CN103421133A - Rare-earth metal catalysis system for catalyzing high-stereoregularity polymerization of alpha-olefin - Google Patents

Abstract

The invention belongs to a rare-earth metal catalytic system for catalyzing the polymerization of alpha-olefin with high stereoregularity. The system is composed of a trivalent rare earth metal complex containing a neutral ligand, an alkylating agent and an organic boron salt; the catalytic reaction monomer is a molecular formula of CH ₂ =CH(CH ₂ ) _n CH ₃ (n=1～9 ) α-olefins, such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, etc.; the ratio of alkylating agent to rare earth metal complex is 2 to 1000:1 , the ratio of organoboron salt to rare earth metal complex is 0-5:1, and the polymerization temperature is 25-80°C. The resulting polymer has an ultrahigh molecular weight (>1 million) and an almost completely isotactic structure (mmmm>99%). The catalytic system has good thermal stability, and can still catalyze the stereoregular polymerization of α-olefin even at a high temperature of 80°C.

Description

A Rare Earth Metal Catalytic System Catalyzing High Stereoregular Polymerization of α-Olefins

technical field

The invention relates to a rare earth metal catalyst system for catalyzing the polymerization of alpha-olefin with high stereoregularity.

Background technique

As one of the important synthetic materials, polyolefin resin directly affects the development of national economy and the improvement of national consumption level, especially closely related to downstream industries such as packaging, agriculture, construction, automobile, electrical and electronics. The coordination polymerization of olefins is carried out using a catalytic system composed of transition metal compounds and organometallic compounds. This kind of catalytic system has stereospecificity, and can prepare polymer materials with various regular chain structures. In the early 1950s, the appearance of Ziegler-Natta catalytic system and coordination polymerization opened up a new field of polymer synthesis, and promoted the establishment and development of ethylene low-pressure polymerization and propylene directional polymerization industries. Since the 1960s, many experts engaged in the research of metal-organic olefin polymerization catalysts have won the Nobel Prize in Chemistry.

In practical applications, using the traditional heterogeneous Ziegler-Natta catalytic system and Phillips catalytic system, as well as the later developed homogeneous metallocene catalyst and homogeneous non-metallocene catalyst, various types of polyolefin products can be obtained, such as low Density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and high regularity polypropylene (PP), etc. Among these catalytic systems, Group IVB metals (titanium, zirconium, and hafnium) are the most studied as coordination centers, followed by some late transition metals (nickel, palladium, iron, cobalt, etc.), and rare earth metal complexes are used. There are relatively few studies on catalyzed α-olefin polymerization.

my country is a country rich in rare earth resources. The reserves and output of rare earths rank first in the world. The comprehensive utilization of rare earth resources is an important topic of current research. Although rare-earth metal catalysts can catalyze the directional polymerization of styrene and conjugated dienes, and have achieved a series of impressive results, there are few studies on their use to catalyze the stereoregular polymerization of α-olefins. For example, the binary catalytic system (GB943195 (1960)) composed of ScCl ₃ or YCl ₃ and alkylaluminum or tetraalkylaluminum lithium developed by the British Courtalds company can catalyze the polymerization of ethylene or propylene, but the catalytic activity of this system is low. And there is no mention of stereoselectivity for propylene polymerization in the patent. A class of catalytic systems based on trioxazoline chelated trialkyl scandium complexes [( ⁱ Pr-trisox)Sc(CH ₂ SiMe ₂ R) ₃ ](R=Me,Ph) reported by Gade’s research group can achieve high Active and highly stereoregular catalysts for the polymerization of 1-hexene (Ward, BD; Bellemin-Laponnaz, S.; Gade, LH Angew. Chem. Int. Ed., 2005, 44, 1668–1671.). In addition, people have also developed some rare earth metal catalytic systems for catalyzing ethylene polymerization (US4384982 (1983), US4567153 (1986), US4575538 (1986), US4699962 (1987), US4791086 (1988), US5110884 (1992), US5173464 (1992) , US5182244 (1993), US5260244 (1993), US5350816 (1994), US5391659 (1995)). However, the catalytic activity of these systems is relatively low, and the stereoselective polymerization of α-olefins is not mentioned in the patent.

Contents of the invention

The object of the present invention is to provide a rare earth metal catalyst system for catalyzing the high stereoregularity polymerization of α-olefins, which comprises a trivalent rare earth metal complex containing a neutral ligand, an alkylating agent and an organic boron salt.

The trivalent rare earth metal complex containing neutral ligands has a molecular formula of (L) _n LnX ₃ , where:

The rare earth metal element Ln is scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium ( Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu), preferably scandium (Sc);

The neutral ligand L is dimethyl ether, methyl ethyl ether, diethyl ether, n-propyl ether, n-butyl ether, methyl butyl ether, ethyl butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 2,5-dimethyltetrahydrofuran , tetrahydropyran, 2-methyltetrahydropyran, 2,5-dimethyltetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, ethylene glycol Dimethyl ether, 15-crown (ether)-5, 18-crown (ether)-6, dicyclohexane-18-crown (ether)-6, dibenzo-18-crown (ether)-6, Tetrahydrothiophene, 2-methyltetrahydrothiophene, 2,5-dimethyltetrahydrothiophene, NNN'N'-tetramethylethylenediamine, pyridine, 2-methylpyridine, 2,6-dimethyl Pyridine, 1,3,5-Trimethyl-1,3,5-Triazacyclohexane, 1,3,5-Triethyl-1,3,5-Triazacyclohexane, 1, 3,5-triisopropyl-1,3,5-triazacyclohexane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7 -Triethyl-1,4,7-triazacyclononane, 1,4,7-triisopropyl-1,4,7-triazacyclononane, 1,4,7,10- Tetraazacyclododecane, 2,6-bis(4'-methyl-2'-oxazolinyl)pyridine, 2,6-bis(4'-ethyl-2'-oxazolinyl) Pyridine, 2,6-bis(4'-isopropyl-2'-oxazolinyl)pyridine, 1,1,1-tris(4'-methyl-2'-oxazolinyl)ethane, 1,1,1-tris(4'-ethyl-2'-oxazolinyl)ethane or 1,1,1-tris(4'-isopropyl-2'-oxazolinyl)ethane , preferably tetrahydrofuran, ethylene glycol dimethyl ether, tetrahydrothiophene or pyridine;

X is one or both of halogen, alkyl, amino, alkoxy, aryloxy, carboxyl, nitro, BH ₄ ^- or BF ₄ ^- ;

The halogen is selected from F ^- , Cl ^- , Br ^- or I ^- ;

The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, allyl, CH ₂ SiMe ₃ , CH ₂ C ₆ H ₄ -6-N( CH ₃ ) ₂ , CH(SiMe ₃ ) ₂ or CH ₂ C ₆ H ₅ ;

The amino group is selected from N(CH ₃ ) ₂ , N(CH ₂ CH ₃ ) ₂ , N[CH(CH ₃ ) ₂ ] ₂ , N[C(CH ₃ ) ₃ ] ₂ , N[Si(CH 3 ) 2 , ₃ ) ₃ ] ₂ or N[SiH(CH ₃ ) ₂ ] ₂ ;

The alkoxy group is selected from OCH ₃ , OCH ₂ CH ₃ , OCH(CH ₃ ) ₂ or OC(CH ₃ ) ₃ ;

The aryloxy group is selected from OC ₆ H ₅ , OC ₆ H ₃ -2,6-(CH ₃ ) ₂ , OC ₆ H ₃ -2,6-(CH ₂ CH ₃ ) ₂ , OC ₆ H ₃ -2,6-(CH(CH ₃ ) ₂ ) ₂ , OC ₆ H ₃ -2,6-(C(CH ₃ ) ₃ ) ₂ , OC ₆ H ₃ -4-CH ₃ -2,6-(C (CH ₃ ) ₃ ) ₂ or OC ₆ H ₃ -2,4,6-(C(CH ₃ ) ₃ ) ₂ ;

The carboxyl group is selected from acetyloxy, propionyloxy, hexanoyloxy, 2-ethylhexanoyloxy, octanoyloxy, neodecanoyloxy or cycloalkanoyloxy;

The alkylating agent is an alkylaluminum with a molecular formula of _AlR3 , an alkylaluminum hydride with a molecular formula of _HAlR2 , an alkylaluminum chloride with a molecular formula of _R2AlCl , aluminoxane, an alkylmagnesium or an alkylzinc ;

The described molecular formula is AlR ₃ alkylaluminum is trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisopropylaluminum, triisobutylaluminum, tripentylaluminum , trihexylaluminum, tricyclohexylaluminum, trioctylaluminum, triphenylaluminum, tri-p-cresylaluminum, tribenzylaluminum, ethyldibenzylaluminum, ethyldi-p-tolylaluminum or diethylbenzyl base aluminum; preferably triisobutyl aluminum; the molar ratio to the trivalent rare earth metal complex containing neutral ligands is 2-1000:1, preferably 5-100:1.

The described molecular formula is that the alkyl aluminum hydride of _HAlR2 is dimethyl aluminum hydride, diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisopropyl aluminum hydride, diisobutyl aluminum hydride Aluminum hydride, dipentyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, ethylbenzyl aluminum hydride Aluminum or ethyl-p-tolyl aluminum hydride;

Described molecular formula is that the alkyl aluminum chloride of R ₂ AlCl is dimethyl aluminum chloride, diethyl aluminum chloride, di-n-propyl aluminum chloride, di-n-butyl aluminum chloride, diisopropyl chloride Aluminum chloride, diisobutylaluminum chloride, dipentylaluminum chloride, dihexylaluminum chloride, dicyclohexylaluminum chloride, dioctylaluminum chloride, diphenylaluminum chloride, di-p-tolyl chloride Aluminum chloride, dibenzyl aluminum chloride, ethyl benzyl aluminum chloride or ethyl p-tolyl aluminum chloride;

The aluminoxane is methylalumoxane, ethylalumoxane, n-propylalumoxane, n-butylalumoxane, isopropylalumoxane or isobutylalumoxane;

Described magnesium alkyl is dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, di-n-butylmagnesium, diisopropylmagnesium, diisobutylmagnesium, dipentylmagnesium, dihexylmagnesium, Dicyclohexylmagnesium, dioctylmagnesium, diphenylmagnesium, di-p-tolylmagnesium, dibenzylmagnesium, ethylbenzylmagnesium or ethylp-tolylmagnesium;

Described alkyl zinc is dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisopropyl zinc, diisobutyl zinc, dipentyl zinc, dihexyl zinc, Zinc dicyclohexyl, dioctylzinc, diphenylzinc, di-p-tolylzinc, dibenzylzinc, ethylbenzylzinc or ethyl-p-tolylzinc;

The organic boron salts are [B(C ₆ H ₅ ) ₃ ], [Ph ₃ C][B(C ₆ H ₅ ) ₄ ], [PhNHMe ₂ ][B(C ₆ H ₅ ) ₄ ], [ HN(C ₂ H ₅ ) ₃ ][B(C ₆ H ₅ ) ₄ ], [B(C ₆ F ₅ ) ₃ ], [Ph ₃ C][B(C ₆ F ₅ ) ₄ ], [PhNHMe ₂ ][B(C ₆ F ₅ ) ₄ ] or [HN(C ₂ H ₅ ) ₃ ][B(C ₆ F ₅ ) ₄ ], preferably [Ph ₃ C][B(C ₆ F ₅ ) ₄ ]; The molar ratio to the neutral ligand-containing trivalent rare earth metal complex is 0-5:1, preferably 2:1.

The α-olefin is ethylene or a terminal olefin with a general molecular formula of CH ₂ ═CH(CH ₂ ) _n CH ₃ (n=1-9).

The reaction solvent of described catalytic system is selected from n-hexane, n-heptane, n-octane, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene or dibromobenzene, preferably toluene, xylene, ethylbenzene Benzene or chlorobenzene.

The method that the present invention catalyzes α-olefin polymerization is as follows:

The solvent is toluene, xylene, ethylbenzene or chlorobenzene, the polymerization reaction temperature is 25°C-80°C, the molar ratio of the alkylating agent to the rare earth metal compound is 5-20:1, the molar ratio of the organic boron salt to the rare earth metal compound The ratio is 2:1. When the polymerization temperature is 25°C, the polymerization reaction is carried out in the glove box, and the polymerization reaction at other temperatures is carried out outside the glove box. The rare earth metal compound, the solvent and the alkylating agent are sequentially added into the reaction bottle and stirred for 5-10 minutes. Then add organic boron salt, and the resulting mixed solution is stirred for 10-15 minutes. The corresponding α-olefin monomer is added, the molar ratio of the monomer to the rare earth metal compound is 500-2000, and the reaction time is 15 minutes-10 hours. After the reaction was completed, a methanol solution containing 10% (v/v) hydrochloric acid was added to terminate it. Pour the polymerization solution into a large amount of methanol containing 10% (v/v) hydrochloric acid and allow it to settle. The resulting polymer was washed three times with methanol and then dried under vacuum at 70°C to constant weight.

The molecular weight of the obtained polyalphaolefin was determined by gel permeation chromatography (Agilent1260 type); the thermal analysis data of the obtained polyalphaolefin was obtained by differential scanning calorimetry (DSC); the regularity of polyalphaolefin was determined by NMR The carbon resonance spectrum was calculated.

The beneficial effects of the present invention are:

(1) The rare earth metal catalyst system has mild reaction conditions and high polymer selectivity; the selected rare earth metal catalyst has a simple structure and is easy to prepare.

(2) Polyα-olefins with ultra-high molecular weight and complete isotactic structure can be prepared by using the rare earth metal catalyst system. At room temperature, its molecular weight is greater than 1 million, and its isotactic structure is greater than 99%.

(3) The rare earth metal catalyst system can also be used to catalyze high isotactic polyα-olefins at a high temperature of 80 ° C, showing good thermal stability and selectivity.

Description of drawings

Fig. 1 is the ¹³ C NMR spectrum of poly-1-pentene obtained at 25°C by using the present invention.

Fig. 2 is the GPC spectrogram of poly-1-hexene obtained by using the present invention at 25°C.

Fig. 3 utilizes the 13C NMR spectrogram of poly-1-hexene obtained at 25 DEG C of the present invention.

Fig. 4 utilizes the 13C NMR spectrogram of poly-1-hexene obtained at 80 DEG C of the present invention.

Fig. 5 utilizes the 13C NMR spectrogram of poly-1-octene obtained at 25 DEG C of the present invention.

Fig. 6 utilizes the 13C NMR spectrogram of poly-1-decene obtained at 25 DEG C of the present invention.

Fig. 7 utilizes the 13C NMR spectrogram of poly-1-dodecene obtained at 25 DEG C of the present invention.

Detailed ways

The specific application examples of the present invention will be described in detail below in conjunction with the technical solutions.

Application example 1

In the glove box, take a 20 mL reaction bottle with a magnetic stirrer, add 10 μmol of ScCl ₃ (THF) ₃ , 10 mL of toluene and 10 times the equivalent of triisobutylaluminum in sequence, and stir for 10 minutes. Then 2 times equivalent of [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] was added, and the resulting mixed solution was stirred for 10 minutes. 500 equivalents of 1-hexene were added, and the reaction was carried out at 25°C for 10 hours. After the reaction was completed, a methanol solution containing 10% (v/v) hydrochloric acid was added to terminate it. Pour the polymerization solution into a large amount of methanol containing 10% (v/v) hydrochloric acid and allow it to settle. The resulting polymer was collected by filtration, washed three times with methanol, and then vacuum-dried at 70°C to constant weight to obtain 0.42 g of poly-1-hexene, with a conversion rate of 100%. According to the GPC analysis of the obtained poly-1-hexene, M _n =87.4×10 ^-4 , and M _w /M _n =1.9. According to ¹³ C NMR analysis, the obtained poly-1-hexene has an isotactic structure of more than 99% (mmmm>99%).

See Tables 1–6 for other application examples.

Application example ^a of different catalysts in table 1

^a Reaction conditions: catalyst (10 μmol), ^Ali Bu ₃ (100 μmol), [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (20 μmol), toluene (10 mL), 1-hexene (420 mg, 500 times equivalent), 25°C, 120 minutes. ^b THF: Tetrahydrofuran, THP: Tetrahydropyran, DME: Ethylene glycol dimethyl ether, DMDE: Diethylene glycol dimethyl ether, THT: Tetrahydrothiophene, TMEDA: NNN'N'-tetramethylethylene glycol Amine, Py: pyridine, Me ₃ [6]aneN ₃ : 1,3,5-trimethyl-1,3,5-triazacyclohexane, ⁱ Pr-Pybox: 2,6-bis(4'-isopropyl-2'-oxazolinyl)pyridine, ⁱ Pr-trisox: 1,1,1-tris(4'-isopropyl-2'-oxazolinyl)ethane. ^c calculation method: polymer mass (g) / added monomer mass (g) × 100. ^d was determined by gel permeation chromatography (GPC). ^e is calculated from the ¹³ C NMR spectrum.

Table 2 Application examples of different aluminum alkyls ^a

^a Reaction conditions: ScCl ₃ (THF) ₃ (10μmol), [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (20μmol), toluene (10mL), 1-hexene (420mg, 500 times equivalent), 25°C, 120 minutes. ^b calculation method: polymer mass (g) / added monomer mass (g) × 100. ^c is determined by gel permeation chromatography (GPC). ^d is calculated from the ¹³ C NMR spectrum.

Application ^example a of different organoboron salts of table 3

^a Reaction conditions: ScCl ₃ (THF) ₃ (10 μmol), Ali ^Bu ₃ (100 μmol), toluene (10 mL), 1-hexene (420 mg, 500 times equivalent), 25°C, 120 minutes. ^b calculation method: polymer mass (g) / added monomer mass (g) × 100. ^c is determined by gel permeation chromatography (GPC). ^d is calculated from the ¹³ C NMR spectrum.

Application ^example a of different reaction temperatures of table 4

^a Reaction conditions: ScCl ₃ (THF) ₃ (10 μmol), ^Ali Bu ₃ (100 μmol), [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (20 μmol), toluene (10 mL), 1-hexene (420mg, 500 times equivalent), 120 minutes. ^b calculation method: polymer mass (g) / added monomer mass (g) × 100. ^c is determined by gel permeation chromatography (GPC). ^d is calculated from the ¹³ C NMR spectrum. ^e 70 minutes.

Table 5 Application examples of different solvents ^a

^a Reaction conditions: ScCl ₃ (THF) ₃ (10 μmol), ^Ali Bu ₃ (100 μmol), [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (20 μmol), solvent (10 mL), 1-hexene (420mg, 500 times equivalent), 25°C, 120 minutes. ^b calculation method: polymer mass (g) / added monomer mass (g) × 100. ^c is determined by gel permeation chromatography (GPC). ^d is calculated from the ¹³ C NMR spectrum.

Table 6 Application examples of different α-olefin monomers ^a

^a Reaction conditions: ScCl ₃ (THF) ₃ (10 μmol), ^Ali Bu ₃ (100 μmol), [Ph ₃ C][B(C ₆ F ₅ ) ₄ ] (20 μmol), toluene (10 mL), α-olefin mono Body (500 times the equivalent), 25 ° C, 120 minutes. ^b calculation method: polymer mass (g) / added monomer mass (g) × 100. ^c is determined by gel permeation chromatography (GPC). ^d is calculated from the ¹³ C NMR spectrum.

Claims (4)

1. the catalyzing of rare-earth metal system of the high taxis polymerization of catalysis alpha-olefin is characterized in that: described catalyzing of rare-earth metal system comprises trivalent rare earth metals title complex, alkylating reagent and the organic boron salt containing neutral ligand;

The described trivalent rare earth metals title complex containing neutral ligand, its molecular formula is (L) _nLnX ₃, in formula:

Ln is thulium, is selected from scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) or lutetium (Lu);

L is neutral ligand, is selected from dme, methyl ethyl ether, ether, positive propyl ether, n-butyl ether, methyl-n-butyl ether, b-butyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, tetrahydropyrans, 2-methyl tetrahydropyrans, 2,5-dimethyl tetrahydro pyrans, Isosorbide-5-Nitrae-dioxane, diethylene glycol dimethyl ether, the tirethylene glycol dme, 15-is preced with (ether)-5, 18-is preced with (ether)-6, bicyclohexane also-18-is preced with (ether)-6, dibenzo-18-crown-6-6, tetramethylene sulfide, 2-methyl tetramethylene sulfide, 2,5-dimethyl tetrahydro thiophene, NNN ' N '-Tetramethyl Ethylene Diamine, pyridine, the 2-picoline, 2,6-lutidine, 1,3,5-trimethylammonium-1,3, the 5-Trianacyclohexane, 1,3,5-triethyl-1,3, the 5-Trianacyclohexane, 1,3,5-triisopropyl-1,3, the 5-Trianacyclohexane, Isosorbide-5-Nitrae, 7-trimethylammonium-Isosorbide-5-Nitrae, 7-7-triazacyclononane, Isosorbide-5-Nitrae, 7-triethyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, Isosorbide-5-Nitrae, 7-triisopropyl-Isosorbide-5-Nitrae, 7-7-triazacyclononane, Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand, two (4 '-methyl-2 ', the-oxazolinyls) pyridines of 2,6-, two (4 '-ethyl-2 ', the-oxazolinyls) pyridines of 2,6-, two (4 '-sec.-propyl-2 ', the-oxazolinyls) pyridines of 2,6-, 1,1,1-tri-(4 '-methyl-2 ' ,-oxazolinyls) ethane, 1,1,1-tri-(4 '-ethyl-2 ' ,-oxazolinyls) ethane or 1,1,1-tri-(4 '-sec.-propyl-2 ' ,-oxazolinyls) ethane,

N is 1≤n≤5;

X is halogen, alkyl, amino, alkoxyl group, aryloxy, carboxyl, nitro, BH ₄ ^-Or BF ₄ ^-In one or both;

Described halogen, be selected from F ^-, Cl ^-, Br ^-Or I ^-

Described alkyl, be selected from methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, allyl group, CH ₂SiMe ₃, CH ₂C ₆H ₄-6-N (CH ₃) ₂, CH (SiMe ₃) ₂Or CH ₂C ₆H ₅

Described amino, be selected from N (CH ₃) ₂, N (CH ₂CH ₃) ₂, N[CH (CH ₃) ₂] ₂, N[C (CH ₃) ₃] ₂, N[Si (CH ₃) ₃] ₂Or N[SiH (CH ₃) ₂] ₂

Described alkoxyl group, be selected from OCH ₃, OCH ₂CH ₃, OCH (CH ₃) ₂Or OC (CH ₃) ₃

Described aryloxy, be selected from OC ₆H ₅, OC ₆H ₃-2,6-(CH ₃) ₂, OC ₆H ₃-2,6-(CH ₂CH ₃) ₂, OC ₆H ₃-2,6-(CH (CH ₃) ₂) ₂, OC ₆H ₃-2,6-(C (CH ₃) ₃) ₂, OC ₆H ₃-4-CH ₃-2,6-(C (CH ₃) ₃) ₂Or OC ₆H ₃-2,4,6-(C (CH ₃) ₃) ₂

Described carboxyl, be selected from acetoxyl group, propionyloxy, hexylyloxy, 2-ethyl hexyl acyl-oxygen base, hot acyloxy, new last of the ten Heavenly stems acyloxy or cycloalkanes acyloxy;

Described alkylating reagent is that molecular formula is AlR ₃Aluminum alkyls, molecular formula be HAlR ₂Alkyl-al hydride, molecular formula be R ₂The alkyl aluminum chloride of AlCl, aikyiaiurnirsoxan beta, molecular formula are MgR ₂Alkyl magnesium or molecular formula be ZnR ₂Zinc alkyl(s), with the molar ratio of the described trivalent rare earth metals title complex containing neutral ligand be 2～1000:1;

Described molecular formula is AlR ₃Aluminum alkyls be selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, three n-butylaluminum, triisopropylaluminiuand, triisobutyl aluminium, three amyl group aluminium, three hexyl aluminium, thricyclohexyl aluminium, trioctylaluminum, triphenyl aluminum, three p-methylphenyl aluminium, tribenzyl aluminium, ethyl dibenzyl aluminium, ethyl di-p-tolyl aluminium or diethyl benzyl aluminium.

Described molecular formula is HAlR ₂Alkyl-al hydride be selected from dimethyl hydrogenation aluminium, ADEH, diη-propyl aluminum hydride, di-n-butyl aluminum hydride, di-isopropyl aluminum hydride, diisobutyl aluminium hydride, diamyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, dioctyl aluminum hydride, phenylbenzene aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, Ethylbenzyl aluminum hydride or ethyl p-methylphenyl aluminum hydride.

Described molecular formula is R ₂The alkyl aluminum chloride of AlCl is selected from dimethylaluminum chloride, diethyl aluminum chloride, diη-propyl aluminum chloride, di-n-butyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride, diamyl aluminum chloride, dihexylaluminum chloride, dicyclohexyl aluminum chloride, dioctyl aluminum chloride, phenylbenzene aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, Ethylbenzyl chlorination aluminium or ethyl p-methylphenyl aluminum chloride.

Described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, n-propyl aikyiaiurnirsoxan beta, normal-butyl alumina alkane, sec.-propyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.

Described molecular formula is MgR ₂Alkyl magnesium be selected from dimethyl magnesium, magnesium ethide, diη-propyl magnesium, di-n-butyl magnesium, di-isopropyl magnesium, diisobutyl magnesium, diamyl magnesium, dihexyl magnesium, dicyclohexyl magnesium, dioctyl magnesium, diphenyl magnesium, di-p-tolyl magnesium, dibenzyl magnesium, Ethylbenzyl magnesium or ethyl p-methylphenyl magnesium.

Described molecular formula is ZnR ₂Zinc alkyl(s) be selected from zinc methide, zinc ethyl, diη-propyl zinc, di-n-butyl zinc, di-isopropyl zinc, diisobutyl zinc, diamyl zinc, dihexyl zinc, dicyclohexyl zinc, dioctyl zinc, phenylbenzene zinc, di-p-tolyl zinc, dibenzyl zinc, Ethylbenzyl zinc or ethyl p-methylphenyl zinc.

Described organic boron salt is [B (C ₆H ₅) ₃], [Ph ₃C] [B (C ₆H ₅) ₄], [PhNHMe ₂] [B (C ₆H ₅) ₄], [HN (C ₂H ₅) ₃] [B (C ₆H ₅) ₄], [B (C ₆F ₅) ₃], [Ph ₃C] [B (C ₆F ₅) ₄], [PhNHMe ₂] [B (C ₆F ₅) ₄] or [HN (C ₂H ₅) ₃] [B (C ₆F ₅) ₄], with the molar ratio of the described trivalent rare earth metals title complex containing neutral ligand be 0～5:1.

2. catalyzing of rare-earth metal system according to claim 1, it is characterized in that: described alpha-olefin is that general molecular formula is CH ₂=CH (CH ₂) _nCH ₃The end position alkene of (n=1～9).

3. catalyzing of rare-earth metal system according to claim 1, it is characterized in that: the reaction solvent of described catalyst system is selected from normal hexane, normal heptane, octane, toluene, dimethylbenzene, ethylbenzene, chlorobenzene, dichlorobenzene, bromobenzene or dibromobenzene.

4. the method for described catalyzing of rare-earth metal system catalysis alpha-olefine polymerizing claimed in claim 3, is characterized in that following steps,

Solvent is selected toluene, dimethylbenzene, ethylbenzene or chlorobenzene, and polymeric reaction temperature is 25 ℃～80 ℃, and the molar ratio of alkylating reagent and rare earth compound is 5～20:1, and the molar ratio of organic boron salt and rare earth compound is 2:1; Rare earth compound, solvent and alkylating reagent add in reaction flask successively, stir 5～10 minutes; Then add organic boron salt, the gained mixing solutions stirs 10～15 minutes; Add corresponding 'alpha '-olefin monomers, the molar ratio of monomer and rare earth compound is 500～2000, and the reaction times is 15 minutes～10 hours; After reaction finishes, adding and contain 10%(v/v) methanol solution of hydrochloric acid makes its termination; Polymer fluid is poured into and is contained in a large number 10%(v/v) in the methyl alcohol of hydrochloric acid, make it sedimentation; Resulting polymers methanol wash three times, then in 70 ℃ of vacuum-dryings to constant weight.

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