CN110283214A - A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl - Google Patents
A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl Download PDFInfo
- Publication number
- CN110283214A CN110283214A CN201910571858.6A CN201910571858A CN110283214A CN 110283214 A CN110283214 A CN 110283214A CN 201910571858 A CN201910571858 A CN 201910571858A CN 110283214 A CN110283214 A CN 110283214A
- Authority
- CN
- China
- Prior art keywords
- alpha
- benzhydryl
- catalyst
- preparation
- diimine
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 30
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000002199 base oil Substances 0.000 claims abstract description 25
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 239000004711 α-olefin Substances 0.000 claims abstract description 15
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 14
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 239000011592 zinc chloride Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 7
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims 1
- 230000004913 activation Effects 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 229920013639 polyalphaolefin Polymers 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 101150003085 Pdcl gene Proteins 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 238000006384 oligomerization reaction Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- CTTGKCKJYDKMRM-UHFFFAOYSA-N 4-benzhydryl-2,6-diethylaniline Chemical compound C1(=CC=CC=C1)C(C1=CC(=C(N)C(=C1)CC)CC)C1=CC=CC=C1 CTTGKCKJYDKMRM-UHFFFAOYSA-N 0.000 description 2
- OEBWBJUAXHPGAU-UHFFFAOYSA-N 4-benzhydryl-2,6-dimethylaniline Chemical compound CC1=C(N)C(C)=CC(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 OEBWBJUAXHPGAU-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 benzhydryl Palladium (II) Chemical compound 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000563 toxic property Toxicity 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- C10G50/02—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation of hydrocarbon oils for lubricating purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
It mainly include containing preparation, the preparation containing the alpha-diimine ligand that benzhydryl replaces is aligned, three processing steps of preparation containing alpha-diimine palladium (II) complex for aligning benzhydryl substitution for aligning the anil that benzhydryl replaces the invention discloses a kind of alpha-diimine palladium (II) catalyst and preparation method thereof containing contraposition benzhydryl substitution.Alpha-diimine palladium (II) catalyst that the present invention is prepared can be used in being catalyzed alpha-olefin oligomerisation preparation PAO base oil, there is obtained PAO base oil many advantages, the using effects of PAO base oil such as pour point is low, Viscosity Index is high to be significantly enhanced.
Description
Technical field
The invention belongs to technical field of lubricating oil, and in particular to a kind of alpha-diimine palladium replaced containing contraposition benzhydryl
(II) catalyst and preparation method thereof, the catalyst for be catalyzed alpha-olefin it is oligomeric and according to oligomeric alpha-olefin prepare PAO profit
Lubricant base oil.
Background technique
As lubricating oil updating speed is getting faster, market drives PAO base oil for the demand of high-end lube product
Demand growth is rapid.Currently, catalyst used in oligomeric production poly alpha olefin (PAO) technique of alpha-olefin is mainly lewis acid
Catalyst and metallocene catalyst.
Lewis acid catalyst is mainly AlCl3And BF3。AlCl3The oligomeric preparation PAO oil of catalyzed alkene has at low cost, behaviour
Making the advantages that simple and strong to adaptability to raw material, (Zhang Lianhong, Feng Zhigang, Qin Shi wait polymerization of Alpha-olefin to prepare lube base
Study of Novel Catalyst [J] the Fusun PetroleumCollege journal of oil, 2001,21 (2): 13-16.), but the catalytic process can generate
A large amount of AlCl3By-product, processing environmental protection pressure are big.BF3The product viscosity index that catalyst obtains is high, high-quality, but BF3It is toxic
Property, centainly injury can be caused to human body, and (Sun Wei, Xu Tingting, Huo Hongliang wait alpha-olefine polymerizing low-viscosity poly alpha olefin to be catalyzed
Progress [J] the Speciality Petrochemicals of agent is in progress, 2017 (06): 25-28).
Metallocene catalyst (MAO) catalysis alpha-olefine polymerizing prepares lube base oil, lubricating oil excellent combination property (Zhao
Beautiful jade Qi, Ding Hongsheng, Zhang Yu metallocene/triisobutyl aluminium/B (C6F5)3[J] application is studied in catalyst system catalyzed 1-octylene oligomerisation
Chemical industry, 2012,41 (12): 2106-2108.), but it is at high cost using MAO catalyst, while MAO is easily anti-with the water in air
It answers, therefore, the oligomerization condition is extremely harsh, and technology difficulty is very big.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, provide it is a kind of containing contraposition benzhydryl replace
Alpha-diimine palladium (II) catalyst and preparation method thereof, the catalyst can be catalyzed alpha-olefin oligomerisation preparation PAO base oil, and low
Poly- reaction process mild condition, PAO base oil obtained have many advantages such as pour point is low, Viscosity Index is high.
Technical solution: to achieve the above object, the present invention provides a kind of alpha-diimine replaced containing contraposition benzhydryl
Palladium (II) catalyst, shown in the structural formula of the catalyst such as formula (I):
Wherein R=Me, Et,iPr。
Further, the catalyst is oligomeric for being catalyzed alpha-olefin, and the oligomeric alpha-olefin is used to prepare the basis PAO
Oil.
The oligomeric method of the catalyst alpha-olefin are as follows: catalyst and aromatic solvent are added into polymerization bottle and stirs
It mixes, and solution is deaerated, heat, alpha-olefin is added, reacts under fast stirring, after reaction, evaporate solvent, obtain oily
Oligomer.Wherein, the reaction temperature are as follows: 20~70 DEG C；The reaction time are as follows: 0.1h-2h；The reaction pressure are as follows: 1-
8atm。
The PAO base oil the preparation method comprises the following steps: by oily oligomer obtained through conventional hydrofinishing, vacuum distillation is cut
Light component is gone, products therefrom is PAO base oil.
A kind of preparation method of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl, including walk as follows
It is rapid:
S1: the anil that preparation replaces containing contraposition benzhydryl
By anil and benzohydrol to be mixed and heated, anhydrous zinc chloride and dense salt are added into mixture
Then acid heats up, after complete reaction, be cooled to room temperature, and CH is added2Cl2, washed with saturation NaOH aqueous solution, use is anhydrous
MgSO4It is dry, it is concentrated under reduced pressure, ethyl alcohol is added, white solid is precipitated, filtration drying obtains the aniline that contraposition benzhydryl replaces and spreads out
Biology；
S2: the alpha-diimine ligand that preparation replaces containing contraposition benzhydryl
Using ethyl alcohol as solvent, using formic acid as catalyst, the anil that benzhydryl replaces will be aligned and mixed with acenaphthenequinone,
After back flow reaction, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2It is heavy that solid is precipitated in mixed solvent recrystallization
It forms sediment, filtration drying must contain the alpha-diimine ligand that contraposition benzhydryl replaces；
S3: alpha-diimine palladium (II) complex that preparation replaces containing contraposition benzhydryl
Under nitrogen protection, using methylene chloride as solvent, by containing the alpha-diimine ligand that replaces of contraposition benzhydryl and
The palladium chloride mixing activated by acetonitrile, after reaction is stirred at room temperature, filters suspension, mother liquor removes solvent under vacuum conditions
Afterwards, it is washed with ether, is dried in vacuo, obtains pulverulent solids complex.
Further, the anil in the step S1 be 2,6- dimethylaniline, 2,6- diethylaniline and 2,
One of 6- diisopropyl aniline.
Further, anil and benzohydrol are mixed with the molar ratio of 1:1.1~1:1.2 in the step S1
It closes, and is heated to 100 DEG C~140 DEG C；The additional amount of anhydrous zinc chloride and concentrated hydrochloric acid is respectively the mole of anil
0.5 times and equal molar amount, and 150 DEG C~170 DEG C are warming up to after being added, it heats 0.8~1.2 hour.
Further, the anil and acenaphthenequinone that benzhydryl substitution is aligned in the step S2 are with 2.1:1~2.2:1
Molar ratio mixing, the temperature range of back flow reaction is 45~55 DEG C, and the reaction time is 12~24 hours.
Further, the dosage of catalyst formic acid is 0.02~0.1 times of acenaphthenequinone mole in the step S2.
Further, it is activated containing the alpha-diimine ligand for aligning benzhydryl substitution in the step S3 and by acetonitrile
Palladium chloride is mixed with the molar ratio of 1:1~1:1.2, and the time being stirred to react is 12~24 hours.
Further, it is described by acetonitrile activate palladium chloride the preparation method comprises the following steps: by palladium chloride and acetonitrile with 1:8~1:50
Molar ratio mixing, at 60~70 DEG C flow back 5~10h, filter, be concentrated, vacuum drying, obtain pulverulent solids PdCl2
(MeCN)2。
The utility model has the advantages that compared with prior art, the present invention catalyst is applied to the basis catalysis alpha-olefin oligomerisation preparation PAO
Oil has following advantage:
1, using catalyst of the present invention compared with MAO catalyst, reaction condition is mild, simple production process, and cost drops
It is low；
2, catalyst of the present invention and AlCl are utilized3And BF3Equal catalyst ratio, not only obtained PAO base oil has pour point
It is low, Viscosity Index is high etc., and advantages, the performance of PAO lubricating oil are improved, and technique obviously has more the feature of environmental protection, environmental pressure
Small, processing environmental protection pressure is also greatly reduced.
Specific embodiment
Combined with specific embodiments below, the present invention is furture elucidated.
Embodiment 1:
The present embodiment prepares catalyst Pd-A, and specific preparation process is as follows:
S1: 2,6- dimethylaniline (1.21g, 10mmol) and benzohydrol (1.84g, 10mmol) are placed in 50ml circle
In the flask of bottom, after stirring and being warming up to 120 DEG C, anhydrous zinc chloride (0.681g, 5mmol) is added into mixture, concentrated hydrochloric acid
(37%H2O, 0.365g, 10mmol) is warming up to 160 DEG C, reacts 1 hour (heat release and strongly bubbling), after being cooled to room temperature,
Solid is dissolved in 70mL CH2Cl2In, it is washed with saturation NaOH aqueous solution, with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, is added a large amount of
White solid is precipitated in ethyl alcohol, and filtration drying obtains 4- benzhydryl -2,6- dimethylaniline 2.39g, yield 83%.
Specific synthetic reaction formula is as follows:
S2: by 4- benzhydryl -2,6- dimethylaniline (1.21g, 4.2mmol) and acenaphthenequinone made from step S1
(0.36g, 2.0mmol) is dissolved in 20mL ethyl alcohol, and 0.2ml formic acid, back flow reaction 24 hours at 50 DEG C are added under stiring
Afterwards, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2(v/v=15:2) it is heavy that solid is precipitated in mixed solvent recrystallization
It forms sediment, filtration drying obtains ligand 1 .22g, yield 83%.
Specific synthetic reaction formula is as follows:
S3: PdCl is prepared first2(MeCN)2: palladium chloride is mixed with acetonitrile with the molar ratio of 1:8, is flowed back at 60 DEG C
5h is filtered, and is concentrated, and vacuum drying obtains pulverulent solids PdCl2(MeCN)2。
Under nitrogen protection, be added into 100mL dry reaction tube the made ligand of above-mentioned steps S2 (0.5mmol,
0.37g), the PdCl prepared is added2(MeCN)2(0.5mmol, 0.13g) and methylene chloride 30mL is stirred at room temperature anti-
It answers 16 hours, filters suspension, mother liquor removes solvent under vacuum, and residue is washed three times with ether (3 × 16mL), and vacuum is dry
Solid complexes 0.39g, yield 90% are obtained after dry.
Specific mode formula is as follows:
The structural formula of catalyst Pd-A is as follows:
Embodiment 2:
The present embodiment prepares catalyst Pd-B, and specific preparation process is as follows:
S1: 2,6- diethylaniline (1.21g, 10mmol) and benzohydrol (1.84g, 10mmol) are placed in 50ml circle
In the flask of bottom, after stirring and being warming up to 100 DEG C, anhydrous zinc chloride (0.681g, 5mmol) is added into mixture, concentrated hydrochloric acid
(37%H2O, 0.365g, 10mmol) is warming up to 150 DEG C, reaction 0.8 hour (heat release and strongly bubbling), is cooled to room temperature
Afterwards, solid is dissolved in 70mL CH2Cl2In, it is washed with saturation NaOH aqueous solution, with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, is added
White solid is precipitated in a large amount of ethyl alcohol, and filtration drying obtains 4- benzhydryl -2,6- diethylaniline 2.55g, yield 81%.
S2: by 4- benzhydryl -2,6- diethylaniline (1.32g, 4.2mmol) and acenaphthenequinone made from step S1
(0.36g, 2.0mmol) is dissolved in 20mL ethyl alcohol, and 0.2ml formic acid, back flow reaction 12 hours at 40 DEG C are added under stiring
Afterwards, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2(v/v=15:2) it is heavy that solid is precipitated in mixed solvent recrystallization
It forms sediment, filtration drying obtains ligand 1 .37g, yield 88%.
S3: PdCl is prepared first2(MeCN)2: palladium chloride is mixed with acetonitrile with the molar ratio of 1:50, is flowed back at 70 DEG C
10h is filtered, and is concentrated, and vacuum drying obtains pulverulent solids PdCl2(MeCN)2。
Under nitrogen protection, be added into 100mL dry reaction tube the made ligand of above-mentioned steps S2 (0.5mmol,
0.37g), PdCl is added2(MeCN)2Reaction 12 hours is stirred at room temperature in (0.5mmol, 0.13g) and methylene chloride 30mL,
Suspension is filtered, mother liquor removes solvent under vacuum, and residue is washed three times with ether (3 × 16mL), obtained after vacuum drying
Solid complexes 0.44g, yield 92%.
The structural formula of catalyst Pd-B is as follows:
Embodiment 3:
The present embodiment prepares catalyst Pd-C, and specific preparation process is as follows:
S1: 2,6-DIPA (1.21g, 10mmol) and benzohydrol (1.84g, 10mmol) are placed in 50ml
In round-bottomed flask, after stirring and being warming up to 140 DEG C, anhydrous zinc chloride (0.681g, 5mmol) is added into mixture, concentrated hydrochloric acid
(37%H2O, 0.365g, 10mmol) is warming up to 170 DEG C, reaction 1.2 hours (heat release and strongly bubbling), is cooled to room temperature
Afterwards, solid is dissolved in 70mL CH2Cl2In, it is washed with saturation NaOH aqueous solution, with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, is added
White solid is precipitated in a large amount of ethyl alcohol, and filtration drying obtains 4- benzhydryl -2,6-DIPA 2.82g, yield 82%.
S2: by the benzhydryl of 4- made from step S1-2,6-DIPA (1.44g, 4.2mmol) and acenaphthenequinone
(0.36g, 2.0mmol) is dissolved in 20mL ethyl alcohol, and 0.2ml formic acid, back flow reaction 24 hours at 55 DEG C are added under stiring
Afterwards, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2(v/v=15:2) it is heavy that solid is precipitated in mixed solvent recrystallization
It forms sediment, filtration drying obtains ligand 1 .41g, yield 85%.
S3: PdCl is prepared first2(MeCN)2: palladium chloride is mixed with acetonitrile with the molar ratio of 1:50, is flowed back at 70 DEG C
10h is filtered, and is concentrated, and vacuum drying obtains pulverulent solids PdCl2(MeCN)2。
Under nitrogen protection, be added into 100mL dry reaction tube the made ligand of above-mentioned steps S2 (0.5mmol,
0.37g), PdCl is added2(MeCN)2Reaction 24 hours is stirred at room temperature in (0.5mmol, 0.13g) and methylene chloride 30mL,
Suspension is filtered, mother liquor removes solvent under vacuum, and residue is washed three times with ether (3 × 16mL), obtained after vacuum drying
Solid complexes 0.52g, yield 94%.
The structural formula of catalyst Pd-C is as follows:
Embodiment 4:
The present embodiment carries out oligomerization to 1- hexene using catalyst Pd-A made from embodiment 1, and detailed process is as follows:
Magnetic stir bar is added in 250mL polymerization bottle, 20mL is injected into polymerization bottle and passes through dried toluene
Solution, then 1- hexene is injected into polymerization bottle with syringe, start stirring heating, keep 15min at 20 DEG C, by urging for 5 μm of ol
Agent Pd-A is dissolved in the steamed 2mL methylene chloride of weight, is drawn and is injected into polymerization bottle with syringe, and 30min, knot are reacted
After Shu Fanying, it is cooled to room temperature rear pressure release (reaction pressure in the present embodiment are as follows: 1atm), and the acidified methanol by the way that 50mL is added
(methanol/HCl=50/1) terminates polymerization, evaporates light component solvent, and oily oligomer A is obtained after concentration.
Embodiment 5:
The present embodiment carries out oligomerization to 1- octene using catalyst Pd-A made from embodiment 1, and detailed process is as follows:
Magnetic stir bar is added in 250mL polymerization bottle, 20mL is injected into polymerization bottle and passes through dried toluene
Solution, then 1- octene is injected into polymerization bottle with syringe, start stirring heating, keep 15min at 20 DEG C, by urging for 5 μm of ol
Agent Pd-A is dissolved in the steamed 2mL methylene chloride of weight, is drawn and is injected into polymerization bottle with syringe, and 50min, knot are reacted
After Shu Fanying, it is cooled to room temperature rear pressure release (reaction pressure in the present embodiment are as follows: 8atm), and the acidified methanol by the way that 50mL is added
(methanol/HCl=50/1) terminates polymerization, evaporates light component solvent, and oily oligomer B is obtained after concentration.
Embodiment 6:
The present embodiment carries out oligomerization to 1- decene using catalyst Pd-B made from embodiment 2, and detailed process is as follows:
Magnetic stir bar is added in 250mL polymerization bottle, 20mL is injected into polymerization bottle and passes through dried toluene
Solution, then 1- decene is injected into polymerization bottle with syringe, start stirring heating, keep 15min at 70 DEG C, by urging for 5 μm of ol
Agent Pd-B is dissolved in the steamed 2mL methylene chloride of weight, is drawn and is injected into polymerization bottle with syringe, and 6min, knot are reacted
After Shu Fanying, it is cooled to room temperature rear pressure release (reaction pressure in the present embodiment are as follows: 4atm), and the acidified methanol by the way that 50mL is added
(methanol/HCl=50/1) terminates polymerization, evaporates light component solvent, and oily oligomer C is obtained after concentration.
Embodiment 7:
The present embodiment carries out oligomerization to 1- laurylene using catalyst Pd-C made from embodiment 3, and detailed process is such as
Under:
Magnetic stir bar is added in 250mL polymerization bottle, 20mL is injected into polymerization bottle and passes through dried toluene
Solution, then 1- laurylene is injected into polymerization bottle with syringe, start stirring heating, keep 15min at 50 DEG C, by 5 μm of ol's
Catalyst Pd-C is dissolved in the steamed 2mL methylene chloride of weight, is drawn and is injected into polymerization bottle with syringe, and 2h, knot are reacted
After Shu Fanying, it is cooled to room temperature rear pressure release (reaction pressure in the present embodiment are as follows: 6atm), and the acidified methanol by the way that 50mL is added
(methanol/HCl=50/1) terminates polymerization, and light component solvent is evaporated under reduced pressure, and oily oligomer D is obtained after concentration.
Embodiment 8:
Oligomer A made from embodiment 4~7, oligomer B, oligomer C and oligomer D is utilized respectively in the present embodiment to come
PAO base oil A, PAO base oil B, PAO base oil C and PAO base oil D are prepared, here by taking the preparation of PAO base oil A as an example,
Its specific preparation process are as follows:
Oligomer A is used into the hydrofinishing of conventional olefin saturation catalyst, vacuum distillation cuts light component, and products therefrom is
PAO base oil A.
Pass through AlCl in the present embodiment again3Catalyzed 1-octylene obtains oligomer E, then PAO base is prepared by oligomer E
Plinth oil E.
Following table is the physics and chemistry of PAO base oil A, PAO base oil B, PAO base oil C, PAO base oil D and PAO base oil E
Energy index:
According to upper table it is found that four sections of PAO base oils that catalyst and technique obtain through the invention and the basis traditional PAO
Oily E is compared, and all has low-down pour point, and Viscosity Index is also all very high.
Claims (10)
1. a kind of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl, it is characterised in that: the catalyst
Shown in structural formula such as formula (I):
Wherein R=Me, Et,iPr。
2. a kind of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 1, special
Sign is: alpha-olefin is oligomeric, and the oligomeric alpha-olefin is used to prepare PAO base oil for being catalyzed for the catalyst.
3. a kind of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 2, special
Sign is: the oligomeric method of the catalyst alpha-olefin are as follows: catalyst and aromatic solvent are added into polymerization bottle and stirs,
And solution deaerates, it heats, alpha-olefin is added, reacts under fast stirring, after reaction, evaporate solvent, it is low to obtain oily
Polymers；
The PAO base oil the preparation method comprises the following steps: by oily oligomer obtained obtained after conventional hydrofinishing PAO basis
Oil.
4. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 1
Method, characterized by the following steps:
S1: the anil that preparation replaces containing contraposition benzhydryl
By anil and benzohydrol to be mixed and heated, anhydrous zinc chloride and concentrated hydrochloric acid are added into mixture, so
After heat up, after complete reaction, be cooled to room temperature, be added CH2Cl2, washed with saturation NaOH aqueous solution, with anhydrous MgSO4
It is dry, it is concentrated under reduced pressure, ethyl alcohol is added, white solid is precipitated, filtration drying obtains the anil that contraposition benzhydryl replaces；
S2: the alpha-diimine ligand that preparation replaces containing contraposition benzhydryl
Using ethyl alcohol as solvent, using formic acid as catalyst, the anil that benzhydryl replaces will be aligned and mixed with acenaphthenequinone, passed through
After back flow reaction, solvent is removed, crude product is obtained, then uses C again2H5OH/CH2Cl2Solid precipitating is precipitated in mixed solvent recrystallization,
Filtration drying must contain the alpha-diimine ligand that contraposition benzhydryl replaces；
S3: alpha-diimine palladium (II) complex that preparation replaces containing contraposition benzhydryl
Under nitrogen protection, using methylene chloride as solvent, by the alpha-diimine ligand replaced containing contraposition benzhydryl and by second
The palladium chloride mixing of nitrile activation, after reaction is stirred at room temperature, filters suspension, after mother liquor removes solvent under vacuum conditions,
It is washed with ether, is dried in vacuo, obtains pulverulent solids complex.
5. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4
Method, it is characterised in that: the anil in the step S1 is 2,6- dimethylaniline, 2,6- diethylaniline and 2,6-
One of diisopropyl aniline.
6. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4
Method, it is characterised in that: anil is mixed with benzohydrol with the molar ratio of 1:1.1~1:1.2 in the step S1,
And it is heated to 100 DEG C~140 DEG C；The additional amount of anhydrous zinc chloride and concentrated hydrochloric acid is respectively the mole 0.5 of anil
Times and equal molar amount, and be warming up to 150 DEG C~170 DEG C after being added, heat 0.8~1.2 hour.
7. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4
Method, it is characterised in that: the anil and acenaphthenequinone that benzhydryl substitution is aligned in the step S2 are with 2.1:1~2.2:1
Molar ratio mixing, the temperature range of back flow reaction is 45~55 DEG C, and the reaction time is 12~24 hours.
8. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4
Method, it is characterised in that: the dosage of catalyst formic acid is 0.02~0.1 times of acenaphthenequinone mole in the step S2.
9. a kind of preparation of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4
Method, it is characterised in that: activated in the step S3 containing the alpha-diimine ligand for aligning benzhydryl substitution and by acetonitrile
Palladium chloride is mixed with the molar ratio of 1:1~1:1.2, and the time being stirred to react is 12~24 hours.
10. a kind of alpha-diimine palladium (II) catalyst replaced containing contraposition benzhydryl according to claim 4 or 9
Preparation method, it is characterised in that: the palladium chloride activated by acetonitrile the preparation method comprises the following steps: by palladium chloride and acetonitrile with 1:8~
The molar ratio of 1:50 mixes, and flow back 5~10h at 60~70 DEG C, filters, and is concentrated, and vacuum drying obtains pulverulent solids PdCl2
(MeCN)2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910571858.6A CN110283214A (en) | 2019-06-28 | 2019-06-28 | A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910571858.6A CN110283214A (en) | 2019-06-28 | 2019-06-28 | A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110283214A true CN110283214A (en) | 2019-09-27 |
Family
ID=68019354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910571858.6A Pending CN110283214A (en) | 2019-06-28 | 2019-06-28 | A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110283214A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759710A (en) * | 2021-01-22 | 2021-05-07 | 吴军化 | Para-phenoxy substituted alpha-diimine iron catalyst and preparation method thereof |
| CN112774731A (en) * | 2021-01-22 | 2021-05-11 | 邹育英 | Para-methoxy substituted palladium catalyst and application thereof in Heck reaction |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
| CN115433346A (en) * | 2022-09-30 | 2022-12-06 | 武汉工程大学 | Phenanthrenequinone alpha-diamine-based palladium catalyst and preparation method and application thereof |
| CN117105990A (en) * | 2023-10-19 | 2023-11-24 | 链行走新材料科技(广州)有限公司 | Catalyst for preparing polythiophene and P3HT material by catalysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659622A (en) * | 2012-05-14 | 2012-09-12 | 山东轻工业学院 | Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof |
| CN103102433A (en) * | 2013-01-11 | 2013-05-15 | 西北师范大学 | Alpha-diimine palladium (II) olefin polymerization catalyst containing substituted ortho-phenyls, as well as preparation and application thereof |
| CN107698699A (en) * | 2017-09-27 | 2018-02-16 | 常州大学 | For being catalyzed the α diimine nickels containing contraposition benzhydryl substitution of ethene and 2 hexene oligomerizations（Ⅱ）Complex |
| US20180105478A1 (en) * | 2016-10-19 | 2018-04-19 | Chevron Phillips Chemical Company Lp | Process for Reducing the Light Oligomer Content of Polypropylene Oils |
-
2019
- 2019-06-28 CN CN201910571858.6A patent/CN110283214A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659622A (en) * | 2012-05-14 | 2012-09-12 | 山东轻工业学院 | Large steric hindrance ligand Pd complex catalyst as well as preparation method and application thereof |
| CN103102433A (en) * | 2013-01-11 | 2013-05-15 | 西北师范大学 | Alpha-diimine palladium (II) olefin polymerization catalyst containing substituted ortho-phenyls, as well as preparation and application thereof |
| US20180105478A1 (en) * | 2016-10-19 | 2018-04-19 | Chevron Phillips Chemical Company Lp | Process for Reducing the Light Oligomer Content of Polypropylene Oils |
| CN107698699A (en) * | 2017-09-27 | 2018-02-16 | 常州大学 | For being catalyzed the α diimine nickels containing contraposition benzhydryl substitution of ethene and 2 hexene oligomerizations（Ⅱ）Complex |
Non-Patent Citations (1)
| Title |
|---|
| LIHUA GUO等: "Synthesis of functional and hyperbranched ethylene oligomers using unsymmetrical α-diimine palladium catalysts", 《EUROPEAN POLYMER JOURNAL》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759710A (en) * | 2021-01-22 | 2021-05-07 | 吴军化 | Para-phenoxy substituted alpha-diimine iron catalyst and preparation method thereof |
| CN112774731A (en) * | 2021-01-22 | 2021-05-11 | 邹育英 | Para-methoxy substituted palladium catalyst and application thereof in Heck reaction |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
| CN112759710B (en) * | 2021-01-22 | 2023-09-08 | 吴军化 | Para-phenoxy substituted alpha-diimine iron catalyst and preparation method thereof |
| CN115433346A (en) * | 2022-09-30 | 2022-12-06 | 武汉工程大学 | Phenanthrenequinone alpha-diamine-based palladium catalyst and preparation method and application thereof |
| CN115433346B (en) * | 2022-09-30 | 2024-03-26 | 武汉工程大学 | Palladium catalyst based on phenanthrenequinone alpha-diamine, and preparation method and application thereof |
| CN117105990A (en) * | 2023-10-19 | 2023-11-24 | 链行走新材料科技(广州)有限公司 | Catalyst for preparing polythiophene and P3HT material by catalysis |
| CN117105990B (en) * | 2023-10-19 | 2024-01-30 | 链行走新材料科技(广州)有限公司 | Catalyst for preparing polythiophene and P3HT material by catalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110283214A (en) | A kind of alpha-diimine palladium (II) catalyst and preparation method thereof replaced containing contraposition benzhydryl | |
| RU2668553C2 (en) | Method of producing aluminoxanes | |
| CN101168493B (en) | Preparation method for fluorochlorobenzene | |
| CN101348502B (en) | 2-benzimidazole-1,10-phenanthroline transient metal complex, and preparation and use thereof | |
| CN105017030A (en) | Preparation method of 2,2'-bistrifluoromethyl-4,4'-diaminobiphenyl | |
| CN105504305B (en) | One kind contains 3（4 pyridines）Coordination polymer of pyrazoles propionic acid and preparation method thereof, purposes | |
| CN107011211B (en) | A kind of preparation method of para-Phthalonitrile | |
| CN103265417A (en) | Method for synthesizing 4-[2-(trans-4-alkyl cyclohexyl )ethyl]cyclohexanone | |
| CN109422663B (en) | Method for continuous flow synthesis of quaternary ammonium salt | |
| JP6675492B2 (en) | Method for preparing liquid phase of acrylic ester | |
| CN104418915B (en) | A kind of preparation method and applications of complex | |
| CN1692984A (en) | Method for synthesizing D,L-alpha-tocopherol catalyzed by ion-liquid | |
| CN112495360B (en) | Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof | |
| CN108822237A (en) | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer | |
| CN103480418A (en) | Chiral catalyst in binaphthol synthesis technology | |
| EP3585822A1 (en) | Processes for making polyisobutylene compositions | |
| CN110218225A (en) | The preparation method of ligand, nickel complex and polyolefin compound | |
| CN107744834A (en) | A kind of supported palladium Raney nickel synthesized for alkene epoxidation and Bisphenol F and preparation method | |
| CN105541561A (en) | Method for synthesizing and purifying 1,1,1-tri(4-hydroxy phenyl) ethane | |
| CN106349163A (en) | Cu (I)-based metal organic coordination polymer and preparation method and application thereof | |
| CN104284880A (en) | Hydroxyalkyl (meth)acrylate and method for producing same | |
| CN106831583A (en) | N, N dialkyl group substituted pyrazolecarboxylic ionic liquid, preparation method and its method for catalyzing and synthesizing propene carbonate | |
| CN102604101A (en) | Synthesis method for phenyl organosilicon copolymer with uniformly distributed phenyl units | |
| CN111087417A (en) | Synthesis method of methyl diphenyl silane compound containing C-Si bond | |
| CN110694689A (en) | Polyion liquid supported ruthenium carbene complex catalyst, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190927 |
|
| RJ01 | Rejection of invention patent application after publication |