CN1280315C - Post-transition metal catalytic system for synthesizing branched polyethylene and its use - Google Patents

Abstract

The present invention relates to a post-transition metal catalytic system for synthesizing branched polyethylene, and the use thereof, which belongs to a post-transition metal compounding catalytic system for preparing branched polyethylene, and the use thereof. In the present invention, the interference problem between two catalysts in a main catalyst is solved, and the same cocatalyst can be used. The catalytic system is composed of the main catalyst and the cocatalyst, wherein the main catalyst comprises an oligomerization catalyst and a copolymerization catalyst. The oligomerization catalyst is a post-transition metal catalyst having small substituent group steric hindrance, and the copolymerization catalyst is a post-transition metal catalyst having large substituent group steric hindrance. The catalytic system has favorable catalytic activity, and the activity of the catalysts is from 1*10<5> to 1*10<6>gPE/(mol. h. M), and a monomer insertion rate is from 7 to 3%. Ethylene is used as a unique polymerization monomer to carry out serial connection and polymerization by the main catalyst under the action of the cocatalyst-alkyl aluminoxane to obtain branched polyethylene resin. A molecular weight range of the branched polyethylene resin is from 1*10<5> to 3*10<5>, and a melting point is from 122 to 103 DEG C.

Description

The rear transition metal catalyst system and the application thereof of synthesizing branched polyethylene

Technical field

The invention belongs to the composite catalyst system of rear transition metal and the purposes of preparation branched polyethylene.Regulate and control the performance of polymerisate by the different catalyzed reaction proportioning of conversion, catalyst structure and differential responses condition, realize the controllable structure of polymkeric substance.

Background technology

Branched polyethylene is the polyethylene kind that a class has excellent properties, can be divided into short-chain branched polyethylene and long-chain branched polyethylene according to the length of side chain.Short-chain branched polyethylene refers generally to linear low density polyethylene (LLDPE).It is to be made by ethene and alpha-olefin copolymer, mainly is to be obtained by ethene and butene-1 copolymerization.It occupies about 40% of polyethylene market with the material property of excellence at present.Long-chain branched polyethylene has than the better moulding processability of LLDPE, have elasticity and plasticity simultaneously (degree of branching high be elastomerics, what the degree of branching was low is plastomer), the optical property and the mechanical property of low, the narrow molecular weight distribution of density, excellent skill.Because branched polyethylene has excellent tearing toughness, tensile strength, paracentesis resistance and environmental stress cracking resistance, so, in the production of the coating material of cable and corrosion-resistant, stress crack resistant container very big advantage is arranged in medicine equipment, thin film fabrication.Catalyzer and polymerization technique are the keys of branched polyethylene development always, the progress of catalyzer at present develops into single site catalysts by traditional many site catalysts, this not only makes activity of such catalysts have and increases substantially, can control product density, particle form and globule size, can also accurately control relative molecular mass and form distribution, thus the performance of regulation and control rosin products.

Adopting in-situ polymerization technology is an important method of preparation branched polyethylene, home position polymerization reaction is introduced catalyst for oligomerization and catalyst for copolymerization exactly simultaneously in same reactor, with aluminum alkyls or alkylaluminoxane is promotor, ethene is under the monomeric condition of unique charging, and the preparation branched polyethylene is finished in polyphone catalysis.Beach and Kissin adopt Ti (OR) ₄As ethylene dimerization catalyzer, Z-N catalyzer is catalyst for copolymerization, is the research that promotor has carried out the polymerization catalyzed reaction of ethene original position with the aluminum alkyls, but has shortcomings such as catalytic activity is low, copolymerization performance is poor, side chain skewness.(J Polym SciA:Polym Chem[J], 1984,22; 3027～3042, J Polym Sci A:Polym Chem[J], 1986,24:1069 ~ 1084) people such as Bazen adopts (C ₆H ₅B-OEt) ₂ZrCl ₂Being catalyst for oligomerization, is that catalyst for copolymerization and in-situ copolymerization have made long-chain branched polyethylene with the metallocene of copolymerization performance excellence, is the catalyst for oligomerization instability but exist, and the alpha-olefin poor selectivity of generation can not well be inserted into shortcomings such as polymkeric substance.(J Am Chem Soc, 1998,120:1082～1084) Chinese Academy of Sciences's chemistry Hu Youliang of institute adopts different catalyst for oligomerization and metallocene catalysts to carry out composite, make short-chain branched polyethylene, but had the used promotor of catalyst for oligomerization and catalyst for copolymerization problem (polymer journal, 2001 such as do not match, 4:471～475, Science Bulletin 2001,46:1264～1267, Science Bulletin 2001,15:1261～1264).

Reported the ability that has catalysis in olefine polymerization under the existence of many imines of iron cobalt class agent MAO, MMAO respectively from Brookhart in 1998 and Gibson, this class catalyst olefinic polymerization not only has high catalytic activity, can also be by changing the structure of catalyzer, regulate the size and the distribution of polymer molecular weight, and late transition metal catalyst has weak oxytropism, can with polar monomer copolymerization, catalyst themselves such as stablizes, is easy to synthesize, with low cost at advantage.It is that catalyst for oligomerization, metallocene catalyst are that catalyst for copolymerization has carried out the long-chain branched polyethylene that a large amount of dutys got the degree of branching＜3% for in-situ copolymerization in the presence of MAO that people such as Qujiada and Hu Youliang adopts rear transition metal, has the compatibleness of two kinds of catalyzer of polymerization catalyst system and problem such as mutual interference mutually.(Macromolecules 2001,34:2411-2417; Science Bulletin 2001,15:1264～1267; The polymer journal, 2001,6:751～754).

Up to now, still do not have that to adopt back transition iron system, cobalt be that the diimide pyridine complex is that catalyst for oligomerization and catalyst for copolymerization have carried out the report that in-situ copolymerization prepares branched polyethylene, owing to the back transition catalyst system that is all that adopts, the interference of having avoided two kinds of catalyzer of success is developed this catalyst system for this reason and is had important and practical meanings.

Summary of the invention

The invention solves in the catalyst system, the interference of two kinds of catalyzer and the problem of compatibleness, a kind of rear transition metal bifunctional catalysis system is provided, promptly use same kind of promotor, activate simultaneously for two kinds of Primary Catalystss, thereby make the in-situ copolymerization reaction obtain branched polyethylene.

Technical scheme of the present invention:

The rear transition metal catalyst system of synthesizing branched polyethylene comprises following composition:

Primary Catalysts: form by catalyst for oligomerization and catalyst for copolymerization.According to the late transition metal complex catalyst part at the different sterically hindered different polymerization properties that shows, catalyst for oligomerization is for having small-substituent sterically hindered late transition metal catalyst, and catalyst for copolymerization is the sterically hindered late transition metal catalyst with large-substituent.

The structure of Primary Catalysts is:

R wherein ₁, R ₂, R ₃Be respectively substituted radical, M is rear transition metal Fe or Co, and X is different halo group;

Promotor: be alkylaluminoxane;

The mol ratio of catalyst for oligomerization and catalyst for copolymerization is 1: 20～10: 1 in the Primary Catalysts;

The mol ratio of promotor and Primary Catalysts is 10000: 1～100: 1;

This catalyst system composition, all each component concentration sums are 100%.

Main performance index: during synthesizing branched polyethylene, its catalytic activity is 1 * 10 ⁵～1 * 10 ⁶GPE/ (mo1hM), monomer insertion rate is 7～3%.

Need to prove: the mol ratio of catalyst for oligomerization and catalyst for copolymerization can be 4～9: 1 in the Primary Catalysts; Promoter aluminium alkyl oxygen alkane is methylaluminoxane MAO, and the mol ratio of promotor and Primary Catalysts represents that with Al/M its value is 2000: 1～250: 1.

Above-mentioned Primary Catalysts late transition metal complex is to have the anhydrous of the part of schiff base structure and rear transition metal M (Fe or Co) or contain the three tooth title complexs that the halogenide of crystal water forms, and wherein the halo radicals X is the halo group of chlorine or bromine.The substituent R of schiff base structure part ₁A kind of in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.R ₂A kind of in chlorine halogeno-group, bromine halogeno-group, hydrogen base, alkoxyl group, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl; R wherein ₂Alkoxyl group is a kind of in methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, the tert.-butoxy; R ₃Can be in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl a kind of.R ₁, R ₂And R ₃Be identical or different group.

The rear transition metal catalyst system main application of synthesizing branched polyethylene of the present invention is the preparation branched polyethylene, and promptly the catalyzed ethylene in-situ polymerization becomes branched polyethylene under the effect of promotor.Its reaction principle is that ethene is only monomer, and the alpha-olefin original position that is generated by catalyst for oligomerization catalyzed ethylene monomer is inserted into, in the poly main chain by catalyst for copolymerization catalyzed ethylene reaction generation, and the branched polyethylene that obtains having certain degree of branching; Its molecular weight 1 * 10 ⁵～3 * 10 ⁵, fusing point is 122～103 ℃; Its concrete preparation method is as follows:

By prescription metering weighing catalyst for oligomerization and catalyst for copolymerization, its concentration is respectively 1 * 10 ^-5～1 * 10 ^-3Mol/L joins in the test tube of protection of inert gas, and the toluene that adds dehydration, deoxidation treatment again dissolves catalyzer fully, stirs 30 minutes;

In addition, in process dewaters the reactor there-necked flask of deoxygenation, add the toluene of dehydration, deoxidation treatment, under agitation feed ethene, be metered into promotor MAO by prescription;

Make system keep even, constant temperature with adding catalyst for oligomerization and the catalyst for copolymerization that beginning had been handled in the above-mentioned there-necked flask again, stirring;

Polyreaction finished after 30 minutes, added 10% acidifying ethanol termination at last, the washing and filtering polymkeric substance, and vacuum-drying 6h in 70 ℃ of vacuum drying ovens obtains branched polyethylene again.

Beneficial effect:

The invention provides a kind of rear transition metal catalyst system for preparing branched polyethylene, because catalyst for oligomerization and catalyst for copolymerization in the Primary Catalysts, all adopt the rear transition metal catalyst system, thereby successfully avoided catalyst for oligomerization and the interference of catalyst for copolymerization and the problem of compatibleness in the Primary Catalysts.In addition, owing to use with a kind of promotor, activate simultaneously for two kinds of Primary Catalystss, make the in-situ copolymerization synthesizing branched polyethylene, the copolymerization of its catalyst system is active high, and catalytic activity is 1 * 10 ⁵～1 * 10 ⁶GPE/ (molhM) M (Fe or Co), monomer insertion rate height is 7～3%.Life of catalyst is long, and this catalyzer is synthetic, cheap easily, can obtain good polymerization result at normal temperatures, and polymerization technique is simple, is easy to control.The branched polyethylene that obtains, its molecular weight is higher, and molecular weight is 1 * 10 ⁵～3 * 10 ⁵, fusing point is 122～103 ℃.

Embodiment

Embodiment 1-11 catalyst component and polymerization result see Table 1

Table 1 example 1-10 catalyst component and polymerization result

Embodiment	Catalyst for oligomerization				Catalyst for copolymerization				Help catalysis	Al/M	T ℃	Active (1 * 10 5g gPE/(mol·h·M)	T m(℃)	Mw	Monomer insertion rate * 100
																R 1	R 2	R 3	M	R 1	R 2	R 3	M
	1 2 3 4 5 6 7 8 9 10 11	CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3 CH 3	H Cl C 2H 5 C 3H 7 H Br OCH 3 Br H iPr	H H H H H H H H H H	Fe Fe Fe Fe Fe Fe Co Co Co Co	CH 3 CH 3 CH 3 CH 3 iPr CH 3 CH 3 t-Bu CH 3 CH 3 CH 3	H H Br Br H H H Br Br H H	CH 3 CH 3 CH 3 CH 3 iPr CH 3 CH 3 t-Bu CH 3 CH 3 CH 3	Fe Fe Fe Co Fe Fe Fe Fe Co Co Fe	EAO EAO MAO MAO MAO MAO EAO MAO EAO MAO MAO	500 1000 500 100 250 1500 10000 5000 2500 2000 2000	30 30 20 20 30 40 30 50 40 30 30	16.1 11.2 35.6 22.7 4.32 36.53 10.2 15.5 7.32 5.4 30.2	103 121 116 113 120 121 115 117 122 120 135	23000 19000 30000 25000 32000 25000 19000 16000 15000 14000 20000																5 4 7 6 5 6 7 7 3 4

Annotate: EAO-ethyl aikyiaiurnirsoxan beta; The MAO-methylaluminoxane; The iPr sec.-propyl; The t-Bu-tertiary butyl; OCH ₃-alkoxyl group.

The polymerization result of embodiment 11 for adopting the reaction of late transition metal catalyst ethylene homo to obtain

Embodiment specifies as follows:

Embodiment 1:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; each 0.5g of 6-diacetyl pyridine, 2-aminotoluene 2ml and 2; 6-xylidine 4ml; with above-mentioned a 2; 6-diacetyl pyridine and 2-aminotoluene join in the round-bottomed flask; another part 2,6-diacetyl pyridine and 2,6-xylidine join in another round-bottomed flask; add (30ml) 1 more respectively; the 2-ethylene dichloride respectively adds five formic acid at last, at 50 ℃ of reflux cooling 48h; evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part A and the B.Take by weighing each 0.3g of part A and B; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the 50mg metal halide; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter at last, vacuum-drying 2h under the room temperature obtains blue iron catalyst for oligomerization catA and catalyst for copolymerization catB.

(2) ethene home position polymerization reaction

With the there-necked flask of 250ml, replace twice with ethene again three times through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 30 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Wherein the mol ratio of promotor and main catalytic is Al/M=500, and rear transition metal M is (Fe+Fe); Catalyst for oligomerization and copolymerization catalyst molar ratio are Fe _Oligo/ Fe _Copoly=10; Polyreaction 30min adds 10% acidifying ethanol at last and stops.The washing and filtering polymkeric substance, dry 6h in 70 ℃ of vacuum drying ovens obtains polymkeric substance branched polyethylene 0.4g again.The fusing point of its polymkeric substance branched polyethylene is 103 ℃, Mw=23000.

This catalyst system, its activity are 16.1 * 10 ⁵GPE/ (molhM), monomeric insertion rate is 5%.

Embodiment 2:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; each 0.5g of 6-diacetyl pyridine, 2-methyl-4 chloro aniline (3ml) and 2; 6-xylidine (4ml); with above-mentioned a 2; 6-diacetyl pyridine and 2-methyl-4 chloro aniline join in the round-bottomed flask; another part 2,6-diacetyl pyridine and 2,6-xylidine join in another round-bottomed flask; add (30ml) 1 more respectively; the 2-ethylene dichloride respectively adds five formic acid at last, at 50 ℃ of reflux cooling 48h; evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part C and the D.Take by weighing each 0.3g of part C and D; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 45mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtain blue iron catalyst for oligomerization catC and catalyst for copolymerization catB.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 30 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=1000M (Fe+Fe); Fe _Oligo/ Fe _Copoly=0.05; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.3g.121 ℃ of the fusing points of its polymkeric substance branched polyethylene, Mw=19000.

This catalyst system, its activity are 11.2 * 10 ⁵GPE/ (molhM), monomeric insertion rate is 4%.

Embodiment 3:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; each 0.5g of 6-diacetyl pyridine; 2-methyl-4 ethylaniline (2ml) a 2; 6-diformazan-4 bromo aniline (3ml); with above-mentioned a 2,6-diacetyl pyridine and 2-methyl-4 ethylaniline join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; 6-diformazan-4 bromo aniline joins in another round-bottomed flask, adds (30ml) 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part D and the E.Take by weighing each 0.3g of part E and F; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 44mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtaining blue iron catalyst for oligomerization and catalyst for copolymerization is catD and catE.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 20 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=500M (Fe+Fe); Fe _Oligo/ Fe _Copoly=0.1; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.5g.116 ℃ of melting point polymers, Mw=30000.

This catalyst system, its activity 35.6 * 10 ⁵GPE/ (molhM).Monomeric insertion rate is 7%.

Embodiment 4:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; 6-diacetyl pyridine each (0.5g); 2-methyl-4 propyl group aniline (3ml) a 2; 6-diformazan-4 bromo aniline (3ml); with above-mentioned a 2,6-diacetyl pyridine and 2-methyl-4 propyl group aniline join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; 6-diformazan-4 bromo aniline joins in another round-bottomed flask, adds 30ml 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part F and the E.Take by weighing each 0.3g of part G and H; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 50mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, the cobalt that obtains blue iron catalyst for oligomerization and green is that catalyst for copolymerization is catF and catE.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 20 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization successively.Al/M=100M (Fe+Co); Fe _Oligo/ Co _Copoly=0.12; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.6g.113 ℃ of melting point polymers, Mw=25000.

This catalyst system, its activity 22.7 * 10 ⁵GPE/ (molhM), monomeric insertion rate is 6%

Embodiment 5:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-aminotoluene (2ml) a 2; 6-diisopropyl aniline (4ml); with above-mentioned a 2,6-diacetyl pyridine and 2-aminotoluene join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; the 6-diisopropyl aniline joins in another round-bottomed flask, adds (30ml) 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that a certain amount of low-temperature methanol is freezing to be obtained till light yellow crystal part A and the G.Take by weighing each 0.3g of ligand i and J; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 50mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtain blue iron catalyst for oligomerization and catalyst for copolymerization, i.e. catA and catG.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 30 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=250M (Fe+Fe); Fe _Oligo/ Fe _Copoly=0.05; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.7g.Melting point polymer is 120 ℃, Mw=32000.

This catalyst system, its activity 4.32 * 10 ⁵GPE/ (molhM), monomeric insertion rate is 5%.

Embodiment 6:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-methyl-4 bromo aniline (2ml) a 2; 6-xylidine (4ml); with above-mentioned a 2,6-diacetyl pyridine and 2-aminotoluene join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; the 6-xylidine joins in another round-bottomed flask, adds (30ml) 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part H and the B.Take by weighing each 0.3g of part K and L; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 47mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtain blue iron catalyst for oligomerization and catalyst for copolymerization, i.e. catH and catB.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 40 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=1500M (Fe+Fe); Fe _Oligo/ Fe _Copoly=4; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.6g.121 ℃ of melting point polymers, Mw=25000.

This catalyst system, its activity 36.53 * 10 ⁵GPE/ (molhM), monomeric insertion rate is 6%.

Embodiment 7:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-methyl-4 anisidine (3ml) a 2; 6-xylidine (4ml); with above-mentioned a 2,6-diacetyl pyridine and 2-methyl-4 anisidine join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; the 6-xylidine joins in another round-bottomed flask, adds (30ml) 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that low-temperature methanol is freezing to make it to obtain light yellow crystal part M and N.Take by weighing each 0.3g of part C and B; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 50mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtaining green cobalt is that catalyst for oligomerization and blue iron are catalyst for copolymerization, i.e. catI and catB.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 30 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=10000M (Co+Fe); Co _Oligo/ Fe _Copoly=9; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.4g.115 ℃ of melting point polymers, Mw=19000, monomeric insertion rate is 7%.

This catalyst system, its activity 10.2 * 10 ⁵GPE/ (molhM).

Embodiment 8:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-methyl-4 bromo aniline (3ml) a 2; 6-di-tert-butyl aniline (4ml); with above-mentioned a 2,6-diacetyl pyridine and 2-methyl-4 bromo aniline join in the round-bottomed flask, another part 2; 6-diacetyl pyridine and 2; 6-two-tertiary butyl aniline joins in another round-bottomed flask, adds (30ml) 1,2-ethylene dichloride more respectively; respectively add five formic acid at last; at 50 ℃ of reflux cooling 48h, evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part C and the J.Take by weighing each 0.3g of part M and N; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 49mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtaining green cobalt is that catalyst for oligomerization and blue iron are catalyst for copolymerization, i.e. catI and catJ.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 50 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=5000M (Co+Fe); Co _Oligo/ Fe _Copoly=8; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.5g.117 ℃ of melting point polymers, Mw=16000, monomeric insertion rate is 7%.

This catalyst system, its activity 15.5 * 10 ⁵GPE/ (molhM).

Embodiment 9:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-aminotoluene (3ml) a 2; 6-xylidine (4ml) is with above-mentioned a 2; 6-diacetyl pyridine and 2-methyl-4 bromo aniline join in the round-bottomed flask; another part 2,6-diacetyl pyridine and 2,6-xylidine join in another round-bottomed flask; add (30ml) 1 more respectively; the 2-ethylene dichloride respectively adds five formic acid at last, at 50 ℃ of reflux cooling 48h; evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part O and the P.Take by weighing each 0.3g of part A and B; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 45mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtain green cobalt catalyst for oligomerization and catalyst for copolymerization, i.e. catK and catL.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 50 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=2500, M (Co+Fe); Co _Oligo/ Fe _Copoly=8; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.5g.122 ℃ of melting point polymers, Mw=15000, monomeric insertion rate is 3%.

This catalyst system, its activity 7.32 * 10 ⁵GPE/ (molhM).

Embodiment 10:

(1) catalyzer is synthetic

Under the room temperature; take by weighing two part 2; two parts of 6-diacetyl pyridines (0.5g); 2-methyl-4 isopropyl aniline (3ml) a 2; 6-xylidine (4ml) is with above-mentioned a 2; 6-diacetyl pyridine and 2-methyl-4 isopropyl aniline join in the round-bottomed flask; another part 2,6-diacetyl pyridine and 2,6-two-monomethylaniline join in another round-bottomed flask; add (30ml) 1 more respectively; the 2-ethylene dichloride respectively adds five formic acid at last, at 50 ℃ of reflux cooling 48h; evaporating solvent adds that low-temperature methanol is freezing to be made it to obtain till light yellow crystal part M and the B.Take by weighing each 0.3g of part M and N; join respectively in two the single port flasks that contain 20ml THF that adopt argon shield; each adds the metal halide of 50mg; 2h is at room temperature carried out in reaction; reaction finishes to add the 20ml diethyl ether; filter vacuum-drying 2h under the room temperature at last, obtain green cobalt catalyst for oligomerization and catalyst for copolymerization, i.e. catM and catL.

(2) ethene home position polymerization reaction

The there-necked flask of 250ml is replaced twice with ethene three times again through nitrogen replacement, add the toluene that 50ml refluxes through sodium Metal 99.5, stir and be warmed up to 50 ℃, add promotor, catalyst for oligomerization, catalyst for copolymerization.Al/M=2000, M (Co+Fe); Co _Oligo/ Fe _Copoly=8; The acidifying ethanol of the last adding 10% of reaction 30min stops.Filtration, 70 ℃ of vacuum-drying 6h obtain polymkeric substance 0.5g.120 ℃ of melting point polymers, Mw=14000, monomeric insertion rate is 4%.

This catalyst system, its activity 5.4 * 10 ⁵GPE/ (molhM).

Comparative example (embodiment 11):

Present embodiment has been enumerated, the polymerization result that adopts the reaction of late transition metal catalyst ethylene homo to obtain.Compare with the present invention, its fusing point is apparently higher than the melting point polymer of copolyreaction.

Claims (10)

1. the rear transition metal catalyst system of synthesizing branched polyethylene is characterized in that this catalyst system is made up of following material:

Primary Catalysts: be made up of catalyst for oligomerization and catalyst for copolymerization, catalyst for oligomerization is for having small-substituent sterically hindered late transition metal catalyst, and catalyst for copolymerization is for having large-substituent sterically hindered late transition metal catalyst, and the structure of Primary Catalysts is:

R wherein ₁, R ₂, R ₃Be respectively substituted radical, M is rear transition metal Fe or Co, and X is the halo group;

Promotor: be alkylaluminoxane;

The mol ratio of catalyst for oligomerization and catalyst for copolymerization is 1: 20～10: 1 in the Primary Catalysts;

The mol ratio of promotor and Primary Catalysts is 10000: 1～100: 1;

This catalyst system composition, all each component concentration sums are 100%;

Main performance index: during synthesizing branched polyethylene, its catalytic activity is 1 * 10 ⁵～1 * 10 ⁶GPE/ (molhM), monomer insertion rate is 7～3%.

2. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that the mol ratio of catalyst for oligomerization and catalyst for copolymerization is 4～9: 1 in the Primary Catalysts of this catalyst system.

3. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that described promoter aluminium alkyl oxygen alkane is methylaluminoxane MAO, the mol ratio of promotor and Primary Catalysts represents that with Al/M its value is 2000: 1～250: 1.

4. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that described Primary Catalysts late transition metal complex is to have the part of schiff base structure and rear transition metal M is the three tooth title complexs that the anhydrous of Fe or Co or the halogenide that contains crystal water form, wherein the halo radicals X is the halo group of chlorine or bromine.

5. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that described Primary Catalysts substituent R ₁A kind of in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.

6. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that described Primary Catalysts substituent R ₂A kind of in chlorine halogeno-group, bromine halogeno-group, hydrogen base, alkoxyl group, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl.

7. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 6, it is characterized in that described alkoxyl group is a kind of in methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, the tert.-butoxy.

8. according to the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1, it is characterized in that described Primary Catalysts substituent R ₃Can be in methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl a kind of.

9. according to the rear transition metal catalyst system of claim 1,5,6,7 or 8 described synthesizing branched polyethylenes, it is characterized in that described Primary Catalysts substituent R ₁, R ₂And R ₃Be identical or different group.

10. the rear transition metal catalyst system of the described synthesizing branched polyethylene of claim 1 is used to prepare the purposes of branched polyethylene, that is: be only monomer with ethene, the alpha-olefin original position that is generated by catalyst for oligomerization catalyzed ethylene monomer is inserted into, in the poly main chain by catalyst for copolymerization catalyzed ethylene reaction generation, obtain branched polyethylene; Its molecular weight is

1 * 10 ⁵～3 * 10 ⁵, fusing point is 122～103 ℃; Its concrete preparation method is as follows:

By prescription metering weighing catalyst for oligomerization and catalyst for copolymerization, its concentration is respectively 1 * 10 ^-5～1 * 10 ^-3Mol/L joins it in test tube of protection of inert gas, adds the toluene of dehydration, deoxidation treatment again, and catalyzer is dissolved fully, stirs 30 minutes;

In addition, in process dewaters the reactor there-necked flask of deoxygenation, add the toluene of dehydration, deoxidation treatment, under agitation feed ethene, be metered into promotor MAO by prescription;

Make system keep even, constant temperature with adding catalyst for oligomerization and the catalyst for copolymerization that beginning had been handled in the above-mentioned there-necked flask again, stirring;

Polyreaction finished after 30 minutes, added 10% acidifying ethanol termination at last, the washing and filtering polymkeric substance, and vacuum-drying 6h in 70 ℃ of vacuum drying ovens obtains branched polyethylene again.