CN110041457A - A kind of polymerization of alpha-olefin polymerization catalyst and preparation method thereof, alpha-olefin - Google Patents
A kind of polymerization of alpha-olefin polymerization catalyst and preparation method thereof, alpha-olefin Download PDFInfo
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- CN110041457A CN110041457A CN201810036232.0A CN201810036232A CN110041457A CN 110041457 A CN110041457 A CN 110041457A CN 201810036232 A CN201810036232 A CN 201810036232A CN 110041457 A CN110041457 A CN 110041457A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
Abstract
The invention discloses a kind of preparation methods of alpha-olefin polymerization catalyst, comprising the following steps: S1 Vehicle element: carrier being refined in hexamethylene using Organic Alcohol, carrier alcohol adduct is obtained；The load of S2 active component: active component titanium compound hexamethylene is diluted 2-4 times, then is added dropwise in carrier alcohol adduct and is stirred, obtains major catalyst；The purification of S3 major catalyst: catalyst semi-finished product are washed with hexamethylene, obtain the slurries containing catalyst semi-finished product, the major catalyst after being purified after vacuum dried；The reduction of S4 major catalyst: using co-catalyst as reducing agent, finished catalyst is obtained after reduction.The polymerization of alpha-olefin.The invention also discloses a kind of catalyst and a kind of polymerization of alpha-olefin by above method preparation using catalyst made from above-mentioned preparation method as catalyst.
Description
Technical field
The present invention relates to a kind of alpha-olefin polymerization catalyst and preparation method thereof and by the alpha-olefin of the catalyst
Polymerization more particularly to a kind of alpha-olefin polymerization catalyst as synthetic lubricant base oil and preparation method thereof and
By the polymerization of the alpha-olefin of the catalyst.
Background technique
Lubricating oil is that one kind is coated in the surface of moving object such as machine bearing, can play lubrication, cooling, cleaning, sealing, prevent
The oily liquids or semisolid of the effects of rust, buffering.General lubricating oil is made of base oil and additive, and base oil is lubricating oil
Basis, the quality of base oil has a great impact to the performance of product.The source of base oil is divided into mineral lubricating oil, animals and plants
Oil and synthetic lubricant fluid three classes.Major part lube base oil is all based on mineral lubricating oil at present；Vegetable and animals oils therein
Although environmentally friendly reproducibility is good, has and easily aoxidize, the short disadvantage of service life；Synthetic lubricant fluid therein, is adopted completely
It is synthesized with organic procedures, is that there is certain chemical structure and property lube base oil.
Synthetic lubricant fluid can be divided into following a few classes according to chemical structure:
(1) synthetic hydrocarbon oil, including poly alpha olefin, polyisobutene and alkylbenzene etc.；
(2) organic acid ester synthetic oil；
(3) polyether-type synthetic oil；
(4) phosphate；
(5) fluorine-containing oil；
(6) silicate-containing oil.
Therein, poly alpha olefin is one of synthetic base oil.Poly alpha olefin (PAO) is by the aggregated reaction system of ethylene
At alhpa olefin, it is further aggregated and hydrogenation and be made.It is more common synthetic lubricant base oil, and use scope is most wide
It is general.
Poly alpha olefin base oil has the Temperature-Viscosity feature of slightly-inclined, lower pour point, outstanding launch metrics and work
For the advantage of engine oil.Have the characteristics that as synthetic oil it is very outstanding, first, (thermal stability refers to high thermo oxidative stability
Be that good viscosity index (VI) is able to maintain in wide in range temperature range, engine is easily pacified under arctic weather
Full starting, while can protect engine at high speed and under big weight bearing to the maximum extent) it is special because of synthetic oil minor structure
Property allow it to possess higher flowing and penetrability (and mineral oil compares).Its chemical stability refers to that synthetic oil exists
Any chemical change (oxidation, waxdip etc.) for destroying its service performance will not occur during working in engine, that is to say, that
Stroke incrustation and paint (refer to the very high surface row of temperature at it is transparent, firm, what is be formed of oxide will not melt
The film of change) possibility very little, the advantages of synthetic oil described above is 3 times of mineral oil or more, and pour point is lower than mineral oil
Very much (- 50 DEG C, -60 DEG C), very high viscosity index (VI), that is to say, that the variation of viscosity and little under the variation of temperature, this
Point just can be such that engine easily starts under the weather of severe cold.Second, still maintain higher when operating temperature is higher than 100 DEG C
The viscosity index (VI)-oil film that therefore separates friction surface will not destroy best thermal energy state, and it is whole to can reduce engine
Mechanical loss reduces parts depreciation.These oil possess all advantages of mineral oil simultaneously.They are easily flowed, and can be reduced because of friction
Caused power loss, can reduce oil consumption, it is low lead to oil temperature, that is, can allow for engine in subzero 40 degrees Celsius of feelings
It is worked normally under condition.Volatility under these oily high temperature is all smaller, and the service life this provides for improved oil is more than 30,000 kilometers.
