, the drying then.
The product pale yellow powder, 180.3 ℃ of first fusing points, weight loss on heating≤0.10%, product purity 97%, product yield 97.1%.
Embodiment 2
(1) 1071.5gN-monomethylaniline, 1190g15% ammoniacal liquor are dropped into respectively in the condensation still; After mixing, add 0.32g catalyst acetic acid copper, under 120 rev/mins of rotating speeds, mixed 20 minutes; Air-tight state slowly drips 837.5g dithiocarbonic anhydride down; Temperature remains between 25-30 ℃, reacts after 3 hours, continues to stir 30 minutes.
(2) slow dropping oxidizing agent between temperature 38-40 ℃, the amount of splashing into is 1.15 times of methylphenylamine molar weight; Said oxygenant is 170g ydrogen peroxide 50 and 539g vitriolic mixture.Maintain the temperature at and continue reaction between 30-35 ℃ after 2 hours, get finished product thiofide dimethyldiphenyl thiuram disulfide after separation, the drying then.
The product pale yellow powder, 181.4 ℃ of first fusing points, weight loss on heating≤0.10%, product purity 98%, product yield 97.8%.
Embodiment 3
(1) 1071.5gN-monomethylaniline, 1473.3g15% ammoniacal liquor are dropped into respectively in the condensation still; After mixing, add 0.86g catalyst acetic acid copper, under 120 rev/mins of rotating speeds, mixed 30 minutes; Air-tight state slowly drips 1142.1g dithiocarbonic anhydride down; Temperature remains between 35-40 ℃, reacts after 2 hours, continues to stir 20 minutes.
(2) slow dropping oxidizing agent between temperature 30-35 ℃, the amount of splashing into is 1.15 times of methylphenylamine molar weight; Said oxygenant is 170g ydrogen peroxide 50 and 735g vitriolic mixture.Maintain the temperature at and continue reaction between 35-38 ℃ after 2 hours, get finished product thiofide dimethyldiphenyl thiuram disulfide after separation, the drying then.
The product pale yellow powder, 182.3 ℃ of first fusing points, weight loss on heating≤0.10%, product purity 97.5%, product yield 97.6%.
Claims (4)
1. the preparation method of a thiofide dimethyldiphenyl thiuram disulfide; It is characterized in that: with methylphenylamine, 10-18% ammoniacal liquor and dithiocarbonic anhydride is reactant; With neutralized verdigris as catalyzer; Reaction generates dimethyldiphenyl thiuram disulfide under the oxygenant effect; The mol ratio of described methylphenylamine, 15% ammoniacal liquor and dithiocarbonic anhydride is 1:1.05-1.3:1.1-1.5, and catalyst levels is the 0.03-0.08% of methylphenylamine quality, and said oxygenant is ydrogen peroxide 50 and sulfuric acid mixture liquid.
2. the preparation method of thiofide dimethyldiphenyl thiuram disulfide according to claim 1 is characterized in that: drop into methylphenylamine, 15% ammoniacal liquor respectively in the condensation still (1), after mixing; Add catalyst acetic acid copper; Under 120 rev/mins of rotating speeds, mixed 20-30 minute, air-tight state slowly drips dithiocarbonic anhydride down, and temperature remains between 25-40 ℃; React after 2-3 hour, continue to stir 20-30 minute; (2) slow dropping oxidizing agent between temperature 30-40 ℃, the amount of splashing into is 1.15 times of theoretical molar amount; Maintain the temperature at and continue reaction between 30-40 ℃ after 2-3 hour, get finished product thiofide dimethyldiphenyl thiuram disulfide after separation, the drying then.
3. the preparation method of thiofide dimethyldiphenyl thiuram disulfide according to claim 1 and 2 is characterized in that: the mol ratio of described methylphenylamine, 15% ammoniacal liquor and dithiocarbonic anhydride is 1:1.1:1.15.
4. the preparation method of thiofide dimethyldiphenyl thiuram disulfide according to claim 1 and 2 is characterized in that: ydrogen peroxide 50 and vitriolic mol ratio are 1:1-1.2 in the said oxygenant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110298731.5A CN102408367B (en) | 2011-09-28 | 2011-09-28 | Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110298731.5A CN102408367B (en) | 2011-09-28 | 2011-09-28 | Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102408367A true CN102408367A (en) | 2012-04-11 |
| CN102408367B CN102408367B (en) | 2014-03-19 |
Family
ID=45910758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110298731.5A Active CN102408367B (en) | 2011-09-28 | 2011-09-28 | Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102408367B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116439A (en) * | 2019-12-31 | 2020-05-08 | 鹤壁中昊新材料科技有限公司 | Synthesis process of N, N '-dialkyl-N, N' -diphenyl thiuram disulfide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2835068A1 (en) * | 1978-08-10 | 1980-02-14 | Bayer Ag | METHOD FOR PRODUCING DI- (N-METHYL-N-PHENYL-THIURAM) -DISULFIDE |
| US4468526A (en) * | 1981-02-16 | 1984-08-28 | Akzona Incorporated | Process for the preparation of thiuram disulfides |
| DE19930625A1 (en) * | 1999-07-02 | 2001-01-18 | Chemetall Gmbh | Pure thiuram disulfide preparation in high yield, for use e.g. as rubber vulcanization accelerator or anti-alcoholism drug, by reacting amine with carbon disulfide and lithium hydroxide then oxidizing with hydrogen peroxide |
| CN1299814A (en) * | 1999-12-16 | 2001-06-20 | 王继亭 | One-step preparation process of rubber sulfurizing promoter |
| CN1827596A (en) * | 2006-04-11 | 2006-09-06 | 浙江超微细化工有限公司 | Process for preparing tetra-benzyl thiram disulfide |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
-
2011
- 2011-09-28 CN CN201110298731.5A patent/CN102408367B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2835068A1 (en) * | 1978-08-10 | 1980-02-14 | Bayer Ag | METHOD FOR PRODUCING DI- (N-METHYL-N-PHENYL-THIURAM) -DISULFIDE |
| US4468526A (en) * | 1981-02-16 | 1984-08-28 | Akzona Incorporated | Process for the preparation of thiuram disulfides |
| DE19930625A1 (en) * | 1999-07-02 | 2001-01-18 | Chemetall Gmbh | Pure thiuram disulfide preparation in high yield, for use e.g. as rubber vulcanization accelerator or anti-alcoholism drug, by reacting amine with carbon disulfide and lithium hydroxide then oxidizing with hydrogen peroxide |
| CN1299814A (en) * | 1999-12-16 | 2001-06-20 | 王继亭 | One-step preparation process of rubber sulfurizing promoter |
| CN1827596A (en) * | 2006-04-11 | 2006-09-06 | 浙江超微细化工有限公司 | Process for preparing tetra-benzyl thiram disulfide |
| CN1962627A (en) * | 2006-11-21 | 2007-05-16 | 陕西科技大学 | Process for preparing tetraalkyl thiram |
Non-Patent Citations (1)
| Title |
|---|
| 樊云峰: "《硫化促进剂技术进展》", 《精细石油化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116439A (en) * | 2019-12-31 | 2020-05-08 | 鹤壁中昊新材料科技有限公司 | Synthesis process of N, N '-dialkyl-N, N' -diphenyl thiuram disulfide |
| CN111116439B (en) * | 2019-12-31 | 2023-03-14 | 鹤壁中昊新材料科技有限公司 | Synthesis process of N, N '-dialkyl-N, N' -diphenyl thiuram disulfide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102408367B (en) | 2014-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101717378B (en) | Method for synthesizing rubber vulcanization accelerator DM by oxygen oxidization | |
| CN108395393A (en) | A kind of green synthesis method of thiurams thiofide | |
| CN108530383A (en) | A kind of vulcanization accelerator TBBS and its continuous production method | |
| CN106749816B (en) | Preparation method of brominated butyl rubber | |
| CN108586295B (en) | Continuous production method of vulcanization accelerator DPG | |
| CN106866466A (en) | A kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide | |
| CN101735171A (en) | Method for synthesizing thiofide NS by oxygen oxidation method | |
| CN101215272A (en) | Method of producing rubber vulcanization accelerator DM | |
