CN105777557A - Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof - Google Patents
Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof Download PDFInfo
- Publication number
- CN105777557A CN105777557A CN201410778726.8A CN201410778726A CN105777557A CN 105777557 A CN105777557 A CN 105777557A CN 201410778726 A CN201410778726 A CN 201410778726A CN 105777557 A CN105777557 A CN 105777557A
- Authority
- CN
- China
- Prior art keywords
- aromatic amine
- alkylation
- mixing aromatic
- amine according
- catalyst
- 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
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 55
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 38
- 230000029936 alkylation Effects 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 60
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004061 bleaching Methods 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000004809 thin layer chromatography Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000004519 grease Substances 0.000 claims abstract description 4
- 239000010687 lubricating oil Substances 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 30
- 230000006837 decompression Effects 0.000 claims description 14
- 239000002689 soil Substances 0.000 claims description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 150000005002 naphthylamines Chemical class 0.000 claims description 9
- -1 2-phenyl propyl Chemical group 0.000 claims description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 235000006708 antioxidants Nutrition 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000006069 physical mixture Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YUFFSWGQGVEMMI-JLNKQSITSA-N (7Z,10Z,13Z,16Z,19Z)-docosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCCCC(O)=O YUFFSWGQGVEMMI-JLNKQSITSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- ZLNMGXQGGUZIJL-UHFFFAOYSA-N n-octyl-n-phenylnaphthalen-1-amine Chemical compound C=1C=CC2=CC=CC=C2C=1N(CCCCCCCC)C1=CC=CC=C1 ZLNMGXQGGUZIJL-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
An alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof, wherein the method comprises the steps of carrying out alkylation reaction on a mixture of C8 and C9 olefins and aromatic amine at 80-150 ℃ for 10-22 hours in the presence of a bleaching earth type supported catalyst, tracking the condition that the content of diphenylamine or naphthylamine in a reactant is not changed by using thin layer chromatography, adjusting the temperature to 80-160 ℃, adding a second batch of olefin to continue to react for 1-5 hours, carrying out reduced pressure distillation on the obtained product to collect olefins with different temperature fractions, filtering and collecting a solid catalyst, and finally obtaining an orange viscous liquid product; the alkylated aromatic amine comprises at least the following two compounds: 1)2)
Description
Technical field
The present invention relates to and a kind of mix the alkylation of aromatic amine, alkylation aromatic amine and application thereof.
Background technology
Amine type antioxidant has excellent antioxygenic property and higher heat stability, good oil-soluble and the ashless feature such as without phosphorus, therefore it is widely used in various fields, through laboratory exploration discovery, adopt alkylation aromatic amine type anti-oxidant performance prepared by mixed material to be better than the physical mixture of two kinds of single products, show more excellent high-temperature stability and antioxygenic property.
Conventional alkylation fragrance amine type antioxidant preparation method is as follows: with aromatic amine for raw material, under catalyst action, head product is prepared by the alkylated reaction with alkene, then pass through a series of post processing and obtain alkylation aromatic amine, how the difficult point of this reaction is in that by controlling reaction condition, control the content in component of mixture, it is thus achieved that higher active component also reduces residue aromatic amine content.
US2943112 is disclosed using a large amount of acid clays as catalyst and in the presence of a mineral acid, is reacted the alkylated diphenylamine kind antioxidant of preparation by diphenylamines and olefine, and the method diphenylamines surplus, generally 6%～12%, is reacted incomplete.
FR1508785 is published under the existence of aluminum chloride type lewis acid catalyst, and the extent of reaction is greatly improved, and diphenylamines surplus is generally about 2%.Containing chloride ion in the method product, black, aftertreatment technology is complicated.
US6315925 discloses the 2.0～25.0wt% acid clay based on diphenylamines to be existed in lower and the free protons non-existent situation of acid, and diphenylamines adopts the alkylated reaction that the mixture of excessive nonene or isomer nonene carries out, and diphenylamines surplus is approximately 2%.
EP387979 discloses and includes p, p ' compositions of-branched dioctyldiphenylamine and N-p-branched octyl phenyl-α-naphthylamine, it is necessary to reacting when diphenylamines and alkene 8 times excessive, the method needs the clay of a large amount of acid activations, and raw material availability is not high.
CN1938260A discloses a kind of alkylated pana and the method for DPA mixture, the product that this experiment is obtained by the mixture of olefin alkylation PANA or PANA and DPA, with the method for the mixture with olefin alkylation PANA or PANA and DPA, having according to the compositions of the present invention can by the prominent antioxidation of the method for testing displaying set up.
CN101348720A discloses preparation method and the application of a kind of composite amine antioxidant, and this amine type antioxidant at least contains following two material: (1) alkylated diphenylamine；(2) alkylation N-phenyl-a-naphthylamine.Add diisobutylene for the mixture of diphenylamines and N-phenyl-a-naphthylamine to be alkylated reaction and prepare, but preparation process only adds the alkene of single batch, it is impossible to change the viscosity of product and pH-value and constituent content flexibly.
Summary of the invention
It is an object of the invention to provide a kind of alkylation mixing aromatic amine, under the existence of bleaching soil type supported catalyst, C8, C9 alkene and arylamine blend, it is alkylated reaction 10～22 hours at 80 DEG C～150 DEG C, adding second batch alkene and continue reaction 1～5 hour in 80 DEG C～160 DEG C, product is orange viscous liquid.
It is a further object of the present invention to provide a kind of alkylation aromatic amine and application thereof.
The method include that
1) diphenylamines and naphthylamines are carried out being mixed into mixing aromatic amine for 4:1～3:1 in molar ratio, first olefin component being subsequently adding and mix aromatic amine equimolar amounts and the bleaching soil type supported catalyst of 4wt%～8wt%, it is alkylated reaction at 80 DEG C～150 DEG C, add first olefin component of 1～5 times of mixing aromatic amine molar equivalent after 1～4 hour, continue reaction 9～18 hours；
2) when tracking that in reactant, diphenylamines or naphthylamines content no longer change by thin layer chromatography, temperature is adjusted to 80 DEG C～160 DEG C, be initially added into the second batch olefin component of 1～4 times of mixing aromatic amine molar equivalent, continue reaction 1～5 hour；
3) by step 2) in products therefrom decompression distillation collect different temperatures fraction alkene, then solid collected by filtration catalyst, finally obtain product liquid.
Wherein, step 1) described in first olefin component selected from C8 alkene, C9 alkene or its mixture
Wherein, described C8 or C9 alkene is selected from positive octene, isooctene, diisobutylene, positive nonene, different nonene, tripropylene or its mixture.
Wherein, step 2) described in second batch olefin component selected from isobutene., polyisobutylene, styrene, polystyrene, α-methyl styrene, poly alpha methylstyrene or its mixture.
Wherein, in first olefin component participating in reaction and second batch olefin component, need to add in advance the polymerization inhibitor of 65ppm～95ppm.
Wherein, described polymerization inhibitor is selected from N-Methyl pyrrolidone, Nitrocarbol., beta-naphthylamine or p-tert-butyl catechol.
Wherein, step 1) and step 2) middle use compressive reaction device, pressure limit is 0.2～0.25MPa.
Wherein, step 3) in the vacuum of decompression distillation be 0.075～0.080MPa, temperature is 90 DEG C～130 DEG C, and the time is 2～2.5 hours.
Wherein, step 3) in filter process carry out at 70 DEG C～110 DEG C.
Wherein, step 3) in filter process adopt decompression sucking filtration.
Wherein, step 3) in reclaim catalyst can recycle.
Wherein, when recycling catalyst, it is necessary to add the original bleaching soil type supported catalyst of 20wt%～50wt%.
Wherein, described bleaching soil type supported catalyst is by adopting bleaching earth load aluminum chloride, iron chloride, boron fluoride, fluoroform sulphonate or its mixture to prepare.
The alkylation mixing aromatic amine of described alkylation gained, at least contains following two compound:
1)
Wherein, R1、R2、R3、R4And R5It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2、R3、R4And R5In have at least one for hydrogen；
2)
Wherein, R1、R2And R3It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2And R3In have at least one for hydrogen.
Described alkylation mixing aromatic amine is as the application of antioxidant.
The application in lubricating oil or grease of the described antioxidant.
The preparation of catalyst: after commercially available bleaching earth is activated, supported solid lewis acid catalyst, prepare bleaching soil type supported catalyst.
In reaction, polymerization inhibitor is primarily used to stop highly active olefin component autohemagglutination.Reaction need to control alkene rate of addition, and rate of addition is 6～9 best for controlling to react reflux ratio.
The invention has the beneficial effects as follows:
The present invention is initially with compound amine raw material, alkene with multiple batches reacts, do so obtains benefit and can be by the ratio regulating aromatic amine raw material to control non-oxidizability and product oil-soluble, and by the selection of multiple batches of alkene and adjustment, product viscosity and pH-value and constituent content can be changed, make reaction controlling very flexible, it is possible to prepare the product of different performance by changing experiment condition.
The present invention relates to the preparation participating in high efficient mixed aromatic amine antioxidant with bleaching soil type supported catalyst and multiple batches of alkene, obtain antioxidant product performance and be better than the physical mixture of two kinds of single antioxidant, product is orange viscous liquid, nitrogen content scope 3%～3.6%, diphenylamines surplus is less than 1%, alkene that decompression separation obtains and the catalyst obtained after filtering and all can be recycled, non-wastewater discharge, be conducive to environmental protection.
Detailed description of the invention
Detailed description of the invention is given below, the present invention is described in detail, but not as a limitation of the invention.
A kind of alkylation mixing aromatic amine, including:
1) diphenylamines and naphthylamines are carried out being mixed into mixing aromatic amine for 4:1～3:1 in molar ratio, first olefin component being subsequently adding and mix aromatic amine equimolar amounts and the bleaching soil type supported catalyst of 4wt%～8wt%, it is alkylated reaction at 80 DEG C～150 DEG C, add first olefin component of 1～5 times of mixing aromatic amine molar equivalent after 1～4 hour, continue reaction 9～18 hours；
2) when tracking that in reactant, diphenylamines or naphthylamines content no longer change by thin layer chromatography, temperature is adjusted to 80 DEG C～160 DEG C, be initially added into the second batch olefin component of 1～4 times of mixing aromatic amine molar equivalent, continue reaction 1～5 hour；
3) by step 2) in products therefrom decompression distillation collect different temperatures fraction alkene, then solid collected by filtration catalyst, finally obtain product liquid.
Wherein, step 1) described in first olefin component selected from C8 alkene, C9 alkene or its mixture
Wherein, described C8 or C9 alkene is selected from positive octene, isooctene, diisobutylene, positive nonene, different nonene, tripropylene or its mixture.
Wherein, step 2) described in second batch olefin component selected from isobutene., polyisobutylene, styrene, polystyrene, α-methyl styrene, poly alpha methylstyrene or its mixture.
Wherein, in first olefin component participating in reaction and second batch olefin component, need to add in advance the polymerization inhibitor of 65ppm～95ppm.
Wherein, described polymerization inhibitor is selected from N-Methyl pyrrolidone, Nitrocarbol., beta-naphthylamine or p-tert-butyl catechol.
Wherein, step 1) and step 2) middle use compressive reaction device, pressure limit is 0.2～0.25MPa.
Wherein, step 3) in the vacuum of decompression distillation be 0.075～0.080MPa, temperature is 90 DEG C～130 DEG C, and the time is 2～2.5 hours.
Wherein, step 3) in filter process carry out at 70 DEG C～110 DEG C.
Wherein, step 3) in filter process adopt decompression sucking filtration.
Wherein, step 3) in reclaim catalyst can recycle.
Wherein, when recycling catalyst, it is necessary to add the original bleaching soil type supported catalyst of 20wt%～50wt%.
Wherein, described bleaching soil type supported catalyst is by adopting bleaching earth load aluminum chloride, iron chloride, boron fluoride, fluoroform sulphonate or its mixture to prepare.
The alkylation mixing aromatic amine of described alkylation gained, at least contains following two compound:
1)
Wherein, R1、R2、R3、R4And R5It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2、R3、R4And R5In have at least one for hydrogen；
2)
Wherein, R1、R2And R3It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2And R3In have at least one for hydrogen.
Described alkylation mixing aromatic amine is as the application of antioxidant.
The application in lubricating oil or grease of the described antioxidant.
Embodiment 1
It is being furnished with agitator, thermometer, adding the positive nonene adding the diphenylamines of 67.7g, the naphthylamines of 14.3g and 63g in the 1L glass container of hot jacket, reflux condensing tube, water knockout drum, nitrogen pipeline; pass into nitrogen protection; it is stirred with magnetic stirring apparatus; 3.28g bleaching earth load aluminum chloride catalyst is added after all melting in 80 DEG C; gradually rise temperature to 150 DEG C; the positive nonene of 104g is added after 1～4 hour; control back-flow velocity and heating-up temperature; making temperature of charge be not less than 150 DEG C, the response time is 18 hours.According to TLC follow the tracks of be reacted to DPA content no longer change time, reduce reaction temperature to 130 DEG C, and add α-methyl styrene 60g continuation reaction 4 hours, suitably cool down and alkene is distilled off obtains final products in 70 DEG C of filtrations, decompression, reclaim alkene and catalyst, product is orange viscous liquid, nitrogen content 3.3%, and product property is in Table 1.
Embodiment 2
It is being furnished with agitator, thermometer, adding the different nonene adding the diphenylamines of 101.4g, the naphthylamines of 28.6g and 100.8g in the 1l glass container of hot jacket, reflux condensing tube, water knockout drum, nitrogen pipeline; pass into nitrogen protection; it is stirred with magnetic stirring apparatus; 7.8g bleaching earth load ferric chloride catalyst is added after all melting in 80 DEG C; gradually rise temperature to 150 DEG C; the different nonene of 104g is added after 1～4 hour; control back-flow velocity and heating-up temperature; making temperature of charge be not less than 150 DEG C, the response time is 18 hours.According to TLC follow the tracks of be reacted to DPA content no longer change time, reduce reaction temperature to 130 DEG C, and add isobutene. 90g continuation reaction 4 hours, suitably cool down and alkene is distilled off obtains final products in 70 DEG C of filtrations, decompression, reclaim alkene and catalyst, product is orange viscous liquid, nitrogen content 3.3%, and product property is in Table 1.
Embodiment 3
It is being furnished with agitator, thermometer, adding the positive octene adding the diphenylamines of 101.4g, the naphthylamines of 28.6g and 89.6g in the 1l glass container of hot jacket, reflux condensing tube, water knockout drum, nitrogen pipeline; pass into nitrogen protection; it is stirred with magnetic stirring apparatus; 10.4g bleaching earth load aluminum chloride catalyst is added after all melting in 80 DEG C; gradually rise temperature to 150 DEG C; the positive octene of 112g is added after 1～4 hour; control back-flow velocity and heating-up temperature; making temperature of charge be not less than 140 DEG C, the response time is 18 hours.According to TLC follow the tracks of be reacted to DPA content no longer change time, reduce reaction temperature to 130 DEG C, and add isobutene. 90g continuation reaction 4 hours, suitably cool down and alkene is distilled off obtains final products in 70 DEG C of filtrations, decompression, reclaim alkene and catalyst, product is yellow viscous liquid, nitrogen content 3.6%, and product property is in Table 1.
Properties of product contrast
Market common allcyl groups aromatic amine product is carried out performance evaluation, in Table 1.
Table 1 anti-oxidant performance evaluation
Note: rotary bomb oxidation test and base oil used by scanning differential calorimetry are Yubase6, add dosage 0.25%
As can be seen from Table 1, the antioxygenic property of the product of the present invention is apparently higher than other commercially available prod.
The present invention is initially with compound amine raw material, alkene with multiple batches reacts, do so obtains benefit and can be by the ratio regulating aromatic amine raw material to control non-oxidizability and product oil-soluble, and by the selection of multiple batches of alkene and adjustment, product viscosity and pH-value and constituent content can be changed, make reaction controlling very flexible, it is possible to prepare the product of different performance by changing experiment condition.
The present invention relates to the preparation participating in high efficient mixed aromatic amine antioxidant with bleaching soil type supported catalyst and multiple batches of alkene, obtain antioxidant product performance and be better than the physical mixture of two kinds of single antioxidant, product is orange viscous liquid, nitrogen content scope 3%～3.6%, diphenylamines surplus is less than 1%, alkene that decompression separation obtains and the catalyst obtained after filtering and all can be recycled, non-wastewater discharge, be conducive to environmental protection.
Certainly; the present invention also can have other various embodiments; when without departing substantially from present invention spirit and essence thereof, those of ordinary skill in the art can make various corresponding change and deformation according to the present invention, but these change accordingly and deform the protection domain that all should belong to the claims in the present invention.
Claims (16)
1. the alkylation mixing aromatic amine, it is characterised in that comprise the following steps:
1) diphenylamines and naphthylamines are carried out being mixed into mixing aromatic amine for 4:1～3:1 in molar ratio, first olefin component being subsequently adding and mix aromatic amine equimolar amounts and the bleaching soil type supported catalyst of 4wt%～8wt%, it is alkylated reaction at 80 DEG C～150 DEG C, add first olefin component of 1～5 times of mixing aromatic amine molar equivalent after 1～4 hour, continue reaction 9～18 hours；
2) when tracking that in reactant, diphenylamines or naphthylamines content no longer change by thin layer chromatography, temperature is adjusted to 80 DEG C～160 DEG C, be initially added into the second batch olefin component of 1～4 times of mixing aromatic amine molar equivalent, continue reaction 1～5 hour；
3) by step 2) in products therefrom decompression distillation collect different temperatures fraction alkene, then solid collected by filtration catalyst, finally obtain product liquid.
2. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 1) described in first olefin component selected from C8 alkene, C9 alkene or its mixture.
3. the alkylation of mixing aromatic amine according to claim 2, it is characterised in that described C8 or C9 alkene is selected from positive octene, isooctene, diisobutylene, positive nonene, different nonene, tripropylene or its mixture.
4. the alkylation of mixing aromatic amine according to claim 1, it is characterized in that, step 2) described in second batch olefin component selected from isobutene., polyisobutylene, styrene, polystyrene, α-methyl styrene, poly alpha methylstyrene or its mixture.
5. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that need to add in advance the polymerization inhibitor of 65ppm～95ppm in first olefin component participating in reaction and second batch olefin component.
6. the alkylation of mixing aromatic amine according to claim 5, it is characterised in that described polymerization inhibitor is selected from N-Methyl pyrrolidone, Nitrocarbol., beta-naphthylamine or p-tert-butyl catechol.
7. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 1) and step 2) middle use compressive reaction device, pressure limit is 0.2～0.25MPa.
8. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 3) in decompression distillation vacuum be 0.075～0.080MPa, temperature is 90 DEG C～130 DEG C, and the time is 2～2.5 hours.
9. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 3) in filter process carry out at 70 DEG C～110 DEG C.
10. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 3) in filter process adopt decompression sucking filtration.
11. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that step 3) in reclaim catalyst can recycle.
12. the alkylation of mixing aromatic amine according to claim 11, it is characterised in that when recycling catalyst, it is necessary to add the original bleaching soil type supported catalyst of 20wt%～50wt%.
13. the alkylation of mixing aromatic amine according to claim 1, it is characterised in that described bleaching soil type supported catalyst prepares by adopting bleaching earth load aluminum chloride, iron chloride, boron fluoride, fluoroform sulphonate or its mixture.
14. the alkylation mixing aromatic amine of the alkylation gained described in claim 1, it is characterised in that at least contain following two compound:
Wherein, R1、R2、R3、R4And R5It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2、R3、R4And R5In have at least one for hydrogen；
Wherein, R1、R2And R3It is independently selected from hydrogen, octyl group, isomer octyl group, nonyl, isomer nonyl, normal-butyl, the tert-butyl group, 1-phenylethyl and 2-phenyl propyl, but R1、R2And R3In have at least one for hydrogen.
15. the alkylation mixing aromatic amine described in claim 12 is as the application of antioxidant.
16. the application that the antioxidant described in claim 13 is in lubricating oil or grease.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410778726.8A CN105777557A (en) | 2014-12-15 | 2014-12-15 | Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410778726.8A CN105777557A (en) | 2014-12-15 | 2014-12-15 | Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105777557A true CN105777557A (en) | 2016-07-20 |
Family
ID=56374858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410778726.8A Pending CN105777557A (en) | 2014-12-15 | 2014-12-15 | Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105777557A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574854A (en) * | 2017-09-28 | 2019-04-05 | 中国石油天然气股份有限公司 | Alkylated N-phenyl-a-naphthylamine antioxidant and preparation method thereof |
| WO2022225870A1 (en) * | 2021-04-21 | 2022-10-27 | Lanxess Corporation | LIQUID MONO-ALKYLATED N-PHENYL-α-NAPTHYLAMINE COMPOSITIONS AND METHODS OF MANUFACTURING THE SAME |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348720A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Composite amine antioxidant, preparation and use thereof |
-
2014
- 2014-12-15 CN CN201410778726.8A patent/CN105777557A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348720A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Composite amine antioxidant, preparation and use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574854A (en) * | 2017-09-28 | 2019-04-05 | 中国石油天然气股份有限公司 | Alkylated N-phenyl-a-naphthylamine antioxidant and preparation method thereof |
| WO2022225870A1 (en) * | 2021-04-21 | 2022-10-27 | Lanxess Corporation | LIQUID MONO-ALKYLATED N-PHENYL-α-NAPTHYLAMINE COMPOSITIONS AND METHODS OF MANUFACTURING THE SAME |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW200536813A (en) | Alkylated pana and DPA compositions | |
| CN101528668B (en) | Macromolecular amine-phenolic antioxidant compositions, its production technology and use | |
| US10167383B2 (en) | Process to form ethylene/alpha-olefin interpolymers | |
| CN101283031A (en) | Diaromatic amines | |
| CN102066391A (en) | Phosphite stabilizer for lubricating base stocks and thermoplastic polymers | |
| CN112552978B (en) | Alkyl naphthalene high-temperature heat conduction oil base oil and preparation method and application thereof | |
| CN101273049B (en) | A method of manufacturing an organic silicon compound that contains a methacryloxy group or an acryloxy group | |
| CN105777557A (en) | Alkylation method of mixed aromatic amine, alkylated aromatic amine and application thereof | |
| CN107949626B (en) | Method for producing polyalphaolefins using ionic liquid catalyzed olefin oligomerization | |
| US3773830A (en) | N-aroyl-n'-(alkylhydroxyphenyl)alkanoylhydrazines | |
| CN107835799B (en) | Diarylamine antioxidants prepared from branched olefins | |
| CN105777552B (en) | Process for preparing solid alkylated diphenylamine | |
| CN104628579B (en) | Method for preparing liquidized butyl diphenylamine and liquid octyl diphenylamine | |
| CN103298843B (en) | There is catalyst composition of the flow performance of improvement and production and preparation method thereof | |
| CN105503617B (en) | Highly selective alkylated diphenylamine, its preparation method and application | |
| US8003583B2 (en) | Benzo[b]perhydroheterocyclic arylamines and lubricating oil compositions | |
| CN106479448A (en) | A kind of conduction oil and the method preparing this conduction oil | |
| CN106591547A (en) | Quenching oil composition and manufacturing method thereof | |
| JP2024515712A (en) | Liquid monoalkylated N-phenyl-α-naphthylamine compositions and their method of manufacture - Patents.com | |
| US2183552A (en) | Alkylated poly-isopropyl halobenzenes | |
| US2355257A (en) | Mineral oil composition | |
| CN103289731A (en) | Method for preparing synthetic hydrocarbon containing aromatic hydrocarbon from internal olefin | |
| US2346926A (en) | Condensation product | |
| CN106916605B (en) | A method of PAO12 base oil is synthesized by photoinitiator TPO | |
| CN103122265A (en) | Novel polyethylene synthetic lubricating oil/lubricating oil additive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160720 |