CN106866718A - A kind of preparation method of sesquialter aikyl aluminum halide - Google Patents
A kind of preparation method of sesquialter aikyl aluminum halide Download PDFInfo
- Publication number
- CN106866718A CN106866718A CN201710074500.3A CN201710074500A CN106866718A CN 106866718 A CN106866718 A CN 106866718A CN 201710074500 A CN201710074500 A CN 201710074500A CN 106866718 A CN106866718 A CN 106866718A
- Authority
- CN
- China
- Prior art keywords
- aluminium
- preparation
- aluminum halide
- sesquialter
- aikyl aluminum
- 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
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 106
- -1 aluminum halide Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000004411 aluminium Substances 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 230000001939 inductive effect Effects 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 16
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000013019 agitation Methods 0.000 claims abstract description 11
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 10
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 239000011630 iodine Substances 0.000 claims abstract description 5
- 238000009835 boiling Methods 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical group ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 12
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 12
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 10
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 8
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 6
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 claims description 5
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 claims 1
- 230000006698 induction Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000006184 cosolvent Substances 0.000 abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229940050176 methyl chloride Drugs 0.000 description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 7
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- NCCOOTMRZHTROF-UHFFFAOYSA-N ethylphosphanium;bromide Chemical compound [Br-].CC[PH3+] NCCOOTMRZHTROF-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/064—Aluminium compounds with C-aluminium linkage compounds with an Al-Halogen linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of sesquialter aikyl aluminum halide, comprise the following steps：Inducing agent is added in the mixture of aluminium and organic solvent, a halogenated alkane is added in reactant under agitation, reaction temperature is controlled between 50-160 DEG C；Solvent is that hydrocarbon cosolvent inducing agent of the boiling point values between 60-300 DEG C is bromine Br2, iodine I2, iodomethane CH3I or 1,2 ethylidene periodide C2H4I2；The mol ratio 1 of described inducing agent, aluminium and a halogenated alkane:80‑120:140‑180；One halogenated alkane is 1: 1.5~3 with the weight ratio of solvent；The charging of one halogenated alkane is finished into rear reactant to continue to stir 24 hours；When reaction mass temperature control is at 135 150 DEG C, vacuum distillation obtains sesquialter aikyl aluminum halide.Low cost of the present invention, reaction efficiency is high, safe, is easily purified.
Description
Technical field
The present invention relates to a kind of preparation method of sesquialter aikyl aluminum halide.
Background technology
Sesquialter aikyl aluminum halide（The aluminium of three halogenation of trialkyl two）Be dialkylaluminum halides and alkyl dihalides aluminium phase combine and
Into double aluminium core alkyl halides.It is generated by metallic aluminium and a halogenated alkane direct reaction.Sesquialter methyl aluminum halide master
If preparing trimethyl aluminium, the primary raw material of dimethyl aluminum halide, it is also a kind of semiconductor components and devices high temperature deposition growth oxygen
Change the material of aluminium film.But because it is difficult to prepare, there is presently no the production of sesquialter aikyl aluminum halide product.
It is published in by Gross and Mavity earliest by metallic aluminium and monochloro methane reaction preparation sesquialter methyl chloride aluminium organic
On The Chemicals Journal of Organic Chemistry, vol.5 page 106-121,1940.
It has been investigated that reaction is difficult to carry out, reaction efficiency is extremely low.
Patent US2863894 reports the method for generating sesquialter aikyl aluminum halide by a halogenated alkane and metal reactive aluminum,
The reaction needs to use the sesquialter aikyl aluminum halide as inducing agent just reaction can occur.
1997, Japan Patent JPH0977775 was disclosed and is used aluminium powder and a chloromethane containing 0.01% -3.0% Titanium
Alkane gas reaction prepares sesquialter methyl chloride aluminium, and the reaction also needs to use the sesquialter methyl chloride aluminium could smoothly be sent out as inducing agent
It is raw.
Inducing agent itself is done using sesquialter aikyl aluminum halide, it is not readily available, and because sesquialter aikyl aluminum halide is one
The liquid of easily spontaneous combustion is planted, is preserved and is required for when using and air exclusion, this not only increased equipment, bring very big to operation
Difficulty, and once leakage will trigger fire, in the presence of very big potential safety hazard during production, realize that industrialized production difficulty is big.