Therefore, poly alpha olefine synthetic oil (abbreviation PAO) has good viscosity temperature characteristic and low temperature flow, is to prepare height
The ideal base oil of shelves, special lube.
In face of the fast development of countries in the world mechanical industry, people require to be continuously improved to quality of lubrication oil.High-quality PAO
(poly alpha olefin) synthetic lubricant fluid relies primarily on the statuses such as high price import, develops high performance lubricating oil with realistic meaning.
External existing PAO synthesis technology catalyst system is divided into homogeneous method and two kinds of multi-phases process, and homogeneous method has: BP
Cp2ZrCl2The Et of/MAO metallocene catalyst, Uniroyal3Al/TiCl4The BF of/RCl Ziegler catalyst, Chevron3/
I-BuOH/EtOH and AlCl3The BF of/trimethylamine hydrochloride ionic-liquid catalyst, Neste3/ n-BuOH cationic catalyst,
The AlCl of Indian Oil3/Ti(OBu)4Cationic catalyst etc.；Multi-phases process has: the Cr/MCM-41 molecule of Exxon Mobil
Sieve catalyst and WOX/ZrO2Bimetallic oxide etc..Outstanding Ni Luoyier chemical company is with TiCl4With Et3Al2Br3The catalysis of formation
System is catalyzed the polymerization of 1- decene, and polymer molecular weight is 82.86mm in 500-5000,100 DEG C of viscosity2/ s, viscosity index (VI) reach
To 170.It is 300m that chromic acetate is supported on specific surface area by Mobil Oil Corporation2On the 8-12 mesh silica of/g, maturing temperature is
800 DEG C, CO reduction is carried out at 300 DEG C, and the test of 1- hexene oligomerization, obtained product are carried out with the catalyst prepared under this condition
100 DEG C of viscosity are 151, and viscosity index (VI) 164, using the aggregation test that 1- decene is carried out as raw material, 100 DEG C of viscosity of product are
157.6 viscosity index (VI) 217.2010, the SpectraSyn Elite that Exxon Mobil Corporation releasesTMMetallocene PAO product,
Compared with traditional PAO, feature is embodied in that shear stability is good, viscosity index (VI) is high (viscosity index (VI) of PAO150 is more than 200), beauty
Inspire confidence in (Cp) (Cp of company's design*)MX1X2The non-bridge chain dicyclopentadiene ring single-metal reforming catalyst of type, by the adjustment to luxuriant ring substituents,
The control to reactive polymeric degree can be achieved, produce the PAO of different viscosities.Japanese Chu Guang company uses (Cp1)R1R2(Cp2)M
X1X2Doube bridge chain dicyclopentadiene ring single-metal reforming catalyst catalysis octene-1, decylene-1 prepare hyperviscosity with the mixture of laurylene -1 and refer to
Number PAO, viscosity index (VI) are 296mm up to 215,100 DEG C of kinematic viscosity2/ s, pour point are -30 DEG C.
The country has equally carried out related scientific research work in PAO base oil field, and Beijing University of Chemical Technology is with TiCl4With Et2AlCl
1- decene polymerization studies are carried out, polymerization activity reaches 198.6kg PAO/mol Ti, and tripolymer content is 45%, the tetramer
Content is 31%, and polymerizate exists mostly in the form of head to tail polymerization, excellent product performance.East China University of Science is with Rac-Et (1-
Ind)2ZrCl2/ MAO Dan Qiaolian dicyclopentadiene ring monometallic catalyst system is 8 × 10 in Zr/ decylene-1 molar ratio-5, reaction temperature be
50 DEG C, the reaction time, the conversion ratio of decylene-1 was 91.62% when being 60min.The overall performance of polymerizate is more excellent, and 100
DEG C kinematic viscosity be 393.93mm2/ s, viscosity index (VI) 271.Northeast Petroleum University uses (Cp) MX1X2Dan Qiaolian Dan Maohuan
Metallocene catalyst, borate compounds are co-catalyst, and catalysis decylene-1 prepares PAO, the superelevation prepared when temperature is 60 DEG C
Viscosity index (VI) PAO, viscosity index (VI) (VI) is up to 238.2011, Sinopec Research Institute of Petro-Chemical Engineering was with ionic liquid body
System is catalyst, and kinematic viscosity at 100 DEG C is made and is greater than 40mm2The excellent PAO product of/s.
Wherein, Ziegler-Natta catalyst appearance has nearly 60 years history so far, although during which occurring such as metallocene
With the polyolefin catalysts such as Nonmetallocene, but its industrial problems is more, such as co-catalyst valuableness, major catalyst load there is also
Difficulty etc..Therefore, with regard to current industrial production with from the point of view of occupation rate of market, traditional Z-N catalyst will be following a period of time
The leader of internal olefin polymerization field.
Patent 96106647.4X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2It is dissolved in one
In the mixture of the pure and mild alkane of kind, liquid MgCl is formed2Alcohol adducts, this liquid MgCl2Alcohol adducts and TiCl4Contact, obtains
To olefin polymerization catalysis, but the hydrogen regulation performance of catalyst is poor, and the melt index MFR of polyethylene can only be in 0.1g/10min-
It is adjusted in 220g/10min.
Patent 200480008242.X discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2Directly
It connects and is dissolved in ethyl alcohol and is prepared for solid MgCl2Alcohol adducts, then by TiCl4It is supported on solid MgCl2Alkene has been obtained on alcohol adducts
Polymerization catalyst.
Patent 201110382706.5 discloses a kind of olefin polymerization catalysis and preparation method thereof, by carrier MgCl2It is molten
Solid MgCl is prepared in the organic solvent of isooctanol and ethyl alcohol2Alcohol adduct, then by TiCl4It is supported on solid MgCl2Alcohol adduct
On obtained olefin polymerization catalysis, which has good hydrogen tune effect.But catalyst activity is relatively low, major catalyst
Grain is easily adhered on the wall.
Patent CN85100997A, CN200810227369.0, CN200810227371.8, CN200810223088.8 are public
A kind of olefin polymerization catalysis and preparation method thereof is opened, by MgCl2Particle is dissolved in organic epoxy compound object, organic phosphorus compound
In the system of inert organic solvents, MgCl is obtained2Solution, then with TiCl4Contact, is prepared for the major catalyst of olefinic polymerization.Institute
The effect for the organic phosphorus compound stated is to make MgCl2A necessary component in the dicyandiamide solution of grain dissolution.
Patent 2013105985560 discloses in catalyst preparation process, and it is small that inert organic solvents, carbon atom number is added
In 5 alcohol of monohydric alcohol, carbon atom number greater than 5, MgCl2After grain dissolution, organic phosphorus compound, organo-silicon compound are added
And organoboron compound, prepare liquid MgCl2Alcohol adduct, then by TiCl4With this liquid MgCl2Alcohol adduct contact, adds again later
Enter polyhydroxy solid, obtain olefin polymerization catalysis, particle shape, the catalyst alkene of solid main catalyst can be improved
The bulk density of the hydrogen regulation performance of polymerized hydrocarbon, polyolefin.
Patent 201310034134 discloses in catalyst preparation process, and it is small that inert organic solvents, carbon atom number is added
In 5 alcohol of alcohol, carbon atom number greater than 5, MgCl2After grain dissolution, organic phosphorus compound and organo-silicon compound are added, is made
Standby liquid MgCl2Alcohol adduct, then by TiCl4With this liquid MgCl2Alcohol adduct contact, adds polyhydroxy solid later, obtains
To alkene catalyst structure, the particle shape of solid main catalyst, the hydrogen tune of catalyst olefinic polymerization can be improved
Performance.
Patent 201210436136.8 discloses in catalyst preparation process, and inert organic solvents, carbon atom number are added
Alcohol, carbon atom number less than 5 are greater than 5 alcohol, MgCl2After grain dissolution, organic phosphorus compound and organo-silicon compound are added,
Prepare liquid MgCl2Alcohol adduct, then by TiCl4With this liquid MgCl2Alcohol adduct contact, obtains alkene catalyst structure,
The particle shape of solid main catalyst, the hydrogen regulation performance of catalyst olefinic polymerization can be improved；This patent discovery, in halogenation
After magnesium carrier dissolution, organic phosphorus compound is added, the catalytic activity of catalyst can be significantly improved, solid main reminder can be eliminated
The electrostatic of catalyst particles, primary catalyst particles are not adhere on chamber wall.
Patent CN106519084A provides a kind of preparation method of olefin polymerization catalysis the following steps are included: 1) by magnesium
Compound support dispersion in inert organic solvents, be added carbon atom number be 2 to 15 alcohol, at 90 to 150 DEG C stirring and dissolving 1 to
5h；2) 1) solution is cooled to 30 DEG C to 80 DEG C, starlike organic azepine ether compound, reaction 0.5 to 3h is added；3) -25 to
At 30 DEG C, the system that step 2) is obtained is contacted with transition metal halide, and 0.5-5h is reacted at -25 to 30 DEG C, then will
System is warming up to 50-120 DEG C, reacts 0.5-5h, in temperature-rise period, solid particle is gradually precipitated, after reaction, with toluene
Or n-hexane washed product 4-6 times, it is filtered to remove unreacted reactant；Vacuum drying obtains pulverulent solids major catalyst.Vacuum is dry
Dry temperature is 40 DEG C to 90 DEG C；Vacuum drying time is 0.5 hour to 5 hours, preferably 1 hour to 4 hours.
It is co-catalyst that common similar ziegler natta catalyst, which mostly uses a kind of alkyl aluminum, it is difficult to which control is lived well
Property center reducing degree, such as only formula with triethyl aluminum is co-catalyst, and product viscosity index can guarantee, but polymerization activity will
Decline；Single using aluminium diethyl monochloride as co-catalyst, polymerization activity is high, and product viscosity will be reduced with performance.
Summary of the invention
To solve the above-mentioned problems, the present invention not only ensure that polymerization activity using compound alkyl aluminum as co-catalyst, but also
It can be with synthesized high-performance PAO product.
For this purpose, the present invention provides a kind of preparation method of alpha-olefin polymerization catalyst, comprising the following steps:
S1 Vehicle element: carrier is refined in hexamethylene using Organic Alcohol, carrier alcohol adduct is obtained；
The load of S2 active component: active component titanium compound hexamethylene is diluted 2-4 times, then is added dropwise to the conjunction of carrier alcohol
It is stirred in object, obtains major catalyst；
The purification of S3 major catalyst: catalyst semi-finished product are washed with hexamethylene, are obtained containing catalyst semi-finished product
Slurries, the major catalyst after being purified after vacuum dried；
The reduction of S4 major catalyst: using co-catalyst as reducing agent, finished catalyst is obtained after reduction；
The co-catalyst is selected from trimethyl aluminium, triethyl aluminum, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethyl
Two kinds in aluminium chloride, methylaluminoxane and ethylaluminoxane, the molar ratio of both components is 1:0.1~10.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein two kinds of components in the co-catalyst
Molar ratio is preferably 1:0.1~2；Further preferably 1:0.1~0.5.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the co-catalyst is preferably a chlorine two
Aluminium ethide and triethyl aluminum, the molar ratio of the two are preferably 1:0.1~1；The molar ratio of the two be more preferably 1:0.2~
0.5。
The preparation method of alpha-olefin polymerization catalyst of the present invention, in step S2, the dosage of the active component is excellent
It is selected as 0.1%~10% with the weight of the carrier alcohol adduct.
The preparation method of alpha-olefin polymerization catalyst of the present invention, in step S4, the major catalyst is with active group
Dividing meter and the molar ratio of the co-catalysis component is preferably 1:0.1~10.
The preparation method of alpha-olefin polymerization catalyst of the present invention, in step S4, the major catalyst is with active group
Dividing meter and the molar ratio of the co-catalysis component is preferably 1:1~20.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the step of Vehicle element is preferred
Are as follows: carrier is at 200 DEG C, and in nitrogen protection, heating is for 24 hours；Carrier and hexamethylene are configured to the suspension that molar ratio is 1:20,
At 20-100 DEG C, it is added dropwise to the n-butanol for being 1:1-10 with carrier molar ratio in slow speed, is allowed to generate alcohol conjunction with carrier
Object.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the step of active component loads is excellent
It is selected as: at 10-100 DEG C, active component hexamethylene being diluted 2-4 times, carrier alcohol adduct is added, stirs 1-4h.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the step of catalyst purifies is preferred
Are as follows: multiple hot wash is carried out with hexamethylene and is washed, washing supernatant liquor is transferred out of, and obtains supported catalyst slurries；After vacuum dried
Supported catalyst after being purified.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the titanium compound is preferably selected from tetrachloro
Change at least one of titanium, titanium trichloride and isopropyl titanate.
The preparation method of alpha-olefin polymerization catalyst of the present invention, wherein the carrier is preferably selected from silica gel, three oxygen
Change at least one of two aluminium, magnesium chloride and MCM-41.
It is including the main reminder as made from above-mentioned preparation method the present invention also provides a kind of alpha-olefin polymerization catalyst
Agent and co-catalyst, the major catalyst are made of carrier and active component, and the activated centre is titanium compound, the load
Body can be selected from trimethyl aluminium, three selected from one of silica gel, aluminum oxide, magnesium chloride and MCM-41, the co-catalyst
Two in aluminium ethide, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethylmercury chloride aluminium, methylaluminoxane and ethylaluminoxane
Two kinds in kind, the molar ratio of both components is 1:0.1~10.
The present invention also provides a kind of polymerizations of alpha-olefin, are catalysis with catalyst made from above-mentioned preparation method
Agent, catalyzed linear or non-linear alpha-olefin prepare lube base oil to polymerize, polarity used in polymerization process or non-
Polar solvent is alkane, aromatic hydrocarbons or ionic liquid.
The polymerization of alpha-olefin of the present invention, wherein the linearly or nonlinearly alpha-olefin be preferably selected from 1- oneself
At least one of alkene, 1- octene and 1- decene.
The polymerization of alpha-olefin of the present invention, wherein the reaction condition of the polymerization is preferred are as follows: temperature 20-180
DEG C, pressure 0.1-5MPa, time 1-10h.
Alpha-olefin polymerization catalyst of the invention is specifically to be prepared by the following method:
To three mouthfuls of reaction flasks that blender and thermometer are housed, 3 high pure nitrogen displacements are carried out, are added into reaction vessel
Enter MgCl2With hexamethylene；At 25-100 DEG C, n-butanol is added dropwise in slow speed, is allowed to generate alcohol adduct with carrier；
Temperature is reduced after reaction, at 10-100 DEG C, active component is diluted 2-4 times with hexamethylene and obtains four chlorinations
Titanium dilution adds carrier alcohol adduct, stirs 0.5-3h；
Supported titanium activated centre after reaction, under inert gas protection, filters out reaction solution, to the solid of above-mentioned generation
Material carries out multiple hot wash with hexamethylene and washs, and is transferred out of washing supernatant liquor, obtains carried catalyst slurries；After vacuum dried
Obtain MgCl2Load TiCl4Catalyst.
The polymerization of alpha-olefin of the present invention uses slurry polymerization method, and the specific method is as follows:
Glass there-necked flask is replaced several times through high pure nitrogen, and a certain amount of hexamethylene is added into reactor under nitrogen protection
The MgCl of metering is added in solvent2Load TiCl4Catalyst, is stirred after a certain period of time at room temperature, and co-catalysis is added with slow speed
Agent.After co-catalyst is added dropwise, certain time is stirred, alpha-olefin then is added to reactor, is adjusted to reaction temperature, is reacted
Certain time.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains PAO production
Object.
Compared with the prior art, the invention has the following features: using load-type Titanium series catalyst for major catalyst, select
Two kinds of alkyl aluminums collectively as co-catalyst, using different co-catalysts to the reducing power in primary catalyst metal activated centre not
Deng this characteristic, by choosing co-catalyst type appropriate and proportion, realize to primary catalyst metal activated centre chemical valence
Regulation synthesize to control polymerization catalyst activity and the product degree of polymerization, and then in the way of adjusting catalyst formulation and form
The poly alpha olefin base oil of required viscosity.
Compared with the catalyst of common poly alpha olefine synthetic oil, with the catalyst linearly or nonlinearly alpha-olefines polymerization
It closes, base oil viscosity index, and the adjustment by forming to catalyst formulation can be significantly improved, it is viscous that different target can be synthesized
The poly alpha olefin base oil of degree.
The preparation method of alpha-olefin polymerization catalyst provided by the invention, the preparation method is simple, at low cost, and by this
Catalyst made from method has the characteristics that high catalytic activity, catalyst and product are easily separated, free from environmental pollution.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of alpha-olefin polymerization catalyst of the present invention.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
The related data of polymer are obtained by following test method in embodiment:
(1) it viscosity: is measured according to GB/T 265-1988 oil product kinematic viscosity measuring method and dynamic viscosity calculating method.
(2) it viscosity index (VI): is surveyed according to GB/T 265-1988 oil product kinematic viscosity measuring method and dynamic viscosity calculating method
It is fixed.
Preparation example 1
The preparation of major catalyst 1
Three mouthfuls of reaction flasks equipped with blender and thermometer carry out 3 high pure nitrogen displacements, are added into reaction vessel
15.5gMgCl2With the hexamethylene of 50ml；At 60 DEG C, the n-butanol of 10ml is added dropwise in the speed of 3~4 seconds/drop, is allowed to and carries
Body generates alcohol adduct；
Temperature is reduced after reaction to 25 DEG C, takes the titanium tetrachloride of 2.55ml, twice of volume ratio of hexamethylene system is added
At titanium tetrachloride solution, it is added in carrier alcohol adduct with the speed of 3~4 seconds/drop, is persistently stirred after being added dropwise under stiring
1h；
Supported titanium activated centre after reaction, under inert gas protection, filters out reaction solution, to the material of above-mentioned generation
Multiple hot wash is carried out with hexamethylene to wash, is transferred out of washing supernatant liquor, obtains high-effective carrier catalyst slurries；After vacuum dried
Obtain MgCl2Load TiCl4Catalyst.
Preparation example 2
The preparation of major catalyst 2
Three mouthfuls of reaction flasks equipped with blender and thermometer carry out 3 high pure nitrogen displacements, are added into reaction vessel
15.5gMgCl2With the hexamethylene of 50ml；At 60 DEG C, the n-butanol of 10ml is added dropwise in the speed of 3~4 seconds/drop, is allowed to and carries
Body generates alcohol adduct；
Temperature is reduced after reaction to 25 DEG C, takes the titanium tetrachloride of 3.83ml, twice of volume ratio of hexamethylene system is added
At titanium tetrachloride solution, it is added in carrier alcohol adduct with the speed of 3~4 seconds/drop, is persistently stirred after being added dropwise under stiring
1h；
Supported titanium activated centre after reaction, under inert gas protection, filters out reaction solution, to the material of above-mentioned generation
Multiple hot wash is carried out with hexamethylene to wash, is transferred out of washing supernatant liquor, obtains high-effective carrier catalyst slurries；After vacuum dried
Obtain MgCl2Load TiCl4Catalyst.
Preparation example 3
The preparation of major catalyst 3
Three mouthfuls of reaction flasks equipped with blender and thermometer carry out 3 high pure nitrogen displacements, are added into reaction vessel
15.5gMgCl2With the hexamethylene of 50ml；At 60 DEG C, the n-butanol of 10ml is added dropwise in the speed of 3~4 seconds/drop, is allowed to and carries
Body generates alcohol adduct；
Temperature is reduced after reaction to 25 DEG C, takes the titanium tetrachloride of 5.1ml, and twice of volume ratio of hexamethylene is added and is made
Titanium tetrachloride solution is added in carrier alcohol adduct with the speed of 3~4 seconds/drop under stiring, is persistently stirred after being added dropwise
1h；
Supported titanium activated centre after reaction, under inert gas protection, filters out reaction solution, to the material of above-mentioned generation
Multiple hot wash is carried out with hexamethylene to wash, is transferred out of washing supernatant liquor, obtains high-effective carrier catalyst slurries；After vacuum dried
Obtain MgCl2Load TiCl4Catalyst.
Comparative example 1
Olefin polymerization is carried out using major catalyst 1
This test uses slurry polymerization method.Glass there-necked flask through high pure nitrogen replace 3 times, under nitrogen protection to
The cyclohexane solvent of 20ml is added in reactor, MgCl prepared by 3.11g embodiment 1 is added2Load TiCl4Catalyst, at room temperature
After stirring 5min, major catalyst is restored with the aluminium diethyl monochloride (DEAC) that 1.14ml is added in the speed of 3~4 seconds/drop.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 46.22g.Product analysis the results are shown in Table 1.
Embodiment 1
Olefin polymerization is carried out using major catalyst 1
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 1 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride (DEAC) of 1.14ml is added in degree and 0.25ml triethyl aluminum (TEA) restores supported catalyst.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 25.1g.Product analysis the results are shown in Table 1.
Embodiment 2
Olefin polymerization is carried out using major catalyst 1
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 1 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride of 1.14ml is added in degree and 0.37ml triethyl aluminum restores supported catalyst.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 35.1g.Product analysis the results are shown in Table 1.
Embodiment 3
Olefin polymerization is carried out using major catalyst 1
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 1 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride of 1.14ml is added in degree and 0.50ml triethyl aluminum restores supported catalyst.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 34.3g.Product analysis the results are shown in Table 1.
Embodiment 4
Olefin polymerization is carried out using major catalyst 1
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 1 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride and 0.62ml triethyl aluminum of 1.14ml is added in degree.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 35.7g.Product analysis the results are shown in Table 1.
Comparative example 2
Olefin polymerization is carried out using major catalyst 1
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 1 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
0.50ml triethyl aluminum is added in degree.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 15.6g.Product analysis the results are shown in Table 1.
Embodiment 5
Olefin polymerization is carried out using major catalyst 2
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 2 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride and 0.50ml triethyl aluminum of 1.14ml is added in degree.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 39.6g.Product analysis the results are shown in Table 2.
Embodiment 6
Olefin polymerization is carried out using major catalyst 3
Glass there-necked flask is replaced 3 times through high pure nitrogen, and the hexamethylene that 20ml is added into reactor under nitrogen protection is molten
MgCl prepared by 3.11g embodiment 3 is added in agent2Load TiCl4Catalyst, after stirring 5min at room temperature, with the speed of 3~4 seconds/drop
The aluminium diethyl monochloride and 0.50ml triethyl aluminum of 1.14ml is added in degree.
After co-catalyst is added dropwise, 30min is stirred, α-decene 120ml then is added to reactor, adjusts reaction temperature
To 80 DEG C, 4h is reacted.Dimer of the product through filtering, alkali cleaning, washing, vacuum distillation separation unreacted monomer and generation, obtains
PAO product 53.8g.Product analysis the results are shown in Table 2.
1 decene oligomerization PAO test result of table
As shown in Table 1, it is co-catalyst that aluminium diethyl monochloride, which is used only, in comparative example 1, and polymerization activity is high (such as yield is higher),
Product viscosity will reduce；It is co-catalyst that triethyl aluminum, which is used only, in comparative example 2, and product viscosity index can guarantee, but is polymerize
Activity will decline.Embodiment 1-4 uses a certain proportion of aluminium diethyl monochloride and triethyl aluminum for co-catalyst, while obtaining
The performance and polymerization activity of preferable PAO product.Especially embodiment 2, when the proportion of aluminium diethyl monochloride and triethyl aluminum is
When 1:0.3, under the premise of PAO product property reaches standard, maximum polymerization activity is reached.
The different preparation condition catalysts of table 2 synthesize PAO test result
As shown in Table 2, with the increase of the activated centre Ti load capacity on major catalyst, PAO yield is significantly improved, and PAO is produced
Object viscosity slightly shows downward trend.Therefore it when the activated centre Ti load capacity is 9.75wt% on major catalyst, can obtain simultaneously
To the performance and polymerization activity of optimal PAO product.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (15)
1. a kind of preparation method of alpha-olefin polymerization catalyst, which comprises the following steps:
S1 Vehicle element: carrier is refined in hexamethylene using Organic Alcohol, carrier alcohol adduct is obtained；
The load of S2 active component: active component titanium compound hexamethylene is diluted 2-4 times, then is added dropwise in carrier alcohol adduct
It is stirred, obtains major catalyst；
The purification of S3 major catalyst: washing catalyst semi-finished product with hexamethylene, obtain the slurries containing catalyst semi-finished product,
Major catalyst after being purified after vacuum dried；
The reduction of S4 major catalyst: using co-catalyst as reducing agent, finished catalyst is obtained after reduction；
The co-catalyst is selected from trimethyl aluminium, triethyl aluminum, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethylmercury chloride
Two kinds in aluminium, methylaluminoxane and ethylaluminoxane, the molar ratio of both components is 1:0.1~10.
2. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that in the co-catalyst
The molar ratio of two kinds of components is 1:0.1~2.
3. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the co-catalyst is
Aluminium diethyl monochloride and triethyl aluminum, the molar ratio of the two are 1:0.1~1.
4. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that described in step S2
The dosage of active component is 0.1%~10% with the weight of the carrier alcohol adduct.
5. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that described in step S4
Molar ratio of the major catalyst in terms of active component with the co-catalysis component is 1:0.1~10.
6. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that described in step S4
Molar ratio of the major catalyst in terms of active component with the co-catalysis component is 1:1~20.
7. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the Vehicle element
The step of are as follows: carrier is at 200 DEG C, and in nitrogen protection, heating is for 24 hours；It is 1:20's that carrier and hexamethylene, which are configured to molar ratio,
Suspension is added dropwise to the n-butanol for being 1:1-10 with carrier molar ratio in slow speed at 20-100 DEG C, is allowed to raw with carrier
At alcohol adduct.
8. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the active component is negative
The step of load are as follows: at 10-100 DEG C, active component hexamethylene is diluted 2-4 times, carrier alcohol adduct is added, stirs 1-
4h。
9. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the catalyst purification
The step of are as follows: multiple hot wash is carried out with hexamethylene and is washed, washing supernatant liquor is transferred out of, and obtains supported catalyst slurries；Through vacuum
Supported catalyst after being purified after drying.
10. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the titanium compound
Selected from least one of titanium tetrachloride, titanium trichloride and isopropyl titanate.
11. the preparation method of alpha-olefin polymerization catalyst according to claim 1, which is characterized in that the carrier is selected from
At least one of silica gel, aluminum oxide, magnesium chloride and MCM-41.
12. a kind of alpha-olefin polymerization catalyst is the spy as made from claim 1-11 described in any item preparation methods
Sign is, including major catalyst and co-catalyst, and the major catalyst is made of carrier and active component, and the activated centre is
Titanium compound, the carrier can be selected from one of silica gel, aluminum oxide, magnesium chloride and MCM-41, the co-catalysts
Selected from trimethyl aluminium, triethyl aluminum, aluminium diethyl monochloride, one aluminium ethide of dichloro, sesquialter ethylmercury chloride aluminium, methylaluminoxane and second
Two kinds in two kinds in base aikyiaiurnirsoxan beta, the molar ratio of two kinds of components is 1:0.1~10 in the co-catalyst.
13. a kind of polymerization of alpha-olefin, which is characterized in that with catalyst made from preparation method described in claim 1
For catalyst, catalyzed linear or non-linear alpha-olefin prepare lube base oil to polymerize, pole used in polymerization process
Property or nonpolar solvent be alkane, aromatic hydrocarbons or ionic liquid.
14. the polymerization of alpha-olefin according to claim 13, which is characterized in that the linearly or nonlinearly alpha-olefin
Selected from least one of 1- hexene, 1- octene and 1- decene.
15. the polymerization of alpha-olefin according to claim 13, which is characterized in that the reaction condition of the polymerization are as follows:
20-180 DEG C of temperature, pressure 0.1-5MPa, time 1-10h.
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| CN113136254A (en) * | 2021-04-16 | 2021-07-20 | 华东理工大学 | 1-decene oligomer base oil with narrow composition distribution as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3795616A (en) * | 1971-06-14 | 1974-03-05 | Gulf Research Development Co | Shear stable,multiviscosity grade lubricating oils |
| US4510342A (en) * | 1982-12-29 | 1985-04-09 | The Standard Oil Company | High viscosity index synthetic oils and synthesis thereof |
| JPS63308007A (en) * | 1987-06-09 | 1988-12-15 | Japan Synthetic Rubber Co Ltd | Production of liquid alpha-olefin polymer |
| CN101516921A (en) * | 2006-09-25 | 2009-08-26 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium methoxide based catalyst precursors and catalyst components obtained therefrom |
-
2018
- 2018-01-15 CN CN201810036232.0A patent/CN110041457B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3795616A (en) * | 1971-06-14 | 1974-03-05 | Gulf Research Development Co | Shear stable,multiviscosity grade lubricating oils |
| US4510342A (en) * | 1982-12-29 | 1985-04-09 | The Standard Oil Company | High viscosity index synthetic oils and synthesis thereof |
| JPS63308007A (en) * | 1987-06-09 | 1988-12-15 | Japan Synthetic Rubber Co Ltd | Production of liquid alpha-olefin polymer |
| CN101516921A (en) * | 2006-09-25 | 2009-08-26 | 巴塞尔聚烯烃意大利有限责任公司 | Magnesium methoxide based catalyst precursors and catalyst components obtained therefrom |
Non-Patent Citations (3)
| Title |
|---|
| G. COLLINA ET AL.: ""Effect of the cocatalyst on the copolymerization of propylene and small amount of ethylene with high activity Ziegler-Natta catalyst"", 《POLYMER BULLETIN》 * |
| NICHAPAT SENSO ET AL.: ""The Influence of Mixed Activators on Ethylene Polymerization and Ethylene/1-Hexene Copolymerization with Silica-Supported Ziegler-Natta Catalyst"", 《MOLECULES》 * |
| 张丹枫: "《烯烃聚合》", 30 September 2014, 华东理工大学出版社 * |
Cited By (2)
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|---|---|---|---|---|
| CN113136254A (en) * | 2021-04-16 | 2021-07-20 | 华东理工大学 | 1-decene oligomer base oil with narrow composition distribution as well as preparation method and application thereof |
| CN113136254B (en) * | 2021-04-16 | 2022-05-27 | 华东理工大学 | 1-decene oligomer base oil with narrow composition distribution as well as preparation method and application thereof |
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