CN107188905B - A kind of amino phenolic group phosphorus ligand and its application in vinyl polymerization and oligomerisation - Google Patents
A kind of amino phenolic group phosphorus ligand and its application in vinyl polymerization and oligomerisation Download PDFInfo
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Abstract
A kind of amino phenolic group phosphorus ligand and its application in vinyl polymerization and oligomerisation, are related to catalyst technical field, its structural formula is, in amino phenols structure, amino is in the ortho position of phenolic hydroxyl group, meta or para position；R1Alkyl, naphthenic base, alkoxy, aryl for carbon atom number no more than 10；R2Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10；R3Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10.A kind of phosphorus ligand of multidigit point of this amino phenolic group phosphorus ligand is based on this ligand, by changing the proportion with transition metal and co-catalyst, can neatly be catalyzed the oligomerisation, polymerization and copolyreaction of different types of ethylene.
Description
Technical field:
The present invention relates to catalyst technical fields, and in particular to a kind of amino phenolic group phosphorus ligand and its in vinyl polymerization and neat
Application in poly-.
Background technique:
Alpha-olefin can be used as comonomer for the production of linear low density polyethylene (LLDPE) and close for producing
At products such as lubricating oil, drag reducer for crude oil and surfactants.Pass through the linea low density second of ethylene and alpha-olefin copolymer production
Alkene is widely used synthetic resin, in addition to excellent toughness and environmental stress crack resistance ability, corrosion resistance, shock resistance
Other than intensity, tearing strength and tensile strength, also there is good processing performance, including creep resisting ability, removal, film forming
Property, heat sealability etc., be therefore widely used in manufacture medical instrument, film, the cladding material proof stress container of cable.Commonly
Comonomer has 1- butylene, 1- hexene and 1- octene etc..There is result of study to show the obtained production using 1- octene as comonomer
Product have better performance.Currently, ethylene tetramerization synthesis 1- octene not yet realizes large-scale industrial production, 1- octene mainly by
It is isolated from non-selective ethylene oligomerization mixture, therefore higher cost.
Since the researcher of Sasol company reports the complex of the PNP ligand and second chromic salts that synthesized by isopropylamine for the first time
Efficiently catalysis ethylene selectivity four it is poly- obtain be main oligomerization product with 1- octene since, chromium system ethylene tetramerization is catalyzed
In terms of the research of agent is concentrated mainly on influence of the structure of ligand to catalytic effect.Although in terms of achieved
Many gratifying achievements, but reach the level of ethylene trimer technique far away to the selectivity of 1- octene, and the ligand of new construction
Research and development are to solve the problems, such as this fundamental way.Meanwhile new construction ligand and its complex ethylene polymerization and combined polymerization
In application study be also promote polyethylene industrial technological advancement important impetus.
Summary of the invention:
In place of overcoming above-mentioned the shortcomings of the prior art, and provide a kind of amino phenolic group phosphorus
Ligand and its application in vinyl polymerization and oligomerisation, it provides a kind of phosphorus ligand with multiple coordination sites, the ligand
Major catalyst can be formed in a manner of prefabricated complex or scene mixing from the salt of different transition metal.
In order to solve the problems existing in background technology, the present invention is to adopt the following technical scheme that the ligand is based on ammonia
The phosphorous derivative of base phenol, structural formula are as follows:
Wherein:
In amino phenols structure, amino is in the ortho position of phenolic hydroxyl group, meta or para position；
R1Alkyl, naphthenic base, alkoxy, aryl for carbon atom number no more than 10；
R2Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10；
R3Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10
The application method: the complex that phosphorus ligand and transistion metal compound are formed by prefabricated or extemporaneous preparation
Or mixture, the cation of transition metal salt include Cr (II), Cr (III), Ni (II), Fe (II), Co (III), Pd (II), Zr
(II), Zr (IV), Pt (II), wherein it is preferred that Cr (II), Cr (III), Ni (II), Fe (II) Pd (II)；Transition metal salt is born
Ion includes NO3 -、SO4 2-、Cl-、Br-With acetylacetone,2,4-pentanedione anion.
The molar ratio of phosphorus ligand and transistion metal compound is 0.1:1~10:1 in the complex or mixture.
Catalyst of the complex or mixture as major catalyst and co-catalyst composition, co-catalyst include
One of alkyl aluminum, aikyiaiurnirsoxan beta and chlorination alkyl aluminum or a variety of combinations；Aluminium in the metal and co-catalyst of major catalyst
Molar ratio be 1:1~1:5000.
The alkyl aluminum includes one of trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and tri-n-hexyl aluminum or more
The combination of kind；Aikyiaiurnirsoxan beta includes one of methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide or a variety of combinations；Chlorine
Changing alkyl aluminum includes one in ethyl aluminium sesquichloride, aluminium diethyl monochloride, sesquialter aluminium diethyl monochloride and ethylaluminium dichloride
Kind or a variety of combinations.
Application of the catalyst in the polymerization, combined polymerization and oligomerisation reaction of catalysis ethylene: with ethylene copolymerization
Monomer includes C18 end alkene below, acrylonitrile, acrylamide, N, N- dimethylacrylamide, methyl acrylate, acrylic acid second
Ester, n-butyl acrylate and methyl methacrylate.
Described polymerization temperature is 0~100 DEG C in catalyzed ethylene polymerization, combined polymerization, oligomerization, and polymerization pressure is
0.1~0.5MPa.
The beneficial effects of the invention are as follows a kind of phosphorus ligand of multidigit point is provided, it is based on this ligand, passes through change and mistake
The proportion of metal and co-catalyst is crossed, the oligomerisation, polymerization and copolyreaction of different types of ethylene can be neatly catalyzed.
Detailed description of the invention:
Fig. 1 is the structural schematic diagram of ligand involved in the present invention；
Fig. 2 is the structural schematic diagram of ligand 1 of the present invention；
Fig. 3 is the structural schematic diagram of ligand 2 of the present invention；
Fig. 4 is the structural schematic diagram of ligand 3 of the present invention；
Fig. 5 is the structural schematic diagram of ligand 4 of the present invention.
Specific embodiment:
Referring to Fig.1, the present invention specifically uses and mode is implemented as follows: the ligand is the phosphorous derivative based on amino phenols,
Its structural formula is as follows:
Wherein:
In amino phenols structure, amino is in the ortho position of phenolic hydroxyl group, meta or para position；
R1Alkyl, naphthenic base, alkoxy, aryl for carbon atom number no more than 10；
R2Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10；
R3Alkyl, naphthenic base, aryl, alkoxy for carbon atom number less than 10
The application method: the complex that phosphorus ligand and transistion metal compound are formed by prefabricated or extemporaneous preparation
Or mixture, the cation of transition metal salt include Cr (II), Cr (III), Ni (II), Fe (II), Co (III), Pd (II), Zr
(II), Zr (IV), Pt (II), wherein it is preferred that Cr (II), Cr (III), Ni (II), Fe (II) Pd (II)；Transition metal salt is born
Ion includes NO3 -、SO4 2-、Cl-、Br-With acetylacetone,2,4-pentanedione anion.
The molar ratio of phosphorus ligand and transistion metal compound is 0.1:1~10:1 in the complex or mixture, excellent
Select 0.3:1~3:1.
Catalyst of the complex or mixture as major catalyst and co-catalyst composition, co-catalyst include
One of alkyl aluminum, aikyiaiurnirsoxan beta and chlorination alkyl aluminum or a variety of combinations；Aluminium in the metal and co-catalyst of major catalyst
Molar ratio be 1:1~1:5000, preferably 1:100~1:1000.
The alkyl aluminum includes one of trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and tri-n-hexyl aluminum or more
The combination of kind；Aikyiaiurnirsoxan beta includes one of methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide or a variety of combinations；Chlorine
Changing alkyl aluminum includes one in ethyl aluminium sesquichloride, aluminium diethyl monochloride, sesquialter aluminium diethyl monochloride and ethylaluminium dichloride
Kind or a variety of combinations.
Application of the catalyst in the polymerization, combined polymerization and oligomerisation reaction of catalysis ethylene: with ethylene copolymerization
Monomer includes C18 end alkene below, acrylonitrile, acrylamide, N, N- dimethylacrylamide, methyl acrylate, acrylic acid second
Ester, n-butyl acrylate and methyl methacrylate.Wherein preferred 1- hexene, 1- octene, 1- decene, acrylonitrile, acrylamide, N,
N- dimethylacrylamide, methyl acrylate, methyl methacrylate.
Described polymerization temperature is 0~100 DEG C in catalyzed ethylene polymerization, combined polymerization, oligomerization, and polymerization pressure is
0.1~0.5MPa.
Utilize above-mentioned ligand and transition metal (Cr (II), Cr (III), Ni (II), Fe (II), Co (III), Pd (II), Zr
(II), Zr (IV), Pt (II)) salt pass through complex or mixture that prefabricated or extemporaneous preparation is formed, transition by a certain percentage
The anion of metal salt includes NO3 -、SO4 2-、Cl-、Br-With acetylacetone,2,4-pentanedione anion, wherein it is preferred that Cl-With acetylacetone,2,4-pentanedione bear from
Son.Using complex obtained or mixture as major catalyst, in a certain proportion of co-catalyst (including alkyl aluminum, aikyiaiurnirsoxan beta
With one of chlorination alkyl aluminum or a variety of mixtures) under the action of be catalyzed oligomerisation, polymerization and the ethylene and polarity and non-of ethylene
The copolyreaction of polar monomer.
It is acted on using aminophenols and substituted phosphorus chloride, the active hydrogen on p-aminophenol molecule may be implemented
Replace, to form the phosphorus ligand with multiple coordination sites.This kind of phosphorus ligand can be matched with the compound of transition metal
Position, can form complex or mixture under different proportions.These complexs or mixture are in alkyl aluminum and its derivative
Under the action of object, metal center can be restored, to have the coordination ability with vinyl monomer, realize catalysis second
Oligomerisation, polymerization and copolymerization of alkene and other effects.
Embodiment 1:
The preparation of multidigit point phosphorus ligand 1
In the structure of ligand 1, R1、R2、R3It is hydrogen, amino is in the ortho position of hydroxyl.Its structure is as shown in Fig. 2.
Under high pure nitrogen protection, diphenyl phosphorus chloride 5.8mL and 40mL tetrahydrofuran is added in flask, is sufficiently stirred
After dissolution, triethylamine 4.5mL is added, is cooled to 0 DEG C after stirring half an hour, the solution of o-aminophenol is added dropwise dropwise into solution
(1.24g o-aminophenol is dissolved in 10mL tetrahydrofuran) continues to stir half an hour at 0 DEG C after adding.Remove cold heating naturally
The reaction was continued after to room temperature 12 hours.Mixture is filtered to remove solid, and gained filtrate revolving removal solvent obtains crude product.It is thick to produce
Product dehydrated alcohol recrystallizes and obtains after being dried in vacuo ligand 1, clear crystal, yield 81%.Ligand 1 elemental analysis
C42H34NOP3Theoretical value (%): C, 76.24; H, 5.18; N, 2.12；Measured value (%): C, 75.91; H, 5.46;
N, 1.96。
Embodiment 2:
Ligand 1 is catalyzed ethylene oligomerization reaction
3 will be replaced in 80 DEG C of continuous vacuum drying 2 hours or more 500mL stainless steel autoclaves high pure nitrogen
It is secondary, it then vacuumizes and is replaced 3 times with ethylene again.150mL toluene is injected into kettle under conditions of keeping micro-positive pressure in kettle, is opened
Stirring is opened, the toluene solution dissolved with 7.0mg chromium acetylacetonate and the toluene solution dissolved with 14.5mg ligand 1 is added, adds after 5min
Enter 8.0mL co-catalyst methylaluminoxane (10% toluene solution).Ethylene is injected at 50 DEG C makes pressure in kettle reach and tie up
It holds in 3MPa, measures ethylene usage with mass flowmenter, and be stirred with the speed of 700rpm.Second is cut off after reaction 30min
Alkene charging, pressure release to normal pressure, filtering removes catalyst and polymer after autoclave is cooled to 0 DEG C.Filtrate, which is weighed and sampled, uses gas
Phase chromatography carries out quantitative analysis to its component.Catalytic activity is 2.51 × 106gmolCr -1h-1, polymer yield 1.9%, liquid
It is 73% that 1- hexene yield, which is 14%, 1- octene yield, in phase product.
Embodiment 3:
The preparation of multidigit point phosphorus ligand 2
In the structure of ligand 2, R1For methyl, R2And R3It is hydrogen, amino is in the meta position of hydroxyl.Its structure such as Fig. 3 institute
Show.
The synthesis process of ligand 2 is identical as ligand 1, and only amino phenols raw material changes 5- amino o-cresol into.Crude product is used
Dehydrated alcohol recrystallizes and obtains after being dried in vacuo ligand 2, clear crystal, yield 77%.1HNMR(δ,CDCl3,TMS):
2.10(s,3H), 6.20(d,J=8.0,1H), 6.55(s,1H), 6.79(d,J=8.0,1H), 6.98~7.76 (m,
30H)。
Embodiment 4:
The preparation of the complex 1 of the Ni of phosphorus ligand 2
Anhydrous and oxygen-free condition takes 1.03g (1.52mmol) ligand 2 to be added to stirring and dissolving in 50ml n-butanol at room temperature,
Add 0.468g(1.52mmol) glycol dimethyl ether conjunction Nickel Bromide, it is warming up to after being stirred to react 24 hours at 55 DEG C and removes
Reactor is moved into -15 DEG C of refrigerators and stands 12 hours precipitation brownish black solid complexes by heating.After filtering, the cold first of filter cake
Alcohol elutes twice, and vacuum drying obtains product 1.10g(yield 81%).C43H36Br2NNiOP3Elemental Analysis theory (%):
C, 57.76; H, 4.06; N, 1.57；Measured value C, 57.47; H, 4.35; N, 1.46.
Embodiment 5:
Complex-catalyzed ethylene polymerization
Magnetic stir bar will be built into 130 DEG C of continuous drying 6 hours or more 250m1 glass three neck round bottom and connect
Fill Schlenk standard vacuum-gas ventilator and constant pressure ethylene pipeline.Heating vacuumize and with high pure nitrogen replace 3 times, so
It vacuumizes and is replaced 3 times with ethylene again afterwards.The toluene that 50m1 is injected into flask, is then added the first dissolved with 7.2mg complex 1
Benzole soln,.According to preset A1/Ni ratio (500:1) be added 10.0mL co-catalyst ethyl aluminium sesquichloride (0.4mo1/L's
Hexane solution), at 20 DEG C, keeps the ethylene pressure magnetic stirring apparatus driving of latm in round-bottomed bottle to be vigorously stirred, react
Ethylene feed is cut off after 30min, terminates reaction with 10% hydrochloric acid acidic ethanol solution, polymer precipitating is obtained by filtration.Polymer
With ethyl alcohol, washed several times with water, vacuum drying to constant weight weighs to obtain polymer 16.7g.It is with the Mass Calculation polymerization activity of polymer
4.2×106 g·mol-1(Ni)·h-1, polymer Mw=7.2 × 10 after measured5g·mol-1, Mw/Mn =4.1。
Embodiment 6
The preparation of multidigit point phosphorus ligand 3
The structure of phosphorus ligand 3 is shown in Fig. 4.
The synthesis process of ligand 3 is identical as ligand 1, and only amino phenols raw material changes 4-aminophenol into.Crude product nothing
Water-ethanol recrystallizes and obtains after being dried in vacuo ligand 3, clear crystal, yield 83%.3 elemental analysis C of ligand42H34NOP3Reason
By value (%): C, 76.24; H, 5.18; N, 2.12；Measured value (%): C, 75.87; H, 5.39; N, 1.85.
Embodiment 7
Application of the ligand 3 in ethylene copolymer
Magnetic stir bar will be built into 130 DEG C of continuous drying 6 hours or more 250m1 glass three neck round bottom and connect
Fill Schlenk standard vacuum-gas ventilator and constant pressure ethylene pipeline.Heating vacuumize and with high pure nitrogen replace 3 times, so
It vacuumizes and is replaced 3 times with ethylene again afterwards.Into flask inject 100m1 toluene, then be added 9.1mL (8.61g,
0.1mol) methyl acrylate stirs evenly.4.0mL methylaluminoxane solution (10% toluene solution) is added into reactor, stirs
It mixes 1 hour.Dissolution 6.2mg glycol dimethyl ether is added and closes the toluene solution of nickelous bromide and molten dissolved with the toluene of 8.8mg ligand 3
Liquid.At 30 DEG C, keeps the ethylene pressure magnetic stirring apparatus driving of latm in round-bottomed bottle to be vigorously stirred, cut off second after reacting 1h
Alkene charging terminates reaction with 10% hydrochloric acid acidic ethanol solution, polymer precipitating is obtained by filtration.Polymer ethyl alcohol washes number
Secondary, vacuum drying to constant weight weighs to obtain polymer 10.4g.Polymer Mw=1.8 × 10 after measured5g·mol-1.Polymer sampling
It is dissolved in o-dichlorohenzene-D4, is composed at 110 DEG C with nuclear magnetic resonance spectrometer measurement hydrogen, polar monomer acrylic acid is calculated according to hydrogen modal data
The insertion rate of methyl esters is 4.5%.
Embodiment 8
The preparation of multidigit point phosphorus ligand 4, the structure of ligand 4 are as shown in Figure 5.
The synthesis process of ligand 4 is identical as ligand 1, and only amino phenols raw material changes 3- amino-phenol into, and phosphorus chloride spreads out
Biology is using chlorine two (2- anisyl) phosphine.Crude product dehydrated alcohol recrystallizes and obtains ligand 4, nothing after being dried in vacuo
Color crystal, yield 65%.3 elemental analysis C of ligand48H46NO7P3Theoretical value (%): C, 68.49; H, 5.51; N, 1.66;；
Measured value (%): C, 68.15; H, 5.63; N, 1.75.
Embodiment 9
Application of the ligand 4 in ethylene copolymer will be in 130 DEG C of three neck round bottoms of continuous drying 6 hours or more 250m1 glass
Flask is built into magnetic stir bar and is hinged with Schlenk standard vacuum-gas ventilator and constant pressure ethylene pipeline.Heating is taken out true
Sky is simultaneously replaced 3 times with high pure nitrogen, then vacuumize again and is replaced 3 times with ethylene.The toluene of 100m1 is injected into flask, so
The 1- octene that 15.6mL (11.2g, 0.1mol) is added afterwards stirs evenly.1.5mL co-catalyst ethyl times is added into reactor
Half aluminium chloride (hexane solution of 0.4mo1/L) and 0.14mL methylaluminoxane solution (10% toluene solution) stir 1 hour.
The toluene suspension liquid for having dispersed 1.5mg frerrous chloride and the toluene solution dissolved with 6.7mg ligand 3 is added.At 30 DEG C, circle is kept
The ethylene pressure magnetic stirring apparatus driving of latm is vigorously stirred in the bottle of bottom, ethylene feed is cut off after reacting 1h, with 10% hydrochloric acid
Acidic ethanol solution terminates reaction, and polymer precipitating is obtained by filtration.Polymer ethyl alcohol, washed several times with water, vacuum drying to constant weight,
Weigh to obtain polymer 6.2g.Polymer Mw=3.5 × 10 after measured5 g·mol-1, Mw/Mn=5.3.
Claims (7)
1. a kind of amino phenolic group phosphorus ligand, it is characterised in that: the ligand is the phosphorous derivative based on amino phenols, structural formula
It is as follows:
Wherein:
In amino phenols structure, amino is in the ortho position of phenolic hydroxyl group, meta or para position；
R1It is not more than 10 alkyl for carbon atom number；
R2Alkoxy for carbon atom number less than 10；
R3Alkoxy for carbon atom number less than 10.
2. application of the amino phenolic group phosphorus ligand according to claim 1 in vinyl polymerization and oligomerisation, it is characterised in that: make
It is golden with method: the complex or mixture that phosphorus ligand and transistion metal compound are formed by prefabricated or extemporaneous preparation, transition
The cation for belonging to salt is Cr (II), Cr (III), Ni (II), Fe (II), Co (III), Pd (II), Zr (II), Zr (IV) or Pt
(II)；The anion of transition metal salt is NO3 -、SO4 2-、Cl-、Br-Or acetylacetone,2,4-pentanedione anion.
3. a kind of application of the amino phenolic group phosphorus ligand according to claim 2 in vinyl polymerization and oligomerisation, feature exist
In: the molar ratio of phosphorus ligand and transistion metal compound is 0.1:1~10:1 in complex or mixture.
4. a kind of application of the amino phenolic group phosphorus ligand according to claim 2 in vinyl polymerization and oligomerisation, feature exist
In the catalyst of: complex or mixture as major catalyst and co-catalyst composition, co-catalyst be alkyl aluminum, aikyiaiurnirsoxan beta and
One of chlorination alkyl aluminum or a variety of combinations；The molar ratio of aluminium in the metal and co-catalyst of major catalyst be 1:1~
1:5000。
5. a kind of application of the amino phenolic group phosphorus ligand according to claim 4 in vinyl polymerization and oligomerisation, feature exist
In: alkyl aluminum is one of trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and tri-n-hexyl aluminum or a variety of combinations；Alumina
Alkane is one of methylaluminoxane, ethylaluminoxane and isobutyl aluminium alkoxide or a variety of combinations；Chlorination alkyl aluminum is ethyl
One of sesquichloride, aluminium diethyl monochloride, sesquialter aluminium diethyl monochloride and ethylaluminium dichloride or a variety of combinations.
6. a kind of amino phenolic group phosphorus ligand according to claim 1 is in polymerization, combined polymerization and the oligomerisation reaction of catalysis ethylene
In application, it is characterised in that: with the monomer of ethylene copolymerization be C18 end alkene below, acrylonitrile, acrylamide, N, N- bis-
Methacrylamide, methyl acrylate, ethyl acrylate or n-butyl acrylate.
7. a kind of amino phenolic group phosphorus ligand according to claim 6 is in polymerization, combined polymerization and the oligomerisation reaction of catalysis ethylene
In application, it is characterised in that: in catalyzed ethylene polymerization, combined polymerization, oligomerization, polymerization temperature be 0~100 DEG C, polymerization
Pressure is 0.1~0.5MPa.
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| CN102040624A (en) * | 2009-10-19 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof |
| US9127097B2 (en) * | 2012-01-25 | 2015-09-08 | Nova Chemicals (International) S.A. | P-N-P ligand |
| CN106146555A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of ligand compound and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040624A (en) * | 2009-10-19 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof |
| US9127097B2 (en) * | 2012-01-25 | 2015-09-08 | Nova Chemicals (International) S.A. | P-N-P ligand |
| CN106146555A (en) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of ligand compound and its preparation method and application |
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| 基于[PNP]配体的铬催化剂体系选择性催化乙烯齐聚的研究进展;刘睿 等;《有机化学》;20150526;第35卷;第1861-1888页 * |
| 带有PNP配体的铬系催化剂在乙烯选择性齐聚中的研究进展;刘振华 等;《能源化工》;20160831;第37卷(第4期);第1-10页 * |
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