The content of the invention
The purpose of the present invention is exactly to solve the above-mentioned problems in the prior art, there is provided a kind of low cost, reaction efficiency
Height, safe, the preparation method of the sesquialter aikyl aluminum halide being easily purified.
To achieve the above object, technical solution of the invention is：A kind of preparation method of sesquialter aikyl aluminum halide, its
Comprise the following steps：Aluminium powder and organic solvent are added and is full of in the reactor of inert gas, then inducing agent is added to reaction
In kettle, a halogenated alkane is added in reactant under agitation, reaction temperature is controlled between 50-160 DEG C；Described is molten
Agent is hydrocarbon cosolvent of the boiling point values between 60-300 DEG C；Described inducing agent is bromine Br2, iodine I2, iodomethane CH3I
Or 1,2- ethylidene periodides C2H4I2；The mol ratio 1 of described inducing agent, aluminium and a halogenated alkane:80 -120:140-180；It is described
The weight ratio of a halogenated alkane and solvent be 1: 1.5~3；After described halogenated alkane charging is finished, reaction temperature control
Continue to stir 2-4 hours when system is between 50-160 DEG C；When reaction mass temperature control is at 135-150 DEG C, vacuum distillation is obtained
Obtain sesquialter aikyl aluminum halide.
A halogenated alkane described above is monochloro methane, a bromomethane, monochlorethane, a bromoethane, a chlorobutane, one
NBB, tertiary butyl chloride or tert-butyl bromide.
Hydrocarbon cosolvent described above is saturated alkane or aromatic hydrocarbon.
Saturated alkane described above is such as hexane, hexamethylene, octane, certain herbaceous plants with big flowers alkane, dodecane, hexadecane, eicosane, 20
The mixture of one or more of four alkane and white oil；Aromatic hydrocarbon is one kind or many of tetrahydro chennai, toluene, dimethylbenzene and trimethylbenzene
Plant mixture.
Aluminium described above is aluminum shot or aluminium powder.
Reaction temperature described above is preferably 80-140 DEG C.
Inert gas described above is argon gas or nitrogen.
Present invention production sesquialter aikyl aluminum halide method has advantages below：1）The inducing agent for using is the change being readily available
Material is learned, nonflammable compound without inert gas shielding during the use that preserves and feed, saves equipment, simplified behaviour
Make step, improve processing safety.2）The generation of reaction is promoted using inducing agent, has shortened the reaction time, improve anti-
Efficiency and yield are answered, the manufacturing cost of product is reduce further； 3）After completion of the reaction, the aluminium powder in reactant is almost seen not
To residual, therefore judge the conversion ratio of aluminum shot or aluminium powder close to 100%.The present invention is high with reaction efficiency, and product yield is high, system
Make safe advantage；Thorough due to what is reacted, aluminium powder is without the storage of other unreacted reactants is little, and no introducing
Other impurity, and higher boiling point hydrocarbon compound solvent be free of aerobic and nitrogen ligand, so purification be easy to.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
1st, embodiment 1：A kind of preparation method of sesquialter methyl chloride aluminium, inducing agent iodomethane CH used below3I, aluminium
（Aluminum shot or aluminium powder）Mol ratio with monochloro methane is：1:100:150,（10g：190g：533g）；Monochloro methane and solvent 16
The weight ratio of alkane is 1：2.It is comprised the following steps：1st, aluminium and hexadecane are added into the stainless steel cauldron full of inert gas
In, stirring is opened, reactor temperature-controlling system is opened, add iodomethane；2nd, under agitation, monochloro methane is added, will be anti-
Temperature control is answered at 100 DEG C, plus depending on the speed visual response temperature change of monochloro methane, usual feed time is 5 hours；3rd, add
Material is again controlled at 100 DEG C temperature of charge after finishing, and continues to stir 2 hours；4th, when reaction mass temperature control is at 140 DEG C,
Vacuum distillation obtains sesquialter methyl chloride aluminium product 694g.Calculated by the amount of aluminium, yield is 95.9%.
Embodiment 2, a kind of preparation method of sesquialter methyl bromide aluminium, inducing agent 1 used below, 2- ethylidene periodides
C2H4I2, aluminium（Aluminum shot or aluminium powder）Mol ratio with a bromomethane is：1:120:170,（22g：253g：1260g）；One bromomethane
With solvent dodecane（Eicosane or lignocerane）Weight ratio be 1：1.5.It is comprised the following steps：1st, by aluminium and dodecane
（Eicosane or lignocerane）Add in the stainless steel cauldron full of inert gas, open stirring, open reactor temperature control system
System, adds 1,2- ethylidene periodides C2H4I2；2nd, under agitation, a bromomethane is added, by reaction temperature control at 140 DEG C,
Plus one bromomethane speed visual response temperature change depending on, usual feed time be 6 hours；3rd, again by material temperature after charging is finished
Degree control continues to stir 3 hours at 140 DEG C；4th, when reaction mass temperature control is at 135 DEG C, vacuum distillation obtains sesquialter first
Base aluminium bromide product 1667g.Calculated by the amount of aluminium, yield is 89%.
Embodiment 3, a kind of preparation method of sesquialter ethylmercury chloride aluminium, inducing agent bromine Br used below2, aluminium（Aluminum shot or
Aluminium powder）Mol ratio with monochlorethane is：1:90:140,（6g：91g：339g）；Monochlorethane and solvent hexane（It is hexamethylene, pungent
Alkane or certain herbaceous plants with big flowers alkane）Weight ratio be 1：3.It is comprised the following steps：1st, by aluminium and hexane（Hexamethylene, octane or certain herbaceous plants with big flowers alkane）Addition is full of
In the stainless steel cauldron of inert gas, stirring is opened, open reactor temperature-controlling system, add bromine Br2；2nd, in stirring state
Under, monochlorethane is added, by reaction temperature control at 80 DEG C, plus depending on the speed visual response temperature change of monochlorethane, lead to
Normal feed time is 7 hours；3rd, again by temperature of charge control at 80 DEG C after charging is finished, continue to stir 4 hours；4th, in reactant
At 150 DEG C, vacuum distillation obtains sesquialter methyl chloride aluminium 391g to material temperature control.Through EDTA titrimetries, by the content of aluminium
Calculate, yield is 93.5%.
Embodiment 4, a kind of preparation method of sesquialter ethyl phosphonium bromide aluminium, inducing agent iodine I used below2, aluminium（Aluminum shot or aluminium
Powder）Mol ratio with a bromoethane is：1:120:180,（9g：115g：695g）；The weight ratio of one bromoethane and solvent toluene
It is 1：2.5.It is comprised the following steps：1st, aluminium and toluene are added and are full of in the stainless steel cauldron of inert gas, open stirring,
Reactor temperature-controlling system is opened, iodine I is added2；2nd, under agitation, a bromoethane is added, by reaction temperature control 120
DEG C, plus depending on the speed visual response temperature change of a bromoethane, usual feed time is 5.5 hours；3rd, again will after charging is finished
Temperature of charge is controlled at 120 DEG C, continues to stir 2.5 hours；4th, when reaction mass temperature control is at 138 DEG C, vacuum distillation is obtained
Obtain sesquialter ethyl phosphonium bromide aluminium 745g；Through EDTA titrimetries, by the cubage of aluminium, yield is 92%.
Embodiment 5, a kind of preparation method of sesquialter butyl aluminium chloride, inducing agent 1 used below, 2- ethylidene periodides
C2H4I2, aluminium（Aluminum shot or aluminium powder）Mol ratio with a chlorobutane is：1:110:160,（20g：210g：1051g）；One chlorobutane
It is 1 with the weight ratio of solvent xylene or trimethylbenzene：1.8.It is comprised the following steps：1st, by aluminium and dimethylbenzene（Or trimethylbenzene）Plus
Enter in the stainless steel cauldron full of inert gas, open stirring, open reactor temperature-controlling system ,=add 1,2- ethylidene periodides
C2H4I2；2nd, under agitation, a chlorobutane is added, by reaction temperature control at 130 DEG C, plus the speed of a chlorobutane is regarded
Depending on reaction temperature change, usual feed time is 5.2 hours；3rd, again by temperature of charge control at 130 DEG C after charging is finished, after
Continuous stirring 3.5 hours；4th, when reaction mass temperature control is at 142 DEG C, vacuum distillation obtains sesquialter butyl aluminium chloride 1136g.
Through EDTA titrimetries, by the cubage of aluminium, yield is 90.5%.
Embodiment 6, a kind of preparation method of sesquialter butyl aluminium bromide, inducing agent 1 used below, 2- ethylidene periodides
C2H4I2, aluminium（Aluminum shot or aluminium powder）Mol ratio with a NBB is：1:155:195,（22g：326g：2085g）；One NBB
It is 1 with the weight ratio of dissolvant white oil：2.3.It is comprised the following steps：1st, aluminium and white oil are added into the stainless steel full of inert gas
In reactor, stirring is opened, open reactor temperature-controlling system, add 1,2- ethylidene periodides C2H4I2；2nd, under agitation, then
A NBB is added, by reaction temperature control at 90 DEG C, plus depending on the speed visual response temperature change of a NBB, generally charging
Time is 5.8 hours；3rd, again by temperature of charge control at 90 DEG C after charging is finished, continue to stir 2.8 hours；4th, in reaction mass
At 145 DEG C, vacuum distillation obtains sesquialter butyl aluminium bromide 2217g to temperature control；Through EDTA titrimetries, by the content meter of aluminium
Calculate, yield is 94%.
Embodiment 7, a kind of preparation method of sesquialter tert-butyl group aluminium chloride, inducing agent iodomethane CH used below3I, aluminium
（Aluminum shot or aluminium powder）Mol ratio with tertiary butyl chloride is：1:105:145,（10g：200g：946g）；Tertiary butyl chloride and solvent tetrahydrochysene
It is 1 to change weight how ratio：2.8.It is comprised the following steps：1st, add the stainless steel full of inert gas anti-in aluminium and tetrahydro chennai
Answer in kettle, open stirring, open reactor temperature-controlling system, add iodomethane CH3I；2nd, under agitation, the tert-butyl group is added
Chlorine, by reaction temperature control at 50 DEG C, plus depending on the speed visual response temperature change of tertiary butyl chloride, usual feed time is 6.5
Hour；3rd, again by temperature of charge control at 50 DEG C after charging is finished, continue to stir 2.3 hours；4th, in reaction mass temperature control
At 148 DEG C, vacuum distillation obtains sesquialter tert-butyl group aluminium chloride 1028g.Through EDTA titrimetries, by the cubage of aluminium, produce
Rate is 91%.
Embodiment 8, a kind of preparation method of sesquialter tert-butyl group aluminium bromide, inducing agent iodomethane CH used below3I, aluminium
（Aluminum shot or aluminium powder）Mol ratio with tert-butyl bromide is：1:115:165,（10g：218g：1593g）；Tert-butyl bromide and solvent：Such as
Two or more mixtures in hexane, hexamethylene, octane, certain herbaceous plants with big flowers alkane, dodecane, hexadecane, eicosane, lignocerane and white oil
Weight ratio is 1：2.It is comprised the following steps：1st, by aluminium and such as hexane, hexamethylene, octane, certain herbaceous plants with big flowers alkane, dodecane, hexadecane, 20
Two or more mixtures in alkane, lignocerane and white oil are added in the stainless steel cauldron full of inert gas, open stirring,
Reactor temperature-controlling system is opened, iodomethane CH is added3I；2nd, under agitation, tert-butyl bromide is added, by reaction temperature control
At 160 DEG C, plus depending on the speed visual response temperature change of tert-butyl bromide, usual feed time is 6.2 hours to system；3rd, charging is finished
Afterwards again by temperature of charge control at 160 DEG C, continue to stir 3.3 hours；4th, when reaction mass temperature control is at 140 DEG C, filtering
Obtain sesquialter butyl aluminium bromide 1533g.Through EDTA titrimetries, by the cubage of aluminium, yield is 85.1%.
Embodiment 9, a kind of preparation method of sesquialter methyl chloride aluminium, inducing agent 1 used below, 2- ethylidene periodides
C2H4I2, aluminium（Aluminum shot or aluminium powder）Mol ratio with monochloro methane is：1:85:175,（20g：163g：627g）；Monochloro methane with
Solvent：The weight ratio of the two or more mixtures in monochloro methane, tetrahydro chennai, toluene, dimethylbenzene and trimethylbenzene is 1：3.Its
Comprise the following steps：1st, by the two or more mixtures in aluminium and monochloro methane, tetrahydro chennai, toluene, dimethylbenzene and trimethylbenzene
Add in the stainless steel cauldron full of inert gas, open stirring, open reactor refrigeration system, add 1,2- ethylidene periodides
C2H4I2；2nd, under agitation, monochloro methane is added, by reaction temperature control at 150 DEG C, plus the speed of monochloro methane is regarded
Depending on reaction temperature change, usual feed time is 6.8 hours；3rd, again by temperature of charge control at 150 DEG C after charging is finished, after
Continuous stirring 3.8 hours；4th, when reaction mass temperature control is at 145 DEG C, distillation obtains sesquialter methyl chloride aluminium 558g.Through EDTA
Titrimetry, by the cubage of aluminium, yield is 90.1%.
The merely exemplary explanation principle of the invention of above-described embodiment and its effect, not for the limitation present invention.It is any ripe
The personage for knowing this technology can all change under without prejudice to spirit and scope of the invention to the equivalent technologies that above-described embodiment is carried out
Enter, all within the scope of the present invention.
Claims (10)
1. a kind of preparation method of sesquialter aikyl aluminum halide, it is characterised in that：It is comprised the following steps：Aluminium and organic solvent are added
In entering the reactor full of inert gas, then inducing agent is added in reactor, is under agitation added to a halogenated alkane
In reactant, reaction temperature is controlled between 50-160 DEG C；Described solvent is that boiling point values are hydrocarbon between 60-300 DEG C
Compound solvent；Described inducing agent is bromine Br2, iodine I2, iodomethane CH3I or 1,2- ethylidene periodides C2H4I2；Described induction
The mol ratio 1 of agent, aluminium and a halogenated alkane:80 -120:140-180；A described halogenated alkane is 1 with the weight ratio of solvent:
1.5~3；After described halogenated alkane charging is finished, continue to stir 2-4 when reaction temperature is controlled between 50-160 DEG C
Hour；When reaction mass temperature control is at 135-150 DEG C, vacuum distillation obtains sesquialter aikyl aluminum halide.
2. the preparation method of sesquialter aikyl aluminum halide according to claim 1, it is characterised in that：Described hydrocarbon
Solvent is saturated alkane or aromatic hydrocarbon.
3. the preparation method of sesquialter aikyl aluminum halide according to claim 2, it is characterised in that：Described saturated alkane is
Such as one or more of hexane, hexamethylene, octane, certain herbaceous plants with big flowers alkane, dodecane, hexadecane, eicosane, lignocerane and white oil of mixing
Thing；Aromatic hydrocarbon is one or more mixture of tetrahydro chennai, toluene, dimethylbenzene and trimethylbenzene.
4. the preparation method of the sesquialter aikyl aluminum halide according to claim 1 or 2 or 3, it is characterised in that：A described halogen
It is monochloro methane, a bromomethane, monochlorethane, a bromoethane, a chlorobutane, a NBB, tertiary butyl chloride or tertiary fourth for alkane
Bromide.
5. the preparation method of sesquialter aikyl aluminum halide according to claim 4, it is characterised in that：Described aluminium be aluminum shot or
Aluminium powder.
6. the preparation method of sesquialter aikyl aluminum halide according to claim 5, it is characterised in that：Described reaction temperature is
80-140℃。
7. the preparation method of sesquialter aikyl aluminum halide according to claim 6, it is characterised in that：Described inert gas is
Argon gas or nitrogen.
8. the preparation method of sesquialter aikyl aluminum halide according to claim 4, it is characterised in that：Described reaction temperature is excellent
Elect 80-140 DEG C as.
9. the preparation method of sesquialter aikyl aluminum halide according to claim 8, it is characterised in that：Described inert gas is
Argon gas or nitrogen.
10. the preparation method of the sesquialter aikyl aluminum halide according to claim 1 or 2 or 3, it is characterised in that：Described is anti-
Answer preferably 80-140 DEG C of temperature；Described inert gas is argon gas or nitrogen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710074500.3A CN106866718A (en) | 2017-02-10 | 2017-02-10 | A kind of preparation method of sesquialter aikyl aluminum halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710074500.3A CN106866718A (en) | 2017-02-10 | 2017-02-10 | A kind of preparation method of sesquialter aikyl aluminum halide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106866718A true CN106866718A (en) | 2017-06-20 |
Family
ID=59167293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710074500.3A Pending CN106866718A (en) | 2017-02-10 | 2017-02-10 | A kind of preparation method of sesquialter aikyl aluminum halide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106866718A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358962A (en) * | 2018-04-13 | 2018-08-03 | 山东亿盛实业股份有限公司 | A kind of method for continuously synthesizing of methyl sesquialter aluminium |
| CN109384812A (en) * | 2018-12-03 | 2019-02-26 | 姚磊 | A kind of methylisothiouronium methylphosphite diethylester preparation method |
| CN112480158A (en) * | 2020-12-31 | 2021-03-12 | 江苏爱姆欧光电材料有限公司 | Continuous production process of aluminum sesquiethylate chloride |
| CN112480159A (en) * | 2020-12-31 | 2021-03-12 | 江苏爱姆欧光电材料有限公司 | Continuous production process of sesquimethyl aluminum chloride |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374447C (en) * | 2003-08-18 | 2008-03-12 | 吉万奥丹股份有限公司 | Process for the preparation of methylaluminium dichloride |
-
2017
- 2017-02-10 CN CN201710074500.3A patent/CN106866718A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374447C (en) * | 2003-08-18 | 2008-03-12 | 吉万奥丹股份有限公司 | Process for the preparation of methylaluminium dichloride |
Non-Patent Citations (3)
| Title |
|---|
| 张之晶等: "三乙基铝的合成", 《北京航空学院学报》 * |
| 贾军纪等: "三甲基铝的合成及应用研究述评", 《石化技术与应用》 * |
| 韩亚晓等: "卤代烷基铝的合成及机理", 《山西化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108358962A (en) * | 2018-04-13 | 2018-08-03 | 山东亿盛实业股份有限公司 | A kind of method for continuously synthesizing of methyl sesquialter aluminium |
| CN108358962B (en) * | 2018-04-13 | 2020-07-21 | 山东亿盛实业股份有限公司 | Continuous synthesis method of methyl sesqui-aluminum |
| CN109384812A (en) * | 2018-12-03 | 2019-02-26 | 姚磊 | A kind of methylisothiouronium methylphosphite diethylester preparation method |
| CN112480158A (en) * | 2020-12-31 | 2021-03-12 | 江苏爱姆欧光电材料有限公司 | Continuous production process of aluminum sesquiethylate chloride |
| CN112480159A (en) * | 2020-12-31 | 2021-03-12 | 江苏爱姆欧光电材料有限公司 | Continuous production process of sesquimethyl aluminum chloride |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106866718A (en) | A kind of preparation method of sesquialter aikyl aluminum halide | |
| JP2019509963A (en) | Method for producing polymer sulfur | |
| US2066198A (en) | Process for preparing grignard compounds | |
| Seyferth et al. | The preparation of organolithium reagents by the transmetalation reaction: XI. Crotyllithium | |
| CN106831851A (en) | A kind of preparation method of allyl silicane | |
| Clark et al. | Organoindium chemistry II. Derivatives of dimethylindium (III) and methylindium (III) | |
| CN112028752B (en) | Synthetic method of 3',5' -dichloro-2, 2-trifluoroacetophenone | |
| CN102503968B (en) | The method of one-step process preparation of high-purity triethyl gallium | |
| TW200831411A (en) | Process for the fluorination of boron hydrides | |
| CN106831844B (en) | A kind of preparation method of trimethyl aluminium | |
| NO800092L (en) | HYDROCARBON SOLUBLE DIORGANOMAGNESIUM MIXTURES | |
| Li et al. | Exploring the synthesis of infinite helical chains with 2-carboxycinnamic acid | |
| CN114478351B (en) | Method for synthesizing alpha-alkyl substituted indole-3-formaldehyde compound | |
| CN107602528A (en) | A kind of method for preparing five-membered ring list sulfocarbonate | |
| CN102503969B (en) | The method of preparing high-purity trimethylgallium at one step | |
| CA2704992C (en) | Method for manufacturing dialkylaluminum monohalide | |
| TWI499593B (en) | Producing method of organometallic compound | |
| Sun et al. | Novel lead-organic framework based on 2, 2′-bipyridine-3, 3′-dicarboxylate ligand: Synthesis, structure and luminescence | |
| CN106748835A (en) | A kind of preparation method of stryphnonasal | |
| CN109232385B (en) | Preparation method of magnesium dichloride (2,2,6, 6-tetramethylpiperidine) lithium salt | |
| JPH04221389A (en) | Production of dialkyl zinc | |
| CN108822142A (en) | A kind of preparation method of triethyl-gallium | |
| Leser et al. | Synthesis and crystal structures of coordination polymers, networks and complexes of an adamantane shaped phosphorus–nitrogen cage ligand and cuprous chloride | |
| CN103204864A (en) | Method for preparing high-purity trimethyl indium | |
| Li et al. | A New Coordination Polymer [Pb (1, 4‐BDC)] n Containing a Unique μ6‐Bridging Coordination Mode |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170620 |
|
| WD01 | Invention patent application deemed withdrawn after publication |