CN106582858B - A kind of catalyst and its polymerization preparing alpha-olefin low polymers - Google Patents

A kind of catalyst and its polymerization preparing alpha-olefin low polymers Download PDF

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CN106582858B
CN106582858B CN201611181797.5A CN201611181797A CN106582858B CN 106582858 B CN106582858 B CN 106582858B CN 201611181797 A CN201611181797 A CN 201611181797A CN 106582858 B CN106582858 B CN 106582858B
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catalyst
alpha
olefin
low polymers
olefin low
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CN106582858A (en
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魏峰
鲍建楠
王瑛
张丽婷
董仕晋
刘歌
庞帅
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Shenyang Chemical Research Institute Co Ltd Ningxia Branch
Shenyang Research Institute of Chemical Industry Co Ltd
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    • B01J35/19—
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/06—Halogens; Compounds thereof
    • C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24

Abstract

The present invention relates to the preparation method of alpha-olefin low polymers, specifically a kind of catalyst and its polymerization for preparing alpha-olefin low polymers.The catalyst for being used to prepare alpha-olefin low polymers is SnCl4And RSO3H；Wherein, R is trifluoromethyl or fluorine atom.The oligomeric of alpha-olefin can be realized using preparation method of the invention at higher conversion rates there.High selectivity is shown in terms of the degree of polymerization using the oligomerization product of catalyst preparation of the present invention, for 1- decene, oligomerization product is almost dimer and tripolymer.

Description

A kind of catalyst and its polymerization preparing alpha-olefin low polymers
Technical field
The present invention relates to the preparation method of alpha-olefin low polymers, specifically a kind of catalyst for preparing alpha-olefin low polymers and Its polymerization.
Background technique
Alpha-olefin low polymers have importantly as a kind of high-performance synthetic lubricant base oil in lubricant in the market Position.This material is generally prepared by 1- octene, 1- decene and 1- laurylene catalytic oligomerization, and wherein 1- decylene oligomer has Optimal performance.
WO2015/095336 reports a kind of using AlCl3And AlBr3As catalyst, 1- decene is that raw material prepares α-alkene The method of hydrocarbon oligomer is prepared at 100 DEG C kinematic viscosity in the low of 4.6-11.5cSt in 71-130 DEG C in various embodiments Polymers (is equivalent to pentamer or more).WO2006/078395 uses AlCl3As catalyst, 1- octene, 1- decene, 1- ten Diene and 1-tetradecylene mixture as raw material, be prepared under different catalysts dosage 100 DEG C of kinematic viscosity be 40cSt and Two kinds of oligomer (ten aggressiveness to 30 aggressiveness) of 100cSt, and its pour point is compared.Comparison discovery uses smaller average The oligomer pour point that the raw material olefin of carbon number obtains is lower, has good low temperature service performance.US2009/0240012 is with 1- Decene dimer and decene are collectively as raw material, using metallocene and AlCl3As catalyst, water is prepared for as proton donor Number-average molecular weight 839-1764 (six aggressiveness to ten tripolymers), oligomer of 100 DEG C of range of viscosities in 5.46-27.9cSt.Equally Use AlCl3Research as catalyst there are also very much, such as US5196635, US4906798, US4533782, US4107080 and US4066715 etc..The in general oligomer degree of polymerization that this preparation method is prepared is higher, and it is higher to actually appear viscosity, fits In the synthetic lubricant base oil for preparing medium-viscosity and viscosity higher.
Use BF3The oligomer degree of polymerization as catalyst preparation is smaller.As US8598394 describe it is a kind of using BF3Make For major catalyst, n-butanol-n-butyl acetate is co-catalyst, and 1- octene, 1- decene and 1- laurylene mixture are raw material Synthetic method.This method is prepared for two kinds of oligomer that 100 DEG C of kinematic viscosity are 4cSt and 6cSt, and pour point is at -60 DEG C or so. WO02/092729 reports a kind of similar approach, uses BF3Major catalyst is done, EtOH-EtOAc does co-catalyst, uses 1- Decene, 1- laurylene are prepared for the oligomer that 100 DEG C of kinematic viscosity are 4cSt, 5cSt and 6cSt as raw material.These viscosity are not With oligomer be important criteria product in mass product in the market.Similar report there are also US6646174, US5420373, US5396013, US5284988, US5250750 and US5225588 etc..Use BF3As dominant catalyst system Standby oligomer main component is tripolymer to pentamer, and there are also a small amount of products for being greater than six aggressiveness, and viscosity is lower, be prepare it is low The method of viscosity synthetic lubricant base oil.But BF3Low boiling point is needed using pressure vessel, severe reaction conditions in reaction, And BF3It is toxic, corrosivity is strong, larger to environmental hazard.
Currently, the alpha-olefine polymerizing product of most of degree of polymerization heavy industrialization, the skill of alpha-olefin in actual production Art demand concentrate on extremely low degree of polymerization product (such as dimer, tripolymer) and high degree of polymerization product (i.e. high-viscosity products, 100 DEG C kinematic viscosity is on two kinds of products of 300cSt or more).Although the product that both demands can be produced by metallocene catalyst Met, but the price of metallocene catalyst and the rigors of consersion unit, operational safety can not be ignored.Such as It is mentioned in the patents such as WO2013/055483, US8609923, metallocene catalyst activity is higher, and contacting with air or water can send out Raw burning, needs to carry out under the conditions of anhydrous and oxygen-free, and the co-catalyst price needed is same expensive and dangerous, such as methyl alumina Alkane (MAO), N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate etc..
From actually, develop it is a kind of be easily achieved, prepare the side of extremely low degree of polymerization product (dimer and tripolymer) Method is necessary, and is conducive to the production cost that both the above product is greatly lowered and the potential security risk of production.
Summary of the invention
It is an object of that present invention to provide a kind of catalyst for preparing alpha-olefin low polymers and its polymerization
To achieve the above object, the invention adopts a technical scheme as:
A kind of catalyst preparing alpha-olefin low polymers, the catalyst for being used to prepare alpha-olefin low polymers are SnCl4 And RSO3H；Wherein, R is trifluoromethyl or fluorine atom.
The catalyst is SnCl4:RSO3H=1:60-60:1 in molar ratio.
The catalyst is SnCl4:RSO3H=1:20-20:1 in molar ratio.
The catalyst is SnCl4:RSO3H=1:6-6:1 in molar ratio.
A method of alpha-olefin low polymers being prepared using the polymerization catalyst, raw material is contacted with the catalyst, Oligomerization occurs, generates alpha-olefin low polymers；Raw material is the mixture and solvent of alpha-olefin and solvent or alpha-olefin.
Further, raw material is contacted with the catalyst, in -10-85 DEG C of generation oligomerizations, it is low to generate alpha-olefin Polymers；Catalyst total addition level is the 0.05wt%-40wt% of raw material in the oligomerization.
Temperature is 20-85 DEG C in the oligomerization, and catalyst total addition level is the 1wt%-15wt% of raw material.
The alpha-olefin is 1- hexene, 1- octene, 1- decene, 1- dodecylene, tetradecene, cetene, 1- One or more of alkene in octadecene.
The solvent is C6-C13Saturated hydrocarbons.Preferably, n-hexane, normal heptane, normal octane, n -nonane, hexamethylene is selected to make For solvent.
Use SnCl4With RSO3Method of the H bi-component as catalyst preparation poly alpha olefin (PAO) oligomer, the α-alkene Hydrocarbon oligomer shows excellent selectivity in the degree of polymerization, and showing as main component is dimer and tripolymer.
Advantage for present invention:
The oligomeric of alpha-olefin can be realized using preparation method of the invention at higher conversion rates there.It is catalyzed using the present invention The oligomerization product of agent preparation shows high selectivity in terms of the degree of polymerization, for 1- decene, oligomerization product It is almost dimer and tripolymer.
Specific embodiment
It is described in detail below for general embodiment of the invention.The present invention is not limited to following implementation, Implement after can carrying out condition change in the range described in its claim.
Prepare embodiment
Embodiment 1
The reaction equation of poly alpha olefin (PAO) oligomer is prepared using the bicomponent catalyst are as follows:
Since catalysts are more sensitive to water, raw materials used alkene and solvent are both needed to be dried.Drying process side Method is relatively more, is normally carried out as long as can guarantee that water removing is clean in raw material, does not influence reaction.It is removed water with common molecular sieve For method, after 180 DEG C of 5A molecular sieve activation, it is cooled to room temperature in drier, is subsequently poured into raw material olefin or solvent, stand To get to dry raw material olefin or solvent after for 24 hours, normally current use can be now taken.
It measures 30ml normal heptane to be added in 250ml four round flask, weighs 5.2gSnCl4And 3.0gCF3SO3H is added anti- It answers in bottle, controls temperature at 40 DEG C.100ml 1- decene is slowly dropped in reaction flask using constant pressure funnel, speed is added dropwise About 2ml/min is spent, due to exothermic heat of reaction during dropwise addition, reaction temperature is at 48-55 DEG C.
The reaction was continued after being added dropwise 3h, temperature slowly fall back to 40 DEG C, and reaction terminates.Then with isometric 10% NaOH solution washing, then is washed with deionized water to neutrality, then separates oil reservoir with water layer, oil reservoir vacuum distillation removing solvent and A small amount of water.
This experiment mainly uses exclusion chromatography characterizing to oligomer, gas chromatography-mass spectrometry supplementary table Sign.Used is the 1515-2414 gel permeation chrommatograph of Waters company production, WatersHR series gel color Column is composed, tetrahydrofuran is mobile phase, the Narrow distribution polystyrene standard of Scientific Polymer Products company production Product, the oligomer solution that compound concentration is 2.5 ‰ are tested, and 30 DEG C of column temperature, flow rate of mobile phase 1ml/min.Each product yield Usable floor area normalization method is calculated.
Embodiment 2
For other operation sequences with embodiment 1, solvent for use is n-hexane, and the amount of used catalyst is 2.6gSnCl4With 6.0gCF3SO3H, reaction temperature is at 50-55 DEG C during dropwise addition.
Embodiment 3
For other operation sequences with embodiment 1, solvent for use is normal octane, and the amount of used catalyst is 5.2gSnCl4With 1.5gCF3SO3H, reaction temperature is at 44-47 DEG C during dropwise addition.
Embodiment 4
For other operation sequences with embodiment 1, solvent for use is n -nonane, and the amount of used catalyst is 5.2gSnCl4With 0.6gCF3SO3H, reaction temperature is at 42-46 DEG C during dropwise addition.
Embodiment 5
Other operation sequences are 5.2gSnCl with embodiment 1, the amount of used catalyst4And 0.3gCF3SO3Process is added dropwise in H Middle reaction temperature is at 42-46 DEG C.
Embodiment 6
Other operation sequences are 5.2gSnCl with embodiment 1, the amount of used catalyst4And 0.1gCF3SO3Process is added dropwise in H At 40-43 DEG C, heating is not obvious middle reaction temperature.
Embodiment 7
For other operation sequences with embodiment 1, solvent for use is hexamethylene, and the amount of used catalyst is 1.3gSnCl4With 3.0gCF3SO3H, reaction temperature is at 47-51 DEG C during dropwise addition.
Embodiment 8
Other operation sequences are 0.52gSnCl with embodiment 1, the amount of used catalyst4And 3.0gCF3SO3Process is added dropwise in H Middle reaction temperature is at 41-44 DEG C.
Embodiment 9
Other operation sequences are 0.1gSnCl with embodiment 1, the amount of used catalyst4And 3.0gCF3SO3H, reaction process Middle temperature does not have significant change, maintains 38-42 DEG C always.
Embodiment 10
Other operation sequences are with embodiment 1, and initial temperature becomes 20 DEG C, and the amount of used catalyst is 10.4gSnCl4With 6.0gCF3SO3H, reaction temperature is at 35-40 DEG C during dropwise addition.
Embodiment 11
Other operation sequences are with embodiment 1, and initial temperature becomes 60 DEG C, and the amount of used catalyst is 5.2gSnCl4With 3.0gCF3SO3H, reaction temperature is at 68-74 DEG C during dropwise addition.
Embodiment 12
For other operation sequences with embodiment 1, initial temperature becomes 75 DEG C, the amount of used catalyst be 1.04gSnCl4 and 0.6gCF3SO3H, reaction temperature is at 78-85 DEG C during dropwise addition.
Embodiment 13
Other operation sequences carry out in cryogenic thermostat reactive bath technique with embodiment 1, reaction, and reaction initial temperature becomes -10 DEG C, the amount of used catalyst is 5.2gSnCl4And 3.0gCF3SO3H, temperature is at -5-0 DEG C in reaction process.
Embodiment 14
Other operation sequences before the reaction purge reactor using high pure nitrogen with embodiment 1, and in the reaction phase Between persistently maintain nitrogen atmosphere.Catalyst uses 5.2gSnCl4And 1.15gFSO3H, reaction temperature is in 54-59 during dropwise addition ℃。
Following table 1 lists the test result of above-described embodiment 1-14.
Embodiment SnCl4/g CF3SO3H/g Initial temperature/DEG C Monomer % Dimer % Tripolymer % Total recovery %
1 5.2 3.0 40 8.96 38.81 52.23 91.04
2 2.6 6.0 40 14.65 29.53 55.82 85.35
3 5.2 1.5 40 15.97 44.45 39.58 84.03
4 5.2 0.6 40 34.45 51.02 14.53 65.55
5 5.2 0.3 40 65.32 28.97 5.71 34.68
6 5.2 0.1 40 95.90 4.1 - 4.1
7 1.3 3.0 40 21.25 42.27 36.48 88.75
8 0.52 3.0 40 54.43 30.21 15.36 45.57
9 0.1 3.0 40 99.75 0.25 - 0.25
10 10.4 6.0 20 11.08 30.56 58.36 88.92
11 5.2 3.0 60 8.14 42.82 49.03 91.86
12 1.04 0.6 75 5.45 51.41 43.14 94.55
13 5.2 3.0 -10 42.36 27.44 30.20 57.64
Embodiment SnCl4/g FSO3H/g Initial temperature/DEG C Monomer % Dimer % Tripolymer % Total recovery %
14 5.2 1.15 40 7.75 44.96 47.29 92.25
Embodiment 15-22
For operation sequence with embodiment 1, initial temperature is 38-42 DEG C, monomer use respectively 1- hexene, 1- octene, 1- decene, 1- laurylene, 1-tetradecylene, 1- hexadecylene, 1- octadecylene and alkene mixture (1- octene, 1- decene, 1- laurylene, 1- 14 Alkene, 1- hexadecylene, 1- octadecylene respectively account for 1/6) (volume ratio), and the amount of used catalyst is 5.2gSnCl4 and 3.0gCF3SO3H.
Following table 2 lists the test result of above-described embodiment 15-22.
Embodiment 23 (laboratory scale-up 1)
In 2000ml four-hole bottle, 300ml normal heptane is added, is added in 250ml four round flask, starts stirring, add Enter 52gSnCl4 and 30gCF3SO3H, heating water bath is warming up to 40-42 DEG C.Using constant pressure funnel by 1000ml1- decene It is added drop-wise in reaction flask, rate of addition about 20ml/min, due to exothermic heat of reaction during dropwise addition, reaction temperature is at 46-58 DEG C.
The reaction was continued after being added dropwise 3h, temperature slowly fall back to 40-42 DEG C, and reaction terminates.Then it uses in equal volume The washing of 10%NaOH solution, then be washed with deionized water to neutrality, then oil reservoir is separated with water layer.
Oil reservoir vacuum distillation removes solvent and a small amount of water, vacuum meter reading 0.095Mpa, temperature 60 C；Then it is warming up to 120 DEG C are evaporated in vacuo 1 hour, recycle unreacted 1- decene, vacuum meter reading 0.095Mpa.30 DEG C are cooled to, discharging obtains 670.6 gram oligomer, yield 90.5%.
Embodiment 24 (laboratory scale-up 2)
Other operation sequences are with embodiment 23,40 DEG C of initial temperature, monomer using alkene mixture (1- octene, 1- decene, 1- laurylene respectively accounts for 1/3) (volume ratio), and catalyst is 52gSnCl4 and 30gCF3SO3H, reaction temperature 45-56 during dropwise addition ℃.Discharging, obtains 651.1 grams of oligomer, yield about 88.1%.
Embodiment 25 (workshop pilot scale)
200 liters of glassed steel reaction vessels are added 30 liters of normal heptanes by measuring tank, start stirring, frame type stirring, revolution 85rpm；5.2 kilograms of SnCl4 and 3 kilogram of CF3SO3H are sequentially added, steam heating is led into collet, is warming up to 40-42 DEG C.It is logical It crosses measuring tank and is slowly added into 100 liters of 1- decene, about 2 liters/min of rate of addition, due to exothermic heat of reaction during dropwise addition, reaction is warm Degree is flushed to 65 DEG C, and at this moment collet leads to cooling water temperature, controls 45-60 DEG C of temperature, 55 DEG C of rear temperature is added dropwise.The reaction was continued 3 Hour, do not observe exothermic heat of reaction phenomenon, temperature also slowly falls back to 35 DEG C, and reaction terminates.
By measuring tank be added 50 liters of 10%NaOH solution, stirring 0.5 hour after stand 1 hour, below water layer be put into it is useless Liquid bucket；Oil reservoir is washed 1 time with 50 liters of 10%NaOH solution again, and water layer is put into waste liquid barrel.Oil reservoir washs 0.5 with 50 liters of deionized waters 1 hour is stood after hour, water layer is put into waste liquid barrel；Repetitive operation 3 times, oil reservoir pH ≈ 7 is measured, water layer point is net.
Stirring is started, is slowly heated up, oil reservoir is evaporated in vacuo 2 hours, and vacuum meter reading 0.09Mpa, is returned by 30-60 DEG C of temperature Receive 29.2 liters of normal heptane.It then proceedes to heat up, vacuum meter reading 0.095Mpa, recycles unreacted 1- decene by 100-140 DEG C of temperature 10.3 liters.30 DEG C are cooled to, discharging obtains 66.5 kilograms of oligomer, yield 90.1%.
Following table 3 lists the test result of above-described embodiment 23-25.
Embodiment Monomer % Dimer % Tripolymer % The degree of polymerization > 4 products Total recovery %
23 - 42.63 57.37 - 90.5
24 - 48.52 51.48 - 88.1
25 - 42.31 57.69 - 90.1
Comparative example 1
Operation sequence is individually catalyzed with embodiment 1, catalyst using 5.2gSnCl4, and reaction 336h has no that significant reaction is existing As.GC-MS has a small amount of dimer to generate as the result is shown, and oligomer yield is less than 1%.
Comparative example 2
Operation sequence is individually catalyzed with embodiment 1, catalyst using 6.0gCF3SO3H, and reaction 336h has no significant reaction Phenomenon.GC-MS has trace dimer and isomerization monomer to generate as the result is shown, and oligomer yield is less than 1%.
Comparative example 3
For operation sequence with embodiment 1, catalyst uses 1.33gAlCl3, and co-catalyst uses 0.05g isopropanol, reaction 4h.The number-average molecular weight (Mn) of GPC oligomer as the result is shown is 2520, belongs to the polymer of intermediate molecular weight, rather than dimerization Body or tripolymer.
Comparative example Catalyst Reaction result
1 5.2g SnCl4 Dimer less than 1% generates
2 6.0g CF3SO3H Trace dimer and isomerization monomer
3 1.33gAlCl3 Product number-average molecular weight is 2520 (18 aggressiveness or so)
By above-mentioned comparison it can be found that can be catalyzed alpha-olefine polymerizing using catalyst of the present invention generates the extremely low degree of polymerization Product (dimer and tripolymer), it is simple process, safe and practical, it is easy to accomplish industrialization.And it is used alone one such Same effect is then not achieved in catalyst.

Claims (6)

1. a kind of catalyst for preparing alpha-olefin low polymers, it is characterised in that: the catalyst for being used to prepare alpha-olefin low polymers is SnCl4And RSO3H；Wherein, R is trifluoromethyl or fluorine atom；
The alpha-olefin is 1- hexene, 1- octene, 1- decene, 1- dodecylene, tetradecene, cetene, 1- 18 One or more of alkene in carbene；
The catalyst molar ratio is SnCl4:RSO3H=1:20-20:1。
2. the catalyst according to claim 1 for preparing alpha-olefin low polymers, it is characterised in that: the catalyst molar ratio is SnCl4:RSO3H=1:6-6:1。
3. a kind of utilize the method for preparing alpha-olefin low polymers by polymerization catalyst described in claim 1, it is characterised in that: will be former Material is contacted with the catalyst, and oligomerization occurs, and generates alpha-olefin low polymers；Raw material is alpha-olefin and solvent or alpha-olefin Mixture and solvent；
The alpha-olefin is 1- hexene, 1- octene, 1- decene, 1- dodecylene, tetradecene, cetene, 1- 18 One or more of alkene in carbene.
4. the method according to claim 3 for preparing alpha-olefin low polymers using polymerization catalyst, it is characterised in that: in solvent In, raw material is contacted with the catalyst, in -10-85 DEG C of generation oligomerizations, generates alpha-olefin low polymers；It is described oligomeric anti- Answering middle catalyst total addition level is the 0.05wt%-40wt% of raw material.
5. the method according to claim 4 for preparing alpha-olefin low polymers using polymerization catalyst, it is characterised in that: described low Temperature is 20-85 DEG C in poly- reaction, and catalyst total addition level is the 1wt%-15wt% of raw material.
6. the method according to claim 3 for preparing alpha-olefin low polymers using polymerization catalyst, it is characterised in that: described molten Agent is C6-C13Saturated hydrocarbons.
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