CN106220767B - The preparation method of functional ultra-high molecular weight polyethylene - Google Patents
The preparation method of functional ultra-high molecular weight polyethylene Download PDFInfo
- Publication number
- CN106220767B CN106220767B CN201610693533.1A CN201610693533A CN106220767B CN 106220767 B CN106220767 B CN 106220767B CN 201610693533 A CN201610693533 A CN 201610693533A CN 106220767 B CN106220767 B CN 106220767B
- Authority
- CN
- China
- Prior art keywords
- molecular weight
- high molecular
- weight polyethylene
- ultra
- formula
- 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.)
- Active
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
- C08F210/02—Ethene
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/03—Cp or analog not bridged to a non-Cp X ancillary neutral donor
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 present invention provides a kind of preparation methods of functional ultra-high molecular weight polyethylene; in the preparation process of ultra-high molecular weight polyethylene; polymerized monomer ethylene carries out copolyreaction with the polar comonomers through trialkylaluminium protection in the catalyst system and catalyzing that catalyst and co-catalyst form; obtain functional ultra-high molecular weight polyethylene; catalyst is fluorenyl amine titanium complex, and co-catalyst is methylaluminoxane, modified methylaluminoxane or triphen carbon four (pentafluorophenyl group) borate.The present invention obtains the controllable functional ultra-high molecular weight polyethylene of polar functional mass contg by the copolymerization of ethylene and polar comonomers.Catalyst system of the present invention has very strong copolymerized ability to the polar comonomers that trialkylaluminium is protected, and good chain growth speed is kept, and overcome chain transfer reaction, to effectively obtain functional ultra-high molecular weight polyethylene.
Description
Technical field
The present invention relates to a kind of preparation methods of functional ultra-high molecular weight polyethylene, are specifically to provide a kind of melting temperature
Higher, the controllable functional ultra-high molecular weight polyethylene of polar group content preparation method.
Background technology
Ultra-high molecular weight polyethylene is the unbranched linear poly- second by 1,500,000 or more molecular weight prepared by vinyl polymerization
Alkene.Since ultra-high molecular weight polyethylene not only has excellent mechanical property, also there is excellent chemical mediator-resitant property, wear-resisting
Property and itself lubricating property, impact resistance and ballistic performance, electrical property, it is indispensable in national security and economic construction
Grand strategy goods and materials.There is great advantage in terms of light structures composite material and other products, in modernized war, boat
The numerous areas such as sky, navigation, defence equipment, electronics, weapons, shipbuilding, building materials, sport, medical treatment play very important effect.
Ultra-high molecular weight polyethylene causes hydrophilic also due to the nonpolarity of molecular polyolefin chain itself keeps its surface energy low
Property, printing and dyeing property, poor adhesion and the poor compatibility with polarity macromolecule or other inorganic non-metallic materials.It is existing about changing
The patent of kind ultra-high molecular weight polyethylene performance includes mainly the method being blended with radiation modification, but is usually present modified effect in this way
The shortcomings of fruit difference or the partial loss of the original excellent properties of ultra-high molecular weight polyethylene.
Modification by copolymerization, the functionality containing suspension polar functional group such as obtained by the copolymerization of ethylene and polar comonomers
Ultra-high molecular weight polyethylene under the premise of the mechanical performance for retaining its reason as far as possible, can improve ultra-high molecular weight polyethylene
Nonpolar defect improves its added value, expands its application range.In addition, the copolymer containing suspension polar functional group has
Active reaction is point, can easily and efficiently obtain diversified functional ultra-high molecular weight polyethylene.
The preparation of ultra-high molecular weight polyethylene at present mainly uses heterogeneous Ziegler-Natta catalyst and early transition metal
Based on single site catalysts.But when these catalyst being applied to the copolymerization of ethylene and other monomers, due to catalyst
It is poor to the copolymerized ability of long-chain olefin, cause Copolymerization activity and molecular weight to reduce, and the poor controllability of the content of co-monomer, because
This hardly results in high performance or functional ultra-high molecular weight polyethylene.
When it is co-monomer to select the monomer containing polar functional group, due to the oxytropism and electrophilicity mistake of early transition metal
By force, polar monomer hetero atom is directly coordinated to metal center and forms stable complex, leads to catalyst inactivation.Therefore, in recent years
Come numerous research groups to be copolymerized with ethylene using the polar comonomers of alkyl aluminum protection, improves its hetero atom to central metal
Toxic side effect.For example, Vega et al. have studied bridge metallocenes catalyst system and catalyzing to ethylene and 10- hendecene -1- alcohol or 5- oneself
The Copolymerization behavior of alkene -1- alcohol, hydroxy radical content is up to 5.5mol% in gained copolymer, number-average molecular weight 10~35 myriagrams/
Between mole (J.Appl.Polym.Sci., 2008,109,1529).Recently, Tang and Sun research groups use [ONX]Three teeth
Titanium complex has carried out the copolymerization of ethylene and various polar comonomers, and polymerization system shows very high activity, and acquisition is total to
The molecular weight of polymers is between 2~200,000 grams/mol, and the highest content of polar functional group reaches 3.3mol% in copolymer
(Macromolecules,2013,46,2870).Although single site catalysts can be catalyzed ethylene and polar comonomers
Copolymerization, but with the increase of polar functional group insertion rate in copolymer, Copolymerization activity drastically declines, and chain transfer reaction frequency
Numerous generation can only achieve 350,000 grams/mol so as to cause the highest weight of copolymer, cannot obtain functional super high molecular weight
Polyethylene.
Invention content
The object of the present invention is to provide a kind of preparation methods of functional ultra-high molecular weight polyethylene, are specifically to provide one kind
The preparation method of controllable, with melting temperature the functional ultra-high molecular weight polyethylene of polar group content.
The functional ultra-high molecular weight polyethylene of the present invention includes repetitive unit with formula (I) structure with formula
(II) repetitive unit of structure：
Wherein FG is polar functional group：Hydroxyl, carboxyl, ester group, ether, sulfydryl or amino；
N is 1~16；The size of n represents the length of co-monomer side chain；
The repetitive unit with formula (II) structure is more than in the insertion rate of the functional ultra-high molecular weight polyethylene
Zero and be less than or equal to 6.8mol%；
The weight average molecular weight of the functionality ultra-high molecular weight polyethylene is 102~4,500,000 grams/mol, molecular weight distribution
Ranging from the 1.5~3.0 of index；
The melting temperature of the functionality ultra-high molecular weight polyethylene is 96~135 DEG C, when insertion rate is more than 6.8mol%
When, functional ultra-high molecular weight polyethylene no longer has melting temperature.
The present invention also provides the preparation method of functional ultra-high molecular weight polyethylene, step is：It is urged in catalyst and helping
Under the action of agent, ethylene and the polar comonomers with formula (III) structure are gathered in atent solvent or halogenated solvent
It closes, obtains functional ultra-high molecular weight polyethylene；
Wherein, n is 1~16；
FG is polar functional group：Hydroxyl, carboxyl, ester group, ether, sulfydryl or amino；
The polar comonomers needs with formula (III) structure are protected by trialkylaluminium, and the trialkylaluminium is
Trimethyl aluminium, triethyl aluminum or triisobutyl aluminium；
The catalyst is the fluorenyl amine titanium complex with formula (IV) structure；
Wherein：
R1To R11It is identical or different group, respectively arbitrarily selected from hydrogen, straight chained alkyl, alkyl or adamantane containing branch
Base；
X1With X2Separate selection alkyl or halogen；
The co-catalyst is preferably methylaluminoxane, modified methylaluminoxane or triphen carbon four (pentafluorophenyl group) boric acid
Salt, more preferably modified methylaluminoxane.
As preferred technical solution：
The preparation method of functionality ultra-high molecular weight polyethylene as described above, specific preparation process are：
1) under nitrogen atmosphere, atent solvent or halogenated solvent is added, the trialkylaluminium and polarity with formula (III) structure is total to
Catalyst and co-catalyst is added in monomer after stirring；
2) it is passed through ethylene gas and carries out polymerisation；
3) stop being passed through ethylene, discharging of deflating is filtered, washed and dried.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, ethylene and the pole with formula (III) structure
The molar ratio of property co-monomer is preferably 10~300:1, more preferably 50~150:1.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, the fluorenyl amine titanium complex with there is formula
(III) molar ratio of the polar comonomers of structure is preferably 1:300~2400, more preferably 1:500~1200.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, the fluorenyl amine titanium complex and aluminium methyl
The molar ratio of oxygen alkane or modified methylaluminoxane is preferably 1:200~1500, more preferably 1:400~1000 or fluorenyl amine
Titanium complex and triphen carbon four (pentafluorophenyl group) borate molar ratio are preferably 1:1~4, more preferably 1:1.5~3.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, the trialkylaluminium with there is formula (III)
The molar ratio of the polar comonomers of structure is 1~20:1.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, the atent solvent are aromatic hydrocarbons, alkane
Class or cyclic hydrocar-bons solvent；Aromatic hydrocarbon solvent is preferably toluene, dimethylbenzene or ethylbenzene, more preferably toluene；Alkane solvents are preferred
For n-hexane, normal heptane or normal octane, more preferably n-hexane；Cyclic hydrocar-bons solvent is preferably hexamethylene, cycloheptane or cyclooctane,
More preferably hexamethylene.
The preparation method of functionality ultra-high molecular weight polyethylene as described above, the halogenated solvent are dichloroethanes or chlorine
Benzene.
The temperature of the preparation method of functionality ultra-high molecular weight polyethylene as described above, the polymerization is -20~100
DEG C, the time of the polymerization is preferably 10~120min, more preferably 20~60min, and the pressure of the ethylene is preferably 1~
40bar, more preferably 3~30bar.
During preparing the functional ultra-high molecular weight polyethylene, all experimental procedures sensitive to moisture and oxygen
All carried out under nitrogen protection using standard Schlenk technique.
The preparation method of the functional ultra-high molecular weight polyethylene of functionality of the present invention, in this preparation process, the present invention
Use catalyst for fluorenyl amine titanium complex, co-catalyst is methylaluminoxane, modified methylaluminoxane or (five fluorine of triphen carbon four
Phenyl) polymerization system of borate carries out the polar comonomers (with formula (III) structure) that ethylene is protected with trialkylaluminium and polymerize
When, rate of chain growth is fast, and has very strong copolymerized ability to the polar comonomers of long-chain.Compared to heterogeneous Ziegler-
Natta-catalyzed system is compared with homogeneous catalysis system, and the catalyst system and catalyzing notable is will be appreciated that pole to trialkylaluminium protection
Property functional group tolerance it is good, and β-hydrogen chain transfer reaction is few, can highly active catalytic copolyreaction obtain it is functional super
The ethylene copolymer of high molecular weight and Narrow Molecular Weight Distribution.The result shows that the repetitive unit with formula (II) structure in the present invention
It is more than zero in the insertion rate of the functional ultra-high molecular weight polyethylene and is less than or equal to 6.8mol%, functional super high molecular weight
The melting temperature of polyethylene is 96~135 DEG C, and weight average molecular weight is 102~4,500,000 grams/mol, molecular weight distributing index 1.5
~3.0.
The present invention can prepare functional ultra-high molecular weight polyethylene, be since selected catalyst system and catalyzing is to trialkylaluminium
The polar comonomers of protection have fabulous tolerance and copolymerized ability, and β-hydrogen transfer reaction is not present, poly- to ensure that
High activity, the insertion rate of the super high molecular weight of copolymer and polar comonomers in the copolymer of zoarium system.
Advantageous effect：
The present invention obtains the controllable functional superelevation of polar functional mass contg by the copolymerization of ethylene and polar comonomers
Molecular weight polyethylene.
Catalyst system of the present invention has very strong copolymerized ability to the polar comonomers that trialkylaluminium is protected,
Good chain growth speed is kept, and overcomes chain transfer reaction, to effectively obtain functional superhigh molecular weight polyethylene
Alkene.
Specific implementation mode
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Examples 1 to 6
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Sequentially added in kettle dimethylbenzene, triisobutyl aluminium and with formula (III) structure polar comonomers (n 9, FG are hydroxyl), three
Aluminium isobutyl and the molar ratio of polar comonomers are 1.5:1；At 20 DEG C stir 10min after, be added modified methylaluminoxane and
Fluorenyl amine titanium complex (R with formula (IV) structure1For adamantyl, R2And R3For methyl, R4~R10For tertiary butyl, R11For
Hydrogen, X1And X2For methyl), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure is 1:300, fluorenes
The molar ratio of base amine titanium complex and modified methylaluminoxane is 1:1000；Then nitrogen in kettle is shed, then is passed through ethylene gas,
Pressure in kettle is set to reach certain value；Stop being passed through ethylene after polymerisation 30min under the conditions of 30 DEG C, the gas being vented in kettle goes out
Material, reactant is poured into the ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put into after being washed 3 times with acetone
Dry 8h at 60 DEG C, obtains functional ultra-high molecular weight polyethylene in vacuum drying oven.
When ethylene pressure is 1~30bar, the molar ratio of ethylene and polar comonomers is 50~300:When 1, functional superelevation
The polymerization activity of molecular weight polyethylene, the weight average molecular weight (M of copolymerw), relative molecular weight distribution index (PDI), have formula
(II) the polymerization results data such as insertion rate, melting temperature of the repetitive unit of structure see the table below.
Embodiment 7~11
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Toluene, triisobutyl aluminium and the polar comonomers (n 9, FG are hydroxyl) with formula (III) structure are sequentially added in kettle, three is different
The molar ratio of butyl aluminium and polar comonomers is 1.5:1；After stirring 10min at 20 DEG C, modified methylaluminoxane and tool is added
There is the fluorenyl amine titanium complex (R of formula (IV) structure1For tertiary butyl, R2And R3For methyl, R4And R5For hydrogen, R6~R9For tertiary butyl,
R10~R11For hydrogen, X1And X2For methyl), the molar ratio of fluorenyl amine titanium complex and modified methylaluminoxane is 1:1000；Then
Nitrogen in kettle is shed, then is passed through ethylene gas, pressure in kettle is made to reach 8bar；Stop after polymerisation 30min under the conditions of 30 DEG C
It is only passed through ethylene, the gas discharge being vented in kettle pours into reactant in the ethanol solution containing 10% (V/V) hydrochloric acid；It filters
To product washed 3 times with acetone after be put into vacuum drying oven at 60 DEG C dry 8h, obtain functional ultra-high molecular weight polyethylene.
When the molar ratio of fluorenyl amine titanium complex and polar comonomers is 1:300~2400, ethylene and polar comonomers
Molar ratio is 10~80:When 1, the polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw)、
The polymerization results numbers such as relative molecular weight distribution index (PDI), the insertion rate of repetitive unit with formula (II) structure, melting temperature
According to see the table below.
Embodiment 12~19
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Cyclooctane, triisobutyl aluminium and the polar comonomers (FG is hydroxyl) with formula (III) structure, triisobutyl are sequentially added in kettle
The molar ratio of aluminium and polar comonomers is 1.5:1；After stirring 10min at 20 DEG C, modified methylaluminoxane is added and there is formula
(IV) the fluorenyl amine titanium complex (R of structure1For tertiary butyl, R2And R3For methyl, R4~R10For tertiary butyl, R11For hydrogen, X1And X2
For methyl), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure is 1:1000, fluorenyl amine titanium
The molar ratio of complex and modified methylaluminoxane is 1:1000；Then nitrogen in kettle is shed, then is passed through ethylene gas, is made in kettle
Pressure reaches 8bar, and the molar ratio of ethylene and polar comonomers is 150:1；Stop after polymerisation 30min under the conditions of 30 DEG C
It is passed through ethylene, the gas discharge being vented in kettle pours into reactant in the ethanol solution containing 10% (V/V) hydrochloric acid；It is obtained by filtration
Product washed 3 times with acetone after be put into vacuum drying oven at 60 DEG C dry 8h, obtain functional ultra-high molecular weight polyethylene.
When n is 1~16 in the polar comonomers with formula (III) structure, functional ultra-high molecular weight polyethylene gathers
Close active, copolymer weight average molecular weight (Mw), relative molecular weight distribution index (PDI), with formula (II) structure repetition list
Insertion rate, the polymerization results data such as melting temperature of member see the table below.
Embodiment 20~25
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Sequentially added in kettle normal octane, triisobutyl aluminium and with formula (III) structure polar comonomers (n 9), triisobutyl aluminium with
The molar ratio of polar comonomers is 1.5:1；After stirring 10min at 20 DEG C, modified methylaluminoxane is added and there is formula (IV)
The fluorenyl amine titanium complex (R of structure2And R3For methyl, R1And R4~R11For hydrogen-based, X1And X2For methyl), fluorenyl amine titanium complex
Molar ratio with the polar comonomers with formula (III) structure is 1:1500, fluorenyl amine titanium complex and modified methylaluminoxane
Molar ratio be 1:1000；Then nitrogen in kettle is shed, then is passed through ethylene gas, pressure in kettle is made to reach 8bar, ethylene and pole
Property co-monomer molar ratio be 60:1；Stop being passed through ethylene after polymerisation 30min under the conditions of 30 DEG C, the gas being vented in kettle
Discharging, reactant is poured into the ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put after being washed 3 times with acetone
Enter and dry 8h in vacuum drying oven at 60 DEG C, obtains functional ultra-high molecular weight polyethylene.
When FG is hydroxyl, carboxyl, ester group, ether, sulfydryl or amino in the polar comonomers with formula (III) structure,
The polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw), relative molecular weight distribution index
(PDI), the polymerization results data such as insertion rate, melting temperature of the repetitive unit with formula (II) structure see the table below.
Embodiment 26~33
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Toluene, triisobutyl aluminium and the polar comonomers (n 9, FG are hydroxyl) with formula (III) structure are sequentially added in kettle, three is different
The molar ratio of butyl aluminium and polar comonomers is 1.5:1；After stirring 10min at 20 DEG C, methylaluminoxane is added and there is formula
(IV) the fluorenyl amine titanium complex (R of structure1For adamantyl, R2、R3And R4For methyl, R5And R10For tertiary butyl, R6~R9For
Hydrogen, R11For hydrogen, X1And X2For chlorine atom), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure
It is 1:1200；Then nitrogen pressure in kettle is shed, then is passed through ethylene gas, so that pressure in kettle is reached 35bar, ethylene is total with polarity
The molar ratio of monomer is 80:1；Polymerisation stops being passed through ethylene for a period of time afterwards under the conditions of 30 DEG C, the gas being vented in kettle
Discharging, reactant is poured into the ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put after being washed 3 times with acetone
Enter and dry 8h in vacuum drying oven at 60 DEG C, obtains functional ultra-high molecular weight polyethylene.
When the molar ratio of fluorenyl amine titanium complex and methylaluminoxane is 1:200~1500, polymerization time be 30~
When 120min, the polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw), relative molecular weight point
The polymerization results data such as cloth index (PDI) see the table below.
Embodiment 34~41
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Sequentially added in kettle cycloheptane, triisobutyl aluminium and with formula (III) structure polar comonomers (n 9, FG are hydroxyl), three
Aluminium isobutyl and the molar ratio of polar comonomers are 1.5:1；At 20 DEG C stir 10min after, be added modified methylaluminoxane and
Fluorenyl amine titanium complex (R with formula (IV) structure1For adamantyl, R2And R3For methyl, R4~R10For hydrogen, R11For tertiary fourth
Base, X1And X2For methyl), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure is 1:2000；
Then nitrogen in kettle is shed, then is passed through ethylene gas, pressure in kettle is made to reach 35bar, the molar ratio of ethylene and polar comonomers
It is 150:1；Polymerisation stops being passed through ethylene for a period of time afterwards under the conditions of 30 DEG C, and the gas discharge being vented in kettle will react
Object pours into the ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put into after being washed 3 times with acetone in vacuum drying oven
Dry 8h, obtains functional ultra-high molecular weight polyethylene at 60 DEG C.
When the molar ratio of fluorenyl amine titanium complex and modified methylaluminoxane is 1:200~1500, polymerization time be 30~
When 120min, the polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw), relative molecular weight point
The polymerization results data such as cloth index (PDI) see the table below.
Embodiment 42~46
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Toluene, triisobutyl aluminium and the polar comonomers (n 9, FG are hydroxyl) with formula (III) structure are sequentially added in kettle, three is different
The molar ratio of butyl aluminium and polar comonomers is 2:1；After stirring 10min at 20 DEG C, modified methylaluminoxane is added and has
The fluorenyl amine titanium complex (R of formula (IV) structure1For adamantyl, R2And R3For methyl, R4、R5、R7And R8For hydrogen, R6And R9For uncle
Butyl, R10~R11For hydrogen, X1With X2All it is chlorine atom), fluorenyl amine titanium complex and the polar comonomers with formula (III) structure
Molar ratio be 1:1000, the molar ratio of fluorenyl amine titanium complex and modified methylaluminoxane is 1:1000；Then it sheds in kettle
Nitrogen, then it is passed through ethylene gas, so that pressure in kettle is reached 40bar；Stop being passed through second after polymerisation 30min under certain condition
Alkene, the gas discharge being vented in kettle, reactant is poured into the ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration
It is put into vacuum drying oven dry 8h at 60 DEG C after being washed 3 times with acetone, obtains functional ultra-high molecular weight polyethylene.
When polymerization temperature is 0~80 DEG C, the polymerization activity of functional ultra-high molecular weight polyethylene, copolymer are divided equally again
Son amount (Mw), relative molecular weight distribution index (PDI), the polymerization results data such as melting temperature see the table below.