| CN104610193A (en) | Preparation method of rubber vulcanizing accelerator TBBS | |
| CN103910661B (en) | A kind of method using methanthiol to produce Methyl disulfide with sulfur cross-linking method | |
| CN102408367B (en) | Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide | |
| CN107163002B (en) | A kind of method that oxygen method prepares rubber vulcanization accelerator DM | |
| CN108947845A (en) | A kind of production method of 2,4-dinitrophenol sodium | |
| CN102838561A (en) | Production method of rubber vulcanization accelerator NS (N-tertiary butyl-2-benzothiazole sulfenamide) | |
| CN101906082A (en) | Method for synthesizing TBBS (Tertiarybutyl Benzothiazole Sulfenamide) by mechanically applying mother solution | |
| CN102827104A (en) | Method for synthesizing rubber vulcanization accelerator CZ by two-step process by using sodium hypochlorite as oxidizer | |
| CN104292462A (en) | Polyphenylene sulfide/polyphenylene sulfide sulphone copolymer and preparation method thereof | |
| CN104592161A (en) | Method for producing rubber vulcanization accelerator CBS by crude product MBT | |
| CN101717381A (en) | Method for synthesizing thiofide CZ by taking hydrogen peroxide as oxidant | |
| CN101157663A (en) | Method for producing rubber vulcanization accelerator NS | |
| CN109400509A (en) | Promotor TBzTD and its synthesis technology | |
| CN106745245B (en) | A kind of preparation method of sodium pyroantimonate and sodium metaantimonate | |
| CN108727297A (en) | A kind of hydrogen peroxide oxidation one-step synthesis technique of rubber accelerator dibenzothiazyl disulfide | |
| CN102936335A (en) | Synthetic process of hydrogenized tallow amine polyoxyethylene ether | |
| CN108047161A (en) | A kind of catalysis hydrogen peroxide oxidation synthetic method of vulcanization accelerator TBBS |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Hebi Qibin zone 458030 Henan Province Li Yang Road East Applicant after: Hebi UHOO Rubber Chemicals Co.,Ltd. Address before: Hebi Qibin zone 458030 Henan Province Li Yang Road East Applicant before: Linkwell Rubber Chemicals (Hebi) Co.,Ltd. |
|
| CB03 | Change of inventor or designer information |
Inventor after: Wang Zhenxiang Inventor after: Chen Jianjun Inventor after: Zhang Zhiliang Inventor after: Zi Weiqi Inventor after: Shi Xinjin Inventor after: Zhao Xiaofeng Inventor after: Ding Bingwei Inventor after: Li Hongliang Inventor before: Chen Jianjun Inventor before: Zhang Zhiliang |
|
| CB03 | Change of inventor or designer information | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: CHEN JIANJUN ZHANG ZHILIANG TO: WANG ZHENXIANG CHEN JIANJUN ZHANG ZHILIANG ZI WEIQI SHI XINJIN ZHAO XIAOFENG DING BINGWEI LI HONGLIANG |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of rubber vulcanization accelerator-dimethyl-diphenyl thiuram disulfide Effective date of registration: 20160512 Granted publication date: 20140319 Pledgee: Heshan Hebi Lantian Park Management Co.,Ltd. Pledgor: Hebi UHOO Rubber Chemicals Co.,Ltd. Registration number: 2016990000343 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210225 Granted publication date: 20140319 Pledgee: Heshan Hebi Lantian Park Management Co.,Ltd. Pledgor: HEBI UHOO RUBBER CHEMICALS Co.,Ltd. Registration number: 2016990000343 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 458030 east section of Liyang Road, Qibin District, Hebi City, Henan Province Patentee after: Hebi Lianhao New Material Co.,Ltd. Address before: 458030 east section of Liyang Road, Qibin District, Hebi City, Henan Province Patentee before: Hebi UHOO Rubber Chemicals Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240411 Address after: No. 19 Yuanhao Road, Jijiashan Industrial Park, Heshan District, Hebi City, Henan Province, 458020 Patentee after: Hebi Yuanhao New Material Group Co.,Ltd. Country or region after: China Address before: 458030 east section of Liyang Road, Qibin District, Hebi City, Henan Province Patentee before: Hebi Lianhao New Material Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |