CN109369837A - A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing - Google Patents
A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing Download PDFInfo
- Publication number
- CN109369837A CN109369837A CN201811092333.6A CN201811092333A CN109369837A CN 109369837 A CN109369837 A CN 109369837A CN 201811092333 A CN201811092333 A CN 201811092333A CN 109369837 A CN109369837 A CN 109369837A
- Authority
- CN
- China
- Prior art keywords
- methyl
- aluminium
- dimethyl
- alpha
- complex compound
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/14—Monomers containing five or more carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a kind of metallocene catalyst compositions for alpha-olefine polymerizing and its applications.The metallocene catalysis object includes major catalyst, co-catalyst and chain-transferring agent；The major catalyst is the bridged combined metal compound of a kind of sulfur-bearing or oxa- ring structure, with cis-structure formula or transconfiguration formula.The present invention is major catalyst using the bridged combined metal compound of sulfur-bearing or oxa- ring structure using single or hybrid long chain alpha-olefin as polymer raw, while in the case where cooperating co-catalyst and chain-transferring agent, having synthesized the excellent mPAO of viscosity temperature characteristic.There is relatively high viscosity index using the mPAO that method provided by the invention obtains, and by changing temperature, or the use of different chain-transferring agents, can significantly adjust the kinematic viscosity of mPAO.
Description
Technical field
The present invention relates to a kind of metallocene catalyst compositions for alpha-olefine polymerizing and its applications, and in particular to a kind of
Using single or mixed long-chain alpha-olefin as the polymerization of Material synthesis metallocene poly alpha olefin, belong to alpha-olefine polymerizing preparation
The technical field of poly alpha olefine synthetic oil.
Background technique
Poly alpha olefin (PAO) is one kind of synthetic base oil, is a kind of Synthin profit by chemical synthesis process preparation
Lubricating oil, composition are the long chain alkanes of comparison rule, are a kind of synthetic lubricant base oils haveing excellent performance, and are current synthesis hairs
Most widely used one of oil base stock in motivation oil, gear oil and other iundustrial oils, rouge.Oil pole is synthesized by its modulation
The earth extends application range of the lubricant grease under low temperature, high temperature, high load capacity and other harsh conditions, provides excellent glue
Warm nature energy, thermal oxidation stability, lubrication and wear resistance and detergency, thus the oil draining period is greatly extended, it slows down and sets
Standby corrosion and abrasion, reduces the maintenance cycle of equipment, improves the utilization rate and service life of equipment.
Poly alpha olefin is usually produced by the technology of olefin catalytic polymerization, and the raw material used is C8-C12Alpha-olefin in
Monomer or mixed olefins, polymerization catalyst be lewis acid catalyst or Ziegler-Natta catalyst.It is poly- by improving
Technique and polymerization catalyst are closed to improve the service performance of base oil.By the development of many years, the production technology of poly alpha olefin has
It is very big to improve.
To be different from conventional PAO, the poly- α-alkene of metallocene is referred to as using poly alpha olefin synthesized by metallocene catalyst
Hydrocarbon, i.e. mPAO (metallence PAO).PAO molecule possesses backbone outstanding under normal conditions, stretches from backbone with disordered fashion
Side chain different in size out.And mPAO uses metallocene catalyst synthesis technology, metallocene is single site catalysts, solely
The available very uniform chemical products of special geometry, so mPAO possesses pectinate texture, there is no upright side chains.With it is normal
Rule PAO possesses improved rheological behavior and flow characteristics compared to this shape, so as to preferably provide shear stability, lower
Pour point and higher Viscosity Index, especially because have less side chain and have the shear stable more much higher than conventional PAO
Property.What these characteristics determined mPAO is the application of high severity, including power drive system and gear oil, compression using target
Machine lubricating oil, transmission fluid and industrial lubricant.
Metallocene catalysis synthesis technology has following feature: firstly, metallocene catalysis alpha-olefine polymerizing is with very high
Catalytic activity, up to arrive every gram of catalyst of dozens or even hundreds of kilogram of PAO, thus in the synthesis process consumed by catalysis
The amount of agent and co-catalyst is very small；Secondly as metallocene catalyst is single site catalysts, single active center's polyene
Hydrocarbon catalyst can control the microstructure of synthesized molecular polyolefin well, that is to say, that catalytic polymerization degree can be with technique
It changes and is effectively adjusted, there is very big elasticity, so as to accurately control chemical structure, the molecular weight of molecular polyolefin
And molecular weight distribution, it can directly produce the PAO product of required viscosity grade according to actual needs using this feature, simplify
The technological process of production；Furthermore since the catalyst system has very high catalytic activity, so there was only 2 hours or so reaction time,
The production cycle is substantially reduced, production efficiency is improved；Finally, due to the amount very little of catalyst and co-catalyst used, after
Treatment process is simple, can effectively reduce the discharge of the three wastes.
The Chinese patent of publication number CN1549852 discloses one kind and is prepared for one kind in the presence of single site catalysts
Or the method for a variety of olefin oligomers.Preferred alkenes are alpha-olefins, and the oligomer is poly alpha olefin (PAO).Made of in this way
PAO does not contain the tertiary hydrogen generated due to isomerization completely or substantially.Therefore, which has improved biological degradability, changes
Kind inoxidizability and/or relatively higher viscosity index (VI).The PAO, which has, such as to be answered as many useful of lubricant composition
With.
Publication number CN101617033 Chinese patent invention lubricant oil composite contain 100 DEG C kinematic viscosity be 1~
5mm2The lubricant base of/s and 100 DEG C of kinematic viscosity are 20~2000mm2/ s's is selected from olefin copolymer (OCP) and poly- α-
At least one of alkene (PAO), 100 DEG C of kinematic viscosity are 8.0mm2/ s or less and viscosity index (VI) are 155 or more.
United States Patent (USP) US6548723 discloses a kind of using metallocene or organic metal amine salt catalysis 1- decene and ethylene
The method that oligomerisation prepares lube base oil PAO, catalyst are mainly the cyclopentadienyl metallocene of non-bridging, are in Al/Zr
Gained PAO is low viscosity base oil when 1000.
United States Patent (USP) US6706828 is mainly being faced using the means of special bridged metallocene catalysts that double indenyls of meso silicon bridging replace
Using 1- decene as Material synthesis PAO under hydrogen state, the catalyst catalytic performance of different meso with rac structures is different, passes through change
The configuration ratio and Hydrogen Vapor Pressure of catalyst all have the viscosity temperature characteristic of catalyst system and obtained PAO product biggish
It influences.
The Chinese patent of publication number CN105062555 disclose it is a kind of with fischer-tropsch synthesis process production coal alpha-olefin be
Polymer raw has synthesized viscosity temperature characteristic excellent mPAO under the action of metallocene catalyst；Instead of expensive pure
On the one hand alpha-olefine polymerizing raw material reduces the production cost of PAO, on the other hand, improve the economy of fischer-tropsch synthesis process.
Above-mentioned patent refers to that ethylene oligomerization method obtains 1- decene or 1- octene is raw material to polymerize to obtain mPAO mostly, also has
Patent, which is referred to using coal alpha-olefin as raw material, synthesizes mPAO.Catalyst system disclosed by the invention can not only polymerize single length
Chain alpha-olefin, while class long-chain alpha-olefin, such as the coal alpha-olefin of fischer-tropsch synthesis process production can also be mixed with catalytic polymerization.
Moreover, can polymerize to obtain the excellent mPAO of viscosity temperature characteristic using ternary metallocene catalyst compositions disclosed by the invention, have
There is the features such as high viscosity index (HVI), kinematic viscosity is adjustable.
Summary of the invention
Problem to be solved by this invention is: provide a kind of metallocene catalyst compositions for alpha-olefine polymerizing and its
Polymerization.
To solve the above-mentioned problems, the present invention provides a kind of metallocene catalyst compositions for alpha-olefine polymerizing,
It is characterised in that it includes major catalyst, co-catalyst and chain-transferring agent；The major catalyst is a kind of sulfur-bearing or oxa- ring structure
Bridged combined metal compound, with cis-structure formula, as shown in formula I:
Or transconfiguration formula, as shown in formula II:
Wherein, M Ti, Zr or Hf；A is S or O；R1、R2Be the alkyl or aryl of 1-6 carbon number, and the two it is identical or
It is different；X1、X2It is each independently and forms σ-key ligand with M.
Preferably, the X1、X2For halogen atom or the alkyl with 1-6 carbon number.
It is highly preferred that the halogen atom is chlorine atom, bromine atom, iodine atom or fluorine atom；Described alkyl is methyl, second
Base, propyl, normal-butyl or isobutyl group.
Further, the bridged combined metal compound of the sulfur-bearing or oxa- ring structure is wherein one in following complex compound
Kind:
Complex compound 1: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) zirconium dichloride；
Complex compound 2: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) zirconium dimethyl；
Complex compound 3: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) hafnium dichloride；
Complex compound 4: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) dimethyl hafnium；
Complex compound 5: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) titanium chloride；
Complex compound 6: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) dimethyl titanium；
Complex compound 7: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) zirconium dichloride；
Complex compound 8: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) zirconium dimethyl；
Complex compound 9: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) hafnium dichloride；
Complex compound 10: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) dimethyl hafnium；
Complex compound 11: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) titanium chloride；
Complex compound 12: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) dimethyl titanium.
Preferably, the co-catalyst is alkylaluminoxane reagent or organoboron reagent.
It is highly preferred that alkylaluminoxane reagent is methylaluminoxane, ethylaluminoxane, n-propyl aluminium in the co-catalyst
Any one or a few in oxygen alkane, normal-butyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
It is highly preferred that organoboron reagent is [Ph in the co-catalyst3C][B(C6F5)4]、[PhMe2NH][B(C6F5)4]、
B(C6F5)3In any one or a few.
Preferably, the chain-transferring agent includes aluminon and alkyl zinc reagent, and aluminon uses molecular formula for AlY3Alkane
Base aluminium, molecular formula HAlY2Alkyl-al hydride or molecular formula be AlY2The alkyl aluminum chloride of Cl, wherein Y is alkyl.
It is highly preferred that the alkyl aluminum that aluminon uses in the chain-transferring agent is trimethyl aluminium, triethyl aluminum, three n-propyl
Aluminium, triisobutyl aluminium, three hexyl aluminium, three n-butylaluminums, triisopropylaluminiuand, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three
In p-methylphenyl aluminium, tribenzyl aluminium, three n-butylaluminum, ethyl di-p-tolyl aluminium and diethylbenzyl aluminium any one or
It is several；Alkyl-al hydride be dimethyl hydrogenated aluminium, diethylaluminum hydride, diη-propyl aluminum hydride, diisobutyl aluminium hydride, two oneself
Base aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl hydrogenation
Aluminium, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl aluminum hydride and Ethylbenzyl
Any one or a few in aluminum hydride；Alkyl aluminum chloride is chlorodimethylalumiu, diethylaluminum chloride, chlorination diη-propyl
Aluminium, chlorination diisopropyl aluminium, chlorination di-n-butyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium, chlorination dihexyl aluminium, chlorine
Change dicyclohexyl aluminium, chlorination dioctyl aluminium, chlorinated diphenyl base aluminium, chlorination di-p-tolyl aluminium, chlorination dibenzyl aluminium, tonsilon
Any one or a few in benzyl aluminium and tonsilon p-methylphenyl aluminium.
It is highly preferred that alkyl zinc reagent is in zinc methide, diethyl zinc and diisopropyl zinc in the chain-transferring agent
Any one or a few.
Preferably, the molar ratio of metal is (10-5000) in the aluminium and major catalyst in the co-catalyst: 1 or helping and urges
The molar ratio of metal is (1-200) in boron and major catalyst in agent: 1；In aluminium and major catalyst in the chain-transferring agent
The molar ratio of metal is (1-500): 1 or zinc and major catalyst in chain-transferring agent in the molar ratio of metal be (1-500): 1.
The present invention has also passed through a kind of application of above-mentioned metallocene catalyst compositions for alpha-olefine polymerizing, specifically
Are as follows: in an inert atmosphere, by the major catalyst of single or hybrid long chain alpha-olefin and metallocene catalyst compositions, help
Catalyst, chain-transferring agent successively mix, and carry out polymerization reaction, and reaction temperature is 20~150 DEG C.
Preferably, described single or hybrid long chain alpha-olefin is 1- heptene, 1- octene, 1- nonene, 1- decene, 11 carbon of 1-
Any one or a few mixture in alkene, 1- dodecylene, 1- tridecylene, tetradecene and cetene.
Metallocene catalyst compositions according to the present invention can be used for producing alpha-olefine polymers, be particularly suitable for it is single or
Mixed long-chain alpha-olefin polymerization, and make kinematic viscosity controllable.
Specific embodiment
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Polymerization in embodiment 1-10 are as follows: in an inert atmosphere, by single or hybrid long chain alpha-olefin, main reminder
Agent, co-catalyst, chain-transferring agent successively mix, and carry out polymerization reaction；Reaction temperature is 80~120 DEG C, and the reaction time is general
It is 2 hours.Stop stirring, terminated and reacted with water, centrifuge separation is poured out supernatant liquor, supernatant liquor rotary evaporation is removed
The excellent mPAO of viscosity temperature characteristic can be obtained in unreacted monomer.
The test method of every viscosity temperature characteristic of the mPAO obtained after treatment are as follows:
Oil product kinematic viscosity measuring method and dynamic viscosity calculating method: GB/T 265.
Oil product viscosity index (VI) calculating method: GB/T 1995.
Homogeneous catalytic olefin combined polymerization:
Embodiment 1
Complex compound 1 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of triethyl aluminum (1.0mol/L in toluene) nitrogen protection of 1mL to anti-
It answers in bottle, stirs half an hour.Weigh 20mg complex compound 1, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopentadiene acene
Bithiophene) zirconium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The catalyst solution be added into reaction flask, polymerization starts, keep 90 DEG C reaction.After 2 hours plus water terminates the reaction, is centrifuged
Separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
Embodiment 2
Complex compound 1 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Polymeric reaction condition and operating process difference from example 1 is that: polymerization temperature is maintained at 100 DEG C.
Embodiment 3
Complex compound 1 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Polymeric reaction condition and operating process difference from example 1 is that: polymerization temperature is maintained at 110 DEG C.
Embodiment 4
Complex compound 1 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Polymeric reaction condition and operating process difference from example 1 is that: polymerization temperature is maintained at 120 DEG C.
100 DEG C of kinematic viscosity of poly alpha olefin made from embodiment 1-4, composition are measured, the results are shown in Table 1.
Table 1
Seen from table 1, with the raising of polymerization temperature, the content of the dimer in product increases, trimer content variation
It is unobvious, at the same tetramer and the above constituent content reduce so cause the viscosity of obtained mPAO as the temperature rises and
It reduces.
Embodiment 5
Complex compound 3 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of triethyl aluminum (1.0mol/L in toluene) nitrogen protection of 1mL to anti-
It answers in bottle, stirs half an hour.Weigh 20mg complex compound 3, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopentadiene acene
Bithiophene) hafnium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The catalyst solution be added into reaction flask, polymerization starts, keep 90 DEG C reaction.After 2 hours plus water terminates the reaction, is centrifuged
Separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
Embodiment 6
Complex compound 5 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of triethyl aluminum (1.0mol/L in toluene) nitrogen protection of 1mL to anti-
It answers in bottle, stirs half an hour.Weigh 20mg complex compound 5, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopentadiene acene
Bithiophene) titanium chloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The catalyst solution be added into reaction flask, polymerization starts, keep 90 DEG C reaction.After 2 hours plus water terminates the reaction, is centrifuged
Separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
Embodiment 7
Complex compound 7 and its carbon monoxide-olefin polymeric are catalyzed alpha-olefine polymerizing:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of triethyl aluminum (1.0mol/L in toluene) nitrogen protection of 1mL to anti-
It answers in bottle, stirs half an hour.Weigh 20mg complex compound 7, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopentadiene acene
And furans) zirconium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The catalyst solution be added into reaction flask, polymerization starts, keep 90 DEG C reaction.After 2 hours plus water terminates the reaction, is centrifuged
Separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
MPAO viscosity data synthesized by different major catalysts is shown in Table 2 in embodiment 1,5,6,7.
Table 2
As can be seen from Table 2, the mPAO viscosity index (VI) obtained of embodiment 1,5,6,7 is larger, 200 or more, this illustrates this
When the means of special bridged metallocene catalysts of class heterocycle containing S or O is as major catalyst, the excellent mPAO of viscosity temperature characteristic can get.
Embodiment 8
Alpha-olefine polymerizing is catalyzed using triisobutyl aluminium chain-transferring agent:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of triisobutyl aluminium (1.0mol/L in toluene) nitrogen protection of 1mL to
In reaction flask, half an hour is stirred.Weigh 20mg complex compound 1, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta
Benzothiophene) zirconium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The good catalyst solution is added into reaction flask, and polymerization starts, and keeps 90 DEG C of reactions.After 2 hours plus water terminates the reaction, from
Heart separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
Embodiment 9
Alpha-olefine polymerizing is catalyzed using diethylaluminum hydride chain-transferring agent:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of diethylaluminum hydride (1.0mol/L in toluene) nitrogen protection of 1mL
Into reaction flask, half an hour is stirred.Weigh 20mg complex compound 1, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopentadiene
And benzothiophene) zirconium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will match
The catalyst solution set is added into reaction flask, and polymerization starts, and keeps 90 DEG C of reactions.After 2 hours plus water terminates the reaction,
Centrifuge separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
MPAO.
Embodiment 10
Alpha-olefine polymerizing is catalyzed using diisopropyl zinc chain-transferring agent:
Under high pure nitrogen protective condition, 200mL alpha-olefin is measured in the reaction flask of the 500mL equipped with magnetic agitation
Mixture is warming up to 90 DEG C, will be added under the conditions of diisopropyl zinc (1.0mol/L in toluene) nitrogen protection of 1mL to
In reaction flask, half an hour is stirred.Weigh 20mg complex compound 1, dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta
Benzothiophene) zirconium dichloride, it is dissolved in the methylaluminoxane (MAO) (1.0mol/L in toluene) of 2mL, will configure
The good catalyst solution is added into reaction flask, and polymerization starts, and keeps 90 DEG C of reactions.After 2 hours plus water terminates the reaction, from
Heart separation, is poured out supernatant liquor, and supernatant liquor rotary evaporation is removed unreacted monomer, and viscosity-temperature characteristics can be obtained can be excellent
mPAO。
100 DEG C of kinematic viscosity of poly alpha olefin made from embodiment 1,8,9 and 10 are measured, the results are shown in Table 3.
Table 3
Seen from table 3, in the case where other conditions are identical, only change the type of chain-transferring agent, it can be apparent
Adjust the kinematic viscosity of mPAO.That is, the molecular weight of polymer can significantly be adjusted by introducing different chain-transferring agents, this
Have great importance to the mPAO of production different viscosities.
Claims (10)
1. a kind of metallocene catalyst compositions for alpha-olefine polymerizing, which is characterized in that including major catalyst, co-catalyst
And chain-transferring agent；The major catalyst is the bridged combined metal compound of a kind of sulfur-bearing or oxa- ring structure, with cis- knot
Structure formula, as shown in formula I:
Or transconfiguration formula, as shown in formula II:
Wherein, M Ti, Zr or Hf；A is S or O；R1、R2It is the alkyl or aryl of 1-6 carbon number, and the two is identical or different；
X1、X2It is each independently and forms σ-key ligand with M.
2. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as described in claim 1, which is characterized in that the X1、X2
For halogen atom or the alkyl with 1-6 carbon number.
3. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 2, which is characterized in that the halogen is former
Son is chlorine atom, bromine atom, iodine atom or fluorine atom；Described alkyl is methyl, ethyl, propyl, normal-butyl or isobutyl group.
4. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 3, which is characterized in that the sulfur-bearing
Or the bridged combined metal compound of oxa- ring structure is the one of which in following complex compound:
Complex compound 1: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) zirconium dichloride；
Complex compound 2: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) zirconium dimethyl；
Complex compound 3: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) hafnium dichloride；
Complex compound 4: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) dimethyl hafnium；
Complex compound 5: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) titanium chloride；
Complex compound 6: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzothiophene) dimethyl titanium；
Complex compound 7: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) zirconium dichloride；
Complex compound 8: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) zirconium dimethyl；
Complex compound 9: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) hafnium dichloride；
Complex compound 10: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) dimethyl hafnium；
Complex compound 11: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) titanium chloride；
Complex compound 12: dimethyl-silicon (2- methyl-benzindene) (2- methyl-cyclopenta benzofuran) dimethyl titanium.
5. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as described in claim 1, which is characterized in that described help is urged
Agent is alkylaluminoxane reagent or organoboron reagent；The chain-transferring agent includes aluminon and alkyl zinc reagent, and aluminon is adopted
It is AlY with molecular formula3Alkyl aluminum, molecular formula HAlY2Alkyl-al hydride or molecular formula be AlY2The alkyl aluminum chloride of Cl,
Wherein, Y is alkyl.
6. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 5, which is characterized in that described help is urged
Alkylaluminoxane reagent is methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta, normal-butyl aikyiaiurnirsoxan beta and isobutyl group in agent
Any one or a few in aikyiaiurnirsoxan beta；Organoboron reagent is [Ph in the co-catalyst3C][B(C6F5)4]、[PhMe2NH][B
(C6F5)4]、B(C6F5)3In any one or a few；The alkyl aluminum that aluminon uses in the chain-transferring agent for trimethyl aluminium,
It is triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, three hexyl aluminium, three n-butylaluminums, triisopropylaluminiuand, thricyclohexyl aluminium, three pungent
Base aluminium, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, three n-butylaluminum, ethyl di-p-tolyl aluminium and diethylbenzyl
Any one or a few in aluminium；Alkyl-al hydride is dimethyl hydrogenated aluminium, diethylaluminum hydride, diη-propyl aluminum hydride, two
Isobutylaluminiumhydride, dihexyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl
Aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride, ethyl p-methylphenyl
Any one or a few in aluminum hydride and Ethylbenzyl aluminum hydride；Alkyl aluminum chloride is chlorodimethylalumiu, diethyl base
Aluminium, chlorination diη-propyl aluminium, chlorination diisopropyl aluminium, chlorination di-n-butyl aluminium, di-isobutyl aluminum chloride, chlorination diamyl aluminium,
Chlorination dihexyl aluminium, chlorination dicyclohexyl aluminium, chlorination dioctyl aluminium, chlorinated diphenyl base aluminium, chlorination di-p-tolyl aluminium, chlorination two
Any one or a few in benzyl aluminium, tonsilon benzyl aluminium and tonsilon p-methylphenyl aluminium；Alkane in the chain-transferring agent
Base zincon is any one or a few in zinc methide, diethyl zinc and diisopropyl zinc.
7. being used for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 5, which is characterized in that described help is urged
In aluminium and major catalyst in agent the molar ratio of metal be (10-5000): 1 or boron and major catalyst in co-catalyst in gold
The molar ratio of category is (1-200): 1；In aluminium and major catalyst in the chain-transferring agent molar ratio of metal be (1-500): 1 or
The molar ratio of metal is (1-500) in zinc and major catalyst in chain-transferring agent: 1.
8. the application described in a kind of claim 1-7 any one for the metallocene catalyst compositions of alpha-olefine polymerizing.
9. the application for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 8, which is characterized in that tool
Body are as follows: in an inert atmosphere, by the major catalyst of single or hybrid long chain alpha-olefin and metallocene catalyst compositions,
Co-catalyst, chain-transferring agent successively mix, and carry out polymerization reaction, and reaction temperature is 20~150 DEG C.
10. the application for the metallocene catalyst compositions of alpha-olefine polymerizing as claimed in claim 9, which is characterized in that
Described single or hybrid long chain alpha-olefin be 1- heptene, 1- octene, 1- nonene, 1- decene, 1- endecatylene, 1- dodecylene,
Any one or a few mixture in 1- tridecylene, tetradecene and cetene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811092333.6A CN109369837A (en) | 2018-09-19 | 2018-09-19 | A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811092333.6A CN109369837A (en) | 2018-09-19 | 2018-09-19 | A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109369837A true CN109369837A (en) | 2019-02-22 |
Family
ID=65405553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811092333.6A Pending CN109369837A (en) | 2018-09-19 | 2018-09-19 | A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109369837A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020251247A1 (en) * | 2019-06-13 | 2020-12-17 | 주식회사 엘지화학 | Novel transition metal compound and method for preparing polypropylene using same |
| WO2020251265A1 (en) * | 2019-06-13 | 2020-12-17 | 주식회사 엘지화학 | Hybrid supported metallocene catalyst, and method for preparing polypropylene using same |
| CN112745403A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of poly-alpha-olefin |
| CN112745415A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing poly-alpha-olefin with high viscosity index |
| CN113614119A (en) * | 2019-06-13 | 2021-11-05 | 株式会社Lg化学 | Hybrid supported metallocene catalyst and method for preparing polypropylene using the same |
| CN114534781A (en) * | 2022-02-11 | 2022-05-27 | 天津科技大学 | Soluble organic boron salt cocatalyst and preparation method thereof |
| CN115400797A (en) * | 2022-08-19 | 2022-11-29 | 中国科学院山西煤炭化学研究所 | Heteroatom-containing metallocene catalyst system and method for catalyzing alpha-olefin oligomerization |
| CN116410780A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558401A (en) * | 2012-02-15 | 2012-07-11 | 中国科学院长春应用化学研究所 | Method of preparing telechelic polymer |
| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
| CN105985372A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Bridged metallocene compound with sulfur or oxygen heterocyclic structure, and preparation method and application thereof |
-
2018
- 2018-09-19 CN CN201811092333.6A patent/CN109369837A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558401A (en) * | 2012-02-15 | 2012-07-11 | 中国科学院长春应用化学研究所 | Method of preparing telechelic polymer |
| CN105985372A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Bridged metallocene compound with sulfur or oxygen heterocyclic structure, and preparation method and application thereof |
| CN104877054A (en) * | 2015-05-22 | 2015-09-02 | 浙江大学 | HBPE (hyperbranched polyethylene) functionalized with terminal hydroxyl groups and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020251247A1 (en) * | 2019-06-13 | 2020-12-17 | 주식회사 엘지화학 | Novel transition metal compound and method for preparing polypropylene using same |
| WO2020251265A1 (en) * | 2019-06-13 | 2020-12-17 | 주식회사 엘지화학 | Hybrid supported metallocene catalyst, and method for preparing polypropylene using same |
| CN113614119A (en) * | 2019-06-13 | 2021-11-05 | 株式会社Lg化学 | Hybrid supported metallocene catalyst and method for preparing polypropylene using the same |
| CN112745403A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of poly-alpha-olefin |
| CN112745415A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Method for preparing poly-alpha-olefin with high viscosity index |
| CN112745403B (en) * | 2019-10-30 | 2023-02-17 | 中国石油化工股份有限公司 | Preparation method of poly-alpha-olefin |
| CN116410780A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Synthesis method of high-viscosity metallocene poly alpha-olefin base oil, product and application thereof |
| CN114534781A (en) * | 2022-02-11 | 2022-05-27 | 天津科技大学 | Soluble organic boron salt cocatalyst and preparation method thereof |
| CN115400797A (en) * | 2022-08-19 | 2022-11-29 | 中国科学院山西煤炭化学研究所 | Heteroatom-containing metallocene catalyst system and method for catalyzing alpha-olefin oligomerization |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369837A (en) | A kind of metallocene catalyst compositions and its application for alpha-olefine polymerizing | |
| US5420372A (en) | Alpha-olefin oligomers useful as base stocks and viscosity index improvers, and lubricating oils containing same and method of making the oligomers | |
| CN100390256C (en) | Synthetic lubricating oil and lubricating oil composition | |
| CN105885929B (en) | A kind of preparation method of low viscosity metallocene PAO base oils | |
| CA2642144C (en) | High viscosity polyalphaolefins based on a mixture comprising 1-hexene, i-dodecene and 1-tetradecene | |
| US8067652B2 (en) | Processes for controlling the viscosity of polyalphaolefins | |
| EP2380918B1 (en) | Process for producing alpha-olefin polymer, alpha-olefin polymer, and lubricating oil composition | |
| CA2779627C (en) | Manufacture of oligomers from nonene | |
| US5315053A (en) | Normally liquid alpha-olefin oligomers useful as base stocks and viscosity index improvers, and lubricating oils containing same | |
| CN105062555B (en) | A kind of coal alpha-olefin is the method for Material synthesis metallocene poly alpha olefin | |
| CN104926963A (en) | Method for synthesizing poly alpha-olefin base oil through 1-butene oligomerization | |
| CN109369835A (en) | For the cyclopentadienyl rare-earth metal carbon monoxide-olefin polymeric of alpha-olefine polymerizing and its application | |
| CN109369836A (en) | A kind of cyclopentadienyl rare-earth metal carbon monoxide-olefin polymeric and its application containing heterocycle structure | |
| CN113249141B (en) | Preparation method of poly alpha-olefin base oil | |
| CN104744522B (en) | A kind of benzhydryl bridging cyclopentadienyl-fluorene zirconium compound and its preparation method and application | |
| CN112029020A (en) | Long-chain alpha-olefin polymerization catalyst composition and polymerization method | |
| CN110041457B (en) | Alpha-olefin polymerization catalyst, preparation method thereof and alpha-olefin polymerization method | |
| CN113583158A (en) | Metallocene catalyst and application thereof | |
| CN109749812A (en) | A method of preparing poly alpha olefin synthetic lubricant base oil | |
| CN113150826B (en) | Low-viscosity and high-viscosity index poly alpha-olefin base oil and preparation method thereof | |
| RU2666736C1 (en) | Method for producing synthetic high viscosity polyalphaolefin base oils | |
| CN113185998B (en) | Narrow-distribution PAO base oil taking C8-C10 alpha-olefin tetramer as main component and preparation method thereof | |
| CN118055913A (en) | Process for preparing polyalphaolefins | |
| CN116554924A (en) | Preparation method of medium-high viscosity lubricating oil base oil | |
| CN113046130A (en) | PAO base oil with narrow distribution, low viscosity and high viscosity index and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |