CN102557966A - Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) - Google Patents
Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) Download PDFInfo
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- CN102557966A CN102557966A CN2011104379687A CN201110437968A CN102557966A CN 102557966 A CN102557966 A CN 102557966A CN 2011104379687 A CN2011104379687 A CN 2011104379687A CN 201110437968 A CN201110437968 A CN 201110437968A CN 102557966 A CN102557966 A CN 102557966A
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- CN
- China
- Prior art keywords
- hydroxy diphenylamine
- dtpd
- methyl
- hydroxy
- diphenylamine
- 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.)
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- 238000000034 method Methods 0.000 title claims abstract 9
- 230000003712 anti-aging effect Effects 0.000 title abstract 4
- 238000003795 desorption Methods 0.000 title abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract 9
- JTTMYKSFKOOQLP-UHFFFAOYSA-N 4-hydroxydiphenylamine Chemical compound C1=CC(O)=CC=C1NC1=CC=CC=C1 JTTMYKSFKOOQLP-UHFFFAOYSA-N 0.000 claims abstract 7
- 239000002994 raw material Substances 0.000 claims abstract 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims abstract 3
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 4
- 238000006243 chemical reaction Methods 0.000 claims 4
- PIBIAJQNHWMGTD-UHFFFAOYSA-N 1-n,3-n-bis(4-methylphenyl)benzene-1,3-diamine Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(NC=2C=CC(C)=CC=2)=C1 PIBIAJQNHWMGTD-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 claims 2
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical group C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 239000006227 byproduct Substances 0.000 abstract 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 238000006482 condensation reaction Methods 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing an anti-aging agent differential temperature programmed desorption (DTPD) belongs to the technical field of organic chemistry. Defined amount of o-methylaniline, ferric chloride and toluene are added in about 12%-15% by-product raw material in an anti-aging agent DTPD synthetic process, by means of condensation reaction, 4-hydroxy diphenylamine, 2'-methyl-4-hydroxy diphenylamine in the by-products are converted into effective components of the anti-aging agent DTPD, production cost is reduced, and economic benefits of the DTPD are improved.
Description
Technical field
The present invention relates to organic chemistry filed, relate to the preparation method of a kind of antioxidant D TPD.
Background technology
Antioxidant D TPD is N; N '-diphenyl-para-phenylene diamine, N-phenyl-N '-o-tolyl Ursol D, N; The mixture of N '-di-o-tolyl Ursol D is a p phenylenediamine type antioxidant, can prevent ozone; Anti-deflect crack resistance can be similar with 6PPD with antioxidant 4010NA, to get well more than antioxidant A, D.Antioxidant D TPD long-term behaviour is good; Especially measure and use with 1:1 with anti-aging agent 6PPD or 4010NA; Be to improve tire best anti-ozone system in work-ing life; Its reason is that two types of Ursol D have synergistic effect, and anti-aging agent 6PPD or 4010NA provide necessary short-term protective effect in early days, and antioxidant D TPD then plays secular protective effect.Because connected one or two solubilizing group on the phenyl ring on the molecular structure both sides of antioxidant D TPD, so its solubleness in rubber heightens, bloom property is also much lower, allow in sizing material, to have bigger consumption.Antioxidant D TPD is because its alkalescence is little; Sulfuration and incipient scorch there is not influence basically; Anti-metal toxic is that p phenylenediamine type antioxidant is the strongest, and the performance protection effect time is the longest, therefore is particularly suitable for working conditions harsh load-carrying tire, cross-country tire and each radial tire and oblique tire.Antioxidant D TPD can also thoroughly change and uses the defective that anti-aging agent 6PPD and 4010NA tire outward appearance redden.
Antioxidant D TPD is synthetic to be raw material with Resorcinol, aniline, Ortho Toluidine, accomplishes through condensation, washing, distillation.In still-process, except that steaming aniline, Ortho Toluidine, the 4-hydroxy diphenylamine, the 2 '-methyl-4-hydroxy diphenylamine that do not transform fully also need be accomplished and steam, otherwise can influence the fusing point of DTPD, cause off quality.
In the antioxidant D TPD building-up process, produce about 12% ~ 15% by product, main component is 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine; This by product is if residue among the antioxidant D TPD; Can reduce the content of main component, influence the fusing point of DTPD, cause that DTPD's is off quality.In the therefore synthetic DTPD process, need this by product be separated fully.Isolated by product adopts burning method to handle at present, and burning disposal is a kind of uneconomic method, can increase raw material consumption on the one hand, causes the production cost of DTPD to increase, and does not meet the low-carbon (LC) principle on the other hand.
Summary of the invention
The objective of the invention is to propose a kind of new method for preparing antioxidant D TPD.
It is raw material that the inventive method prepares the by product that generates in the process with DTPD; Add Ortho Toluidine, catalyzer and dewatering agent with suitable proportioning; Make the active princlple in the by product be converted into antioxidant D TPD active princlple, remove catalyzer and lower boiling component acquisition antioxidant D TPD through washing, separation again.The target that realization is turned waste into wealth reduces production costs, and increases economic efficiency.
Main technical schemes of the present invention: comprise following consecutive steps: the distillation component that will contain 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine adds in the reactor drum; According to the amount of 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine wherein; Add Ortho Toluidine, toluene, catalyzer in proportion; Temperature reaction 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mass percent and less than 2% in reaction solution, with after reaction solution cooling, washing, neutralization, the distillation the DTPD finished product.
Usually, 4-hydroxy diphenylamine, 2 '-methyl-4-hydroxy diphenylamine content and be 25% ~ 50% of raw material total mass in the inventive method reaction raw materials, other components are the active princlple of pentanoic and DTPD.
Said Ortho Toluidine add mole number be 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mole number and 1.15 times.
Said catalyzer is an iron(ic)chloride, the adding mole number of iron(ic)chloride be 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mole number and 3% ~ 4%.
The amount that said toluene adds is 0.5 ~ 1% of a raw material total mass.
Compared with prior art, the present invention has following advantage:
The present invention utilizes the synthetic title product DTPD of the by product of DTPD production process, reduces production costs, and increases economic efficiency.
Embodiment
Below in conjunction with specific embodiment the present invention is further described:
Embodiment 1
Get raw material 100 gram, 4-hydroxy diphenylamine content 26.5% wherein, 2 '-methyl-4-hydroxy diphenylamine content 14.3% adds Ortho Toluidine 26.5 grams; Toluene 1 gram, iron trichloride 1.1 grams, temperature reaction is 3.7 grams to generating the water yield; Sampling analysis, 4-hydroxy diphenylamine, 2 '-methyl-4-hydroxy diphenylamine content and be 1.37% in the reaction solution are cooled to 100 ℃ with reaction solution; Add water washing, neutralize, distill the DTPD finished product, 91.4 ℃ of first fusing points.
Embodiment 2
Get raw material 100 gram, 4-hydroxy diphenylamine content 22.9% wherein, 2 '-methyl-4-hydroxy diphenylamine content 11.5% adds Ortho Toluidine 22.4 grams; Toluene 1 gram, iron trichloride 0.9 gram, temperature reaction is 3.2 grams to generating the water yield; Sampling analysis, 4-hydroxy diphenylamine, 2 '-methyl-4-hydroxy diphenylamine content and be 1.26% in the reaction solution are cooled to 100 ℃ with reaction solution; Add water washing, neutralize, distill the DTPD finished product, 90.7 ℃ of fusing points.
Embodiment 3
Get raw material 100 gram, 4-hydroxy diphenylamine content 23.4% wherein, 2 '-methyl-4-hydroxy diphenylamine content 17.2% adds Ortho Toluidine 26.1 grams; Toluene 1 gram, iron trichloride 1.0 grams, temperature reaction is 3.7 grams to generating the water yield; Sampling analysis, 4-hydroxy diphenylamine, 2 '-methyl-4-hydroxy diphenylamine content and be 1.48% in the reaction solution are cooled to 100 ℃ with reaction solution; Add water washing, neutralize, distill the DTPD finished product, 91.9 ℃ of fusing points.
Claims (6)
1. method for preparing antioxidant D TPD; Its characteristic comprises following consecutive steps: the distillation component that will contain 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine adds in the reactor drum; According to the amount of 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine wherein; Add Ortho Toluidine, toluene, catalyzer in proportion; Temperature reaction 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mass percent and less than 2% in reaction solution, with after reaction solution cooling, washing, neutralization, the distillation the DTPD finished product.
2. method according to claim 1 and 2 is characterized in that 4-hydroxy diphenylamine in the reaction raw materials, 2 '-methyl-4-hydroxy diphenylamine content and is 25% ~ 50% of raw material total mass that other components are the active princlple of pentanoic and DTPD.
3. method according to claim 1, it is characterized in that Ortho Toluidine add mole number be 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mole number and 1.15 times.
4. method according to claim 1 is characterized in that said catalyzer is an iron(ic)chloride.
5. according to claim 1 or 4 described methods, the adding mole number that it is characterized in that catalyzer iron(ic)chloride be 4-hydroxy diphenylamine and 2 '-methyl-4-hydroxy diphenylamine mole number and 3% ~ 4%.
6. method according to claim 1, the add-on that it is characterized in that toluene is 0.5 ~ 1% of a raw material total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104379687A CN102557966A (en) | 2011-12-23 | 2011-12-23 | Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104379687A CN102557966A (en) | 2011-12-23 | 2011-12-23 | Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102557966A true CN102557966A (en) | 2012-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011104379687A Pending CN102557966A (en) | 2011-12-23 | 2011-12-23 | Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085017A (en) * | 2016-07-18 | 2016-11-09 | 安徽朗凯奇建材有限公司 | A kind of heat-insulating waterproof coating of butadiene-styrene rubber not chapped and preparation method thereof |
| CN110156607A (en) * | 2019-06-03 | 2019-08-23 | 扬州市业昌助剂有限公司 | A kind of preparation method of tire anti-aging agent 3100 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269763A (en) * | 1980-03-21 | 1981-05-26 | The Goodyear Tire & Rubber Company | Method for the production of low melting ring alkylated diphenyl-para-phenylenediamines |
| US5750786A (en) * | 1997-02-20 | 1998-05-12 | The Goodyear Tire & Rubber Company | Process for the preparation of unsubstituted and substituted diaryl phenylenediamines |
| WO2009076622A2 (en) * | 2007-12-12 | 2009-06-18 | Massachusetts Institute Of Technology | Ligands for transition-metal-catalyzed cross-couplings, and methods of use thereof |
| CN101921193A (en) * | 2010-04-30 | 2010-12-22 | 句容市兴春化工有限公司 | A process for preparing anti-aging agent mixed diaryl-p-phenylenediamine with pressure |
-
2011
- 2011-12-23 CN CN2011104379687A patent/CN102557966A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269763A (en) * | 1980-03-21 | 1981-05-26 | The Goodyear Tire & Rubber Company | Method for the production of low melting ring alkylated diphenyl-para-phenylenediamines |
| US5750786A (en) * | 1997-02-20 | 1998-05-12 | The Goodyear Tire & Rubber Company | Process for the preparation of unsubstituted and substituted diaryl phenylenediamines |
| WO2009076622A2 (en) * | 2007-12-12 | 2009-06-18 | Massachusetts Institute Of Technology | Ligands for transition-metal-catalyzed cross-couplings, and methods of use thereof |
| CN101921193A (en) * | 2010-04-30 | 2010-12-22 | 句容市兴春化工有限公司 | A process for preparing anti-aging agent mixed diaryl-p-phenylenediamine with pressure |
Non-Patent Citations (3)
| Title |
|---|
| KUCZKOWSKI,J.A. 等: "Novel preparation of alkyl-aryl-p-phenylenediamines from hydroquinone", 《POLYMER PREPRINTS》 * |
| ZAGHAL, MUKARRAM H. 等: "The synthesis of the diimine and the radical cation chloride of N,N"-diphenyl-p-phenylenediamine", 《ORGANIC PREPARATIONS AND PROCEDURES INTERNATIONAL》 * |
| 吕咏梅: "对苯二胺类橡胶防老剂技术进展及市场需求分析", 《橡胶科技市场》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106085017A (en) * | 2016-07-18 | 2016-11-09 | 安徽朗凯奇建材有限公司 | A kind of heat-insulating waterproof coating of butadiene-styrene rubber not chapped and preparation method thereof |
| CN110156607A (en) * | 2019-06-03 | 2019-08-23 | 扬州市业昌助剂有限公司 | A kind of preparation method of tire anti-aging agent 3100 |
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| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120711 |