CN110156607A - A kind of preparation method of tire anti-aging agent 3100 - Google Patents
A kind of preparation method of tire anti-aging agent 3100 Download PDFInfo
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- CN110156607A CN110156607A CN201910476163.XA CN201910476163A CN110156607A CN 110156607 A CN110156607 A CN 110156607A CN 201910476163 A CN201910476163 A CN 201910476163A CN 110156607 A CN110156607 A CN 110156607A
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- aging agent
- tire anti
- catalyst
- preparation
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- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000767 polyaniline Polymers 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010792 warming Methods 0.000 claims abstract description 6
- 238000013019 agitation Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- XZDYFCGKKKSOEY-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1CCN(C=2C(=CC=CC=2C(C)C)C(C)C)[C]1 XZDYFCGKKKSOEY-UHFFFAOYSA-N 0.000 description 1
- QFTSXPJTPSOVJG-UHFFFAOYSA-N 4-n-(2-methylphenyl)-1-n-phenylbenzene-1,4-diamine Chemical compound CC1=CC=CC=C1NC(C=C1)=CC=C1NC1=CC=CC=C1 QFTSXPJTPSOVJG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of tire anti-aging agent 3100 belongs to fine chemistry industry synthesis field, and in particular to the production technology of tire anti-aging agent 3100.Mutual-amido two polyaniline, catalyst are placed in reaction kettle, it is kept the temperature after being warming up to 110~140 DEG C, and it is evacuated to -0.06MPa, the mixture being made of phenol and o-cresol is added under agitation, reaction is until it cannot steam water, then 90~100 DEG C are cooled to, Filtration of catalyst is to get tire anti-aging agent 3100.The raw materials technology is easy to get, and reaction process is simple, mild condition, consumes energy low with control；The waste of generation is few, is suitble to large-scale production.
Description
Technical field
The invention belongs to fine chemistry industries to synthesize field, and in particular to the production technology of tire anti-aging agent 3100.
Background technique
The effective component of anti-aging agent 3100 is N- phenyl-N '-o-tolyl p-phenylenediamine, N, N '-diphenyl pair
Phenylenediamine, N, the mixture of N '-di-o-tolyl p-phenylenediamine, is p phenylenediamine type antioxidant, can anti-ozone, it is anti-deflect it is resistance to
The performance that is cracked is similar to antioxidant 4010NA and 6PPD, to get well more than antioxidant A, D.3100 long-term behaviour of anti-aging agent is good, especially
It is used in combination with anti-aging agent 6PPD or 4010NA 1: 1, is to improve the best ozone-resistant system of Life of Tyre, reason
It is that two types p-phenylenediamine has synergistic effect, anti-aging agent 6PPD or 4010NA is providing necessary short-term defences work in early days
With, and anti-aging agent 3100 then plays long-term protective action.Due to drawing on the phenyl ring on the molecular structure both sides of anti-aging agent 3100
Rise one or two solubilizing group because, therefore its solubility in rubber increases, and bloom is also much lower, permission have in sizing material compared with
Big dosage.Anti-aging agent 3100 is since its alkalinity is small, and on vulcanization and incipient scorch substantially without influence, anti-metal toxic is p-phenylenediamine
Class anti-aging agent is strongest, plays protection effect time longest, is therefore particularly suited for the load-carrying tire of use condition harshness, cross-country tire
And each radial tire and bias tire.Anti-aging agent 3100 can also thoroughly change outside using anti-aging agent 6PPD and 4010NA tire
See the defect to redden.
Foreign countries are permitted the formula of the great positive active development anti-aging agent 3100 of rubber tyre company to replace anti-aging agent at present
4010NA, the product have also been widely used in bias tire and radial at home, by tire and rubber processing industry
Popular welcome, have wide application prospect.
Current main preparation process both at home and abroad:
1, US 4269763, CN201210013489 patent document are disclosed is being catalyzed with hydroquinone, aniline and ortho-aminotoluene
Agent effect is lower to carry out condensation dehydration by 230~270 DEG C of hot conditions, neutralization, washing, distillation obtain product.Reaction equation is as follows:
2, proposition p-phenylenediamine and chlorobenzene are under iN/SIPr catalytic action in J.Org.Chem, 2005,690:6169-6177
Following reaction occurs:
3, Green Chem.2007.9:80-84 proposes a kind of friendly process yin, with one cyclohexanedione of Isosorbide-5-Nitrae and arylamine reaction, adopts
With ethanol as solvent, reaction can carry out at room temperature, and conversion ratio can reach 95%, and reaction equation is as follows:
In the above method, 1 reaction temperature of technique is up to 230~270 DEG C, and due to reaction temperature height, energy consumption is high, will also result in material
Coking and heavy corrosion is caused to equipment；2 advantage of technique is that reaction temperature is lower, and catalyst amount is few.But catalyst
Preparation process is extremely complex, industrialized to have little significance；This route of technique 3 meets the concept of atom economy, and reaction condition is mild
It is environmentally protective, but be made since one cyclohexanedione of Isosorbide-5-Nitrae itself is more difficult, it is expensive, limit the industrialized process of the route.
Summary of the invention
The object of the invention is just to provide for a kind of simple process, mild condition, higher 3100 work of anti-aging agent of safety
Industry preparation method.
The technical scheme is that: mutual-amido two polyaniline, catalyst are placed in reaction kettle, after being warming up to 110~140 DEG C
Heat preservation, and it is evacuated to -0.06MPa, the mixture being made of phenol and o-cresol is added under agitation, reacts to not
Until water capable of being steamed, 90~100 DEG C are then cooled to, Filtration of catalyst is to get tire anti-aging agent 3100.
Reaction equation of the present invention is as follows:
Since the present invention is when reacting progress, water generation is had, when no longer generating water in system, then illustrates that reaction is completed.
It is proved repeatedly and shows that the reaction can be carried out normally under the conditions of 110~140 DEG C, the vacuum degree of -0.06MPa
Can guarantee temperature in this range, and can have steam reaction generate water.
Due to 90~100 DEG C be product melting range, can guarantee that product is liquid under the conditions of such temperature, be convenient for
Filter, with separating catalyst.
The raw materials technology is easy to get, and reaction process is simple, mild condition, consumes energy low with control；The waste of generation is few, is suitble to
Large-scale production.
Further, the mixture of phenol and o-cresol composition of the present invention is added in a manner of point 3~5 batches.
Since the reaction is exothermic reaction, reaction temperature can effectively be controlled by being added portionwise, and prevent reaction excessively violent.
It is of the present invention by phenol and adjacent first in order to ensure fully using the heat of reaction production come maintaining reaction temperature
The mixture of phenol composition adds in 2h.
The mixing mass ratio of the mutual-amido two polyaniline, phenol and o-cresol is 3~6: 1: 0.6~2.2.Such ratio
Example can guarantee that primary raw material mutual-amido two polyaniline can react completely, while the ratio of phenol and o-cresol can be certain
Range adjustment, such technical process neither influences product quality, while advantageously reducing cost of material.
The catalyst is CuCl2Or NiCl2.Using CuCl2, NiCl2It urges as catalyst is with higher to the reaction
Change performance, and the catalyst is easily separated after reacting, and cheap is easy to get.
The mixing mass ratio of the catalyst and mutual-amido two polyaniline is 1: 30~34.5.This is because if catalyst is low
In the ratio, then the reaction time, which can lengthen, even reacts incomplete；If being higher than the ratio, catalytic efficiency is improved unknown
It is aobvious, then it causes to waste.
Specific embodiment
Embodiment 1:
By 184g mutual-amido two polyaniline and 5.5gCuCl2It is added in reactor, starts and be stirred, be warming up to 110 DEG C or more, so
After open vacuum, so that vacuum degree is maintained at -0.06MPa, then divide 3 batches be added 33g phenol and 72g o-cresol mixtures,
Control adds in 2h, maintains the temperature in 110~140 DEG C, reaction dehydration, when temperature reaches 130 DEG C and deviates from without water,
Reaction is completed.Reaction solution is cooled to 90~100 DEG C, filters off catalyst while hot, obtains finished product 276g, reacts yield
96.2%, 92.5 DEG C of fusing point.
Embodiment 2:
By 184g mutual-amido two polyaniline and 6gCuCl2It is added in reactor, starts and be stirred, be warming up to 110 DEG C or more, then
Vacuum is opened, vacuum degree is made to be maintained at -0.06MPa, then divides 5 batches of mixtures that 47g phenol and 54g o-cresol is added, control
System adds in 2h, maintains the temperature in 110~140 DEG C, reaction dehydration, when temperature reaches 130 DEG C and deviates from without water, instead
It should complete.Reaction solution is cooled to 90~100 DEG C, filters off catalyst while hot, obtains finished product 280g, reacts yield 98.2%,
92 DEG C of fusing point.
Embodiment 3:
By 184g mutual-amido two polyaniline and 6gNiCl2It is added in reactor, starts and be stirred, be warming up to 110 DEG C or more, then
Vacuum is opened, vacuum degree is made to be maintained at -0.06MPa, then divides 4 batches of mixtures that 61g phenol and 38g o-cresol is added, control
System adds in 2h, maintains the temperature in 110~140 DEG C, reaction dehydration, when temperature reaches 130 DEG C and deviates from without water, instead
It should complete.Reaction solution is cooled to 90~100 DEG C, filters off catalyst while hot, obtains finished product 270g, reacts yield 95.7%,
91.4 DEG C of fusing point.
The finished product that above three obtain is subjected to GC detection respectively, is all tire anti-aging agent 3100.
Claims (6)
1. a kind of preparation method of tire anti-aging agent 3100, it is characterised in that: mutual-amido two polyaniline, catalyst are placed in reaction kettle
It is interior, it keeps the temperature, and be evacuated to -0.06MPa, is added under agitation by phenol and o-cresol after being warming up to 110~140 DEG C
The mixture of composition reacts until it cannot steam water, is then cooled to 90~100 DEG C, Filtration of catalyst is to get tire
Anti-aging agent 3100.
2. the preparation method of tire anti-aging agent 3100 according to claim 1, it is characterised in that: the phenol and o-cresol
The mixture of composition is added in a manner of point 3~5 batches.
3. the preparation method of tire anti-aging agent 3100 according to claim 2, it is characterised in that: described by phenol and adjacent toluene
The mixture of phenol composition adds in 2h.
4. the preparation method of tire anti-aging agent 3100 according to claim 1, it is characterised in that: the mutual-amido two polyaniline,
The mixing mass ratio of phenol and o-cresol is 3~6: 1: 0.6~2.2.
5. the preparation method of tire anti-aging agent 3100 according to claim 1, it is characterised in that: the catalyst is CuCl2Or
NiCl2。
6. the preparation method of tire anti-aging agent 3100 according to claim 5, it is characterised in that: the catalyst with to amino
The mixing mass ratio of diphenylamines is 1: 30~34.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910476163.XA CN110156607A (en) | 2019-06-03 | 2019-06-03 | A kind of preparation method of tire anti-aging agent 3100 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910476163.XA CN110156607A (en) | 2019-06-03 | 2019-06-03 | A kind of preparation method of tire anti-aging agent 3100 |
Publications (1)
| Publication Number | Publication Date |
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| CN110156607A true CN110156607A (en) | 2019-08-23 |
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| CN201910476163.XA Withdrawn CN110156607A (en) | 2019-06-03 | 2019-06-03 | A kind of preparation method of tire anti-aging agent 3100 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103429A (en) * | 1977-02-23 | 1978-09-08 | Mitsui Toatsu Chem Inc | Aromatic secondary amine mixture and preparation process thereof |
| 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 |
| JPS56125343A (en) * | 1980-03-07 | 1981-10-01 | Mitsui Petrochem Ind Ltd | Preparation of phenylenediamine or its n-substituted compound |
| CN102557966A (en) * | 2011-12-23 | 2012-07-11 | 中国石油化工股份有限公司 | Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) |
| CN102584596A (en) * | 2012-01-17 | 2012-07-18 | 宜兴市聚金信化工有限公司 | Method for preparing age inhibitor 3100 |
| CN106608827A (en) * | 2015-10-21 | 2017-05-03 | 江苏圣奥化学科技有限公司 | Preparation method for aryl substituted p-phenylenediamine substance |
-
2019
- 2019-06-03 CN CN201910476163.XA patent/CN110156607A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103429A (en) * | 1977-02-23 | 1978-09-08 | Mitsui Toatsu Chem Inc | Aromatic secondary amine mixture and preparation process thereof |
| JPS56125343A (en) * | 1980-03-07 | 1981-10-01 | Mitsui Petrochem Ind Ltd | Preparation of phenylenediamine or its n-substituted compound |
| 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 |
| CN102557966A (en) * | 2011-12-23 | 2012-07-11 | 中国石油化工股份有限公司 | Method for preparing anti-aging agent differential temperature programmed desorption (DTPD) |
| CN102584596A (en) * | 2012-01-17 | 2012-07-18 | 宜兴市聚金信化工有限公司 | Method for preparing age inhibitor 3100 |
| CN106608827A (en) * | 2015-10-21 | 2017-05-03 | 江苏圣奥化学科技有限公司 | Preparation method for aryl substituted p-phenylenediamine substance |
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Application publication date: 20190823 |