Embodiment 47~52
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Normal heptane, trialkylaluminium and the polar comonomers with formula (III) structure are sequentially added in kettle (n 9, FG are hydroxyl)；20
After stirring 10min at DEG C, modified methylaluminoxane and the fluorenyl amine titanium complex (R with formula (IV) structure is added1For tertiary fourth
Base, R2And R3For methyl, R4~R11For hydrogen atom, X1With X2For methyl), fluorenyl amine titanium complex with formula (III) structure
The molar ratio of polar comonomers is 1:1000, the molar ratio of fluorenyl amine titanium complex and modified methylaluminoxane is 1:1000；So
After shed nitrogen in kettle, then be passed through ethylene gas, pressure made in kettle to reach 8bar, the molar ratio of ethylene and polar comonomers is
50:1；Stop being passed through ethylene after polymerisation 60min under the conditions of -20 DEG C, the gas discharge being vented in kettle pours into reactant
In ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put into vacuum drying oven after being washed 3 times with acetone at 60 DEG C
Dry 8h, obtains functional ultra-high molecular weight polyethylene.
When trialkylaluminium is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium, mole of trialkylaluminium and polar comonomers
Than being 1~2.5:When 1, the polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw), opposite point
Son is measured the polymerization results data such as profile exponent (PDI), the insertion rate of the repetitive unit with formula (II) structure, melting temperature and is seen below
Table.
Embodiment 53~60
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Ethylbenzene, triisobutyl aluminium and the polar comonomers (n 9, FG are hydroxyl) with formula (III) structure are sequentially added in kettle, three is different
The molar ratio of butyl aluminium and polar comonomers is 20:1；After stirring 10min at 20 DEG C, four (pentafluorophenyl group) boron of triphen carbon is added
Hydrochlorate and the fluorenyl amine titanium complex (R with formula (IV) structure1For tertiary butyl, R2And R3For methyl, R4~R11For hydrogen atom, X1
With X2For methyl), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure is 1:2400；Then
Nitrogen in kettle is shed, then is passed through ethylene gas, pressure is made in kettle to reach 8bar, the molar ratio of ethylene and polar comonomers is 50:
1；Polymerisation stops being passed through ethylene for a period of time afterwards under the conditions of 90 DEG C, and the gas discharge being vented in kettle pours into reactant
In ethanol solution containing 10% (V/V) hydrochloric acid；The product being obtained by filtration is put into vacuum drying oven after being washed 3 times with acetone at 60 DEG C
Dry 8h, obtains functional ultra-high molecular weight polyethylene.
When the molar ratio of fluorenyl amine titanium complex and triphen carbon four (pentafluorophenyl group) borate is 1:1~4, polymerization time is
When 10~120min, the polymerization activity of functional ultra-high molecular weight polyethylene, the weight average molecular weight (M of copolymerw), average molecular
The polymerization results data such as amount profile exponent (PDI) see the table below.
Embodiment 61~65
A kind of preparation method of functionality ultra-high molecular weight polyethylene, under nitrogen atmosphere, first in dry polymerisation
Solvent, triisobutyl aluminium and the polar comonomers (n 9, FG are hydroxyl) with formula (III) structure are sequentially added in kettle, three is different
The molar ratio of butyl aluminium and polar comonomers is 5:1；After stirring 10min at 20 DEG C, modified methylaluminoxane is added and has
The fluorenyl amine titanium complex (R of formula (IV) structure1For adamantyl, R2And R3For methyl, R4~R11For hydrogen atom, X1With X2For first
Base), the molar ratio of fluorenyl amine titanium complex and the polar comonomers with formula (III) structure is 1:1000, the cooperation of fluorenyl amine titanium
The molar ratio of object and modified methylaluminoxane is 1:1000；Then nitrogen in kettle is shed, then is passed through ethylene gas, makes pressure in kettle
Reach 8bar, the molar ratio of ethylene and polar comonomers is 50:1；Stop being passed through after polymerisation 30min under the conditions of 100 DEG C
Ethylene, the gas discharge being vented in kettle, reactant is poured into the ethanol solution containing 10% (V/V) hydrochloric acid；The production being obtained by filtration
Product are put into vacuum drying oven dry 8h at 60 DEG C after being washed 3 times with acetone, obtain functional ultra-high molecular weight polyethylene.
When solvent is toluene, n-hexane, hexamethylene, dichloroethanes or chlorobenzene, functional ultra-high molecular weight polyethylene
Weight average molecular weight (the M of polymerization activity, copolymerw), relative molecular weight distribution index (PDI), the polymerization results number such as melting temperature
According to see the table below.
Claims (10)
1. the preparation method of functional ultra-high molecular weight polyethylene, characterized in that step is：In the work of catalyst and co-catalyst
Under, ethylene is polymerize with the polar comonomers with formula (III) structure in atent solvent, functional superelevation point is obtained
Sub- weight northylen；
Wherein, n is 1~16；
FG is polar functional group：Hydroxyl, carboxyl, ester group, ether, sulfydryl or amino；
The polar comonomers needs with formula (III) structure are protected by trialkylaluminium, and the trialkylaluminium is front three
Base aluminium, triethyl aluminum or triisobutyl aluminium；
The catalyst is the fluorenyl amine titanium complex with formula (IV) structure；
Wherein：
R1To R11It is identical or different group, respectively arbitrarily selected from hydrogen, straight chained alkyl, alkyl or adamantyl containing branch；
X1With X2Separate selection alkyl or halogen；
The co-catalyst is aluminium alkoxide compound or triphen carbon four (pentafluorophenyl group) borate, and the aluminium alkoxide compound is first
Base aikyiaiurnirsoxan beta or modified methylaluminoxane.
2. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that specific to prepare
Step is：
1) under nitrogen atmosphere, atent solvent, trialkylaluminium and the polar comonomers with formula (III) structure is added, add after stirring
Enter catalyst and co-catalyst；
2) it is passed through ethylene gas and carries out polymerisation；
3) stop being passed through ethylene, discharging of deflating is filtered, washed and dried.
3. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that ethylene and tool
It is 10~300 to have the molar ratio of the polar comonomers of formula (III) structure:1.
4. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that the fluorenyl
The molar ratio of amine titanium complex and the polar comonomers with formula (III) structure is 1:300~2400.
5. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that the fluorenyl
The molar ratio of amine titanium complex and aluminium alkoxide compound is 1:200~1500 or fluorenyl amine titanium complex and (five fluorine of triphen carbon four
Phenyl) borate molar ratio be 1:1~4.
6. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that three alkane
The molar ratio of base aluminium and the polar comonomers with formula (III) structure is 1~20:1.
7. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that the inertia
Solvent is halogenated solvent, aromatic hydrocarbons, alkanes or cyclic hydrocar-bons solvent.
8. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 7, which is characterized in that described halogenated
Solvent is dichloroethanes or chlorobenzene, and aromatic hydrocarbon solvent is toluene, dimethylbenzene or ethylbenzene, and alkane solvents are n-hexane, normal heptane
Or normal octane, cyclic hydrocar-bons solvent are hexamethylene, cycloheptane or cyclooctane.
9. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that the polymerization
Temperature be -20~100 DEG C, time of the polymerization is 10~120min, and the pressure of the ethylene is 1~40bar.
10. the preparation method of functionality ultra-high molecular weight polyethylene according to claim 1, which is characterized in that functional
Ultra-high molecular weight polyethylene includes the repetitive unit with formula (I) structure and the repetitive unit with formula (II) structure：
Wherein FG is polar functional group：Hydroxyl, carboxyl, ester group, ether, sulfydryl or amino；
N is 1~16；
The repetitive unit with formula (II) structure the insertion rate of the functional ultra-high molecular weight polyethylene be more than zero and
Less than or equal to 6.8mol%；
The weight average molecular weight of the functionality ultra-high molecular weight polyethylene is 102~4,500,000 grams/mol, molecular weight distributing index
Ranging from 1.5~3.0；
The melting temperature of the functionality ultra-high molecular weight polyethylene is 96~135 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610693533.1A CN106220767B (en) | 2016-08-19 | 2016-08-19 | The preparation method of functional ultra-high molecular weight polyethylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610693533.1A CN106220767B (en) | 2016-08-19 | 2016-08-19 | The preparation method of functional ultra-high molecular weight polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106220767A CN106220767A (en) | 2016-12-14 |
| CN106220767B true CN106220767B (en) | 2018-10-23 |
Family
ID=57553359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610693533.1A Active CN106220767B (en) | 2016-08-19 | 2016-08-19 | The preparation method of functional ultra-high molecular weight polyethylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106220767B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030844A (en) * | 2010-09-14 | 2011-04-27 | 中国科学院上海有机化学研究所 | Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight |
| CN104844741A (en) * | 2015-05-13 | 2015-08-19 | 宁波大学 | Preparation method for mixture of ethylene-undecylenyl alcohol copolymer and ultrahigh molecular weight polyethylene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5675162B2 (en) * | 2010-04-30 | 2015-02-25 | 三井化学株式会社 | Method for producing nonpolar-polar olefin copolymer |
-
2016
- 2016-08-19 CN CN201610693533.1A patent/CN106220767B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030844A (en) * | 2010-09-14 | 2011-04-27 | 中国科学院上海有机化学研究所 | Olefin polymerization catalyst and polyethylene with ultralow branching coefficient and ultrahigh molecular weight |
| CN104844741A (en) * | 2015-05-13 | 2015-08-19 | 宁波大学 | Preparation method for mixture of ethylene-undecylenyl alcohol copolymer and ultrahigh molecular weight polyethylene |
Non-Patent Citations (9)
| Title |
|---|
| Catalysts for UHMWPE and UHMWPE-copolymers;Robert L. Jones Jr., et al.;《INORGANICA CHIMICA ACTA》;20101215;第364卷(第1期);第275-281页 * |
| Copolymerizations of ethylene and polar comonomers with bis(phenoxyketimine) group IV complexes: Effects of the central metal properties;Zhang Xiaofan, et al.;《JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY》;20070101;第45卷(第1期);第59-68页 * |
| Ethylene/Polar Monomer Copolymerization Behavior of Bis(phenoxy–imine)Ti Complexes: Formation of Polar Monomer Copolymers;Hiroshi Terao,et al.;《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》;20081231;第130卷(第52期);第17636-17637页 * |
| Highly active copolymerization of ethylene with 10-undecen-1-ol using phenoxy-based zirconium/methylaluminoxane catalysts;Zhang Xiaofan, et al.;《JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY》;20051201;第43卷(第23期);第5944-5952页 * |
| Highly Active Ethylene/Hydroxyl Comonomers Copolymerization Using Metallocene Catalysts;M. T. Exposito, et al.;《JOURNAL OF APPLIED POLYMER SCIENCE》;20080805;第109卷(第3期);第1529-1534页 * |
| Imino-Indolate Half-Titanocene Chlorides: Synthesis and Their Ethylene (Co-)Polymerization;Zuo Weiwei, et al.;《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》;20090115;第47卷(第2期);第357-372页 * |
| Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst;Brian K. Long, et al.;《ANGEWANDTE CHEMIE-INTERNATIONAL EDITION》;20160613;第55卷(第25期);第7106-7110页 * |
| The Influence of t-Butyl and Cyclododecyl Substitution on Ethylene/1-Hexene Copolymerization Using Ansa-Fluorenylamidodimethyltitanium Derivatives;Patcharaporn Kaivalchatchawal, et al.;《MOLECULES》;20110531;第16卷(第5期);第4122-4130页 * |
| 芴基氨基二甲基钛配合物芴环上取代基对乙烯聚合的影响;李天佑 等;《合成纤维》;20150625;第44卷(第6期);第1-4页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106220767A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102614358B1 (en) | Olefin-olefin alcohol copolymer and method for producing the same | |
| RU2017111499A (en) | CATALYTIC SYSTEMS BASED ON TITANIUM PHOSPHINIMIDE AND TITANIUM IMINOIMIDAZOLIDIDE WITH ACTIVATED SUBSTRATES | |
| KR102616710B1 (en) | Copolymers of olefins and unsaturated carboxylic acids or unsaturated carboxylic acid derivatives | |
| CN104177528B (en) | A kind of ethylene/longer chain α-olefin copolymer and preparation method thereof | |
| KR19990006927A (en) | Ethylene Polymerization Method and Heterogeneous Catalyst System | |
| CN106336482A (en) | Functional cyclic olefin copolymer and preparation method thereof | |
| CN108368203A (en) | Carbon monoxide-olefin polymeric and the method for preparing poly- (alpha-olefin) drag reducer of super high molecular weight | |
| CN106243280A (en) | A kind of functional cycloolefin/styrene copolymer and preparation method thereof | |
| CN106220767B (en) | The preparation method of functional ultra-high molecular weight polyethylene | |
| CN106220768A (en) | A kind of high impact polyvinyl resin with super-high molecular weight and preparation method thereof | |
| CN106317282B (en) | The preparation method of ultra-high-molecular-weight polyethylene/styrene copolymer | |
| CN108864338B (en) | Catalyst composition for olefin polymerization and olefin polymerization method | |
| CN107722155A (en) | A kind of alhpa olefin fluorobenzene ethene polymer and preparation method thereof | |
| CN107880170B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN111116810B (en) | Preparation method of olefin-olefin alcohol copolymer | |
| US7172988B2 (en) | Catalyst component for ethylene polymerization, a process for preparing thereof and catalyst comprising the same | |
| JPS63145306A (en) | Preparation of ethylene polymer | |
| CN107880183B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880188B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880186B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880162B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880166B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880177B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880172B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880168B (en) | Catalyst component for olefin polymerization and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |