SU738656A1 - Tetravanadium alkoxy derivatives as catalyst for polymerization of ethylene - Google Patents

Description

(54) ALCOXY DERIVATIVES OF FOUR-VALENT VANADIUM AS CATALYSTS FOR POLYMERIZATION OF ETHYLENE

one

  The invention relates to new chemical compounds - alkoxy derivatives of tetravalent vanadium of the general formula

R2V (,

where R CsFy,, (C ,,

(CHS) s51CH.2;

, (СНз) з31, (ф ,,) з51. Ethyl alkoxy derivatives of tetravalent vanadium can be components of ethylene polymerization catalytic systems and can be used in polyethylene (PE) production processes. low pressure method. tS

These compounds, their properties and method of preparation are not described in the literature.

Compounds of tetravalent vanadium type VR, where CjHs-, or CeHs 1 and 2, are known.

However, these compounds are characterized by low thermal stability.

(the temperature of the onset of thermal decomposition is within

 from -70 ° C to), which limits their use. The low thermal stability of VR type compounds, in particular, completely eliminates

their use in the process of polymerization of ethylene by the method of low pressure.

The aim of the invention is the development of new agosoxy derivatives of vanadium, suitable as thermostable explosion-proof catalysts for the polymerization of ethylene.

This goal is achieved by the structure of alkoxy derivatives of triplet vanadium vanadium, having the general formula

, R2V (aR) 2,

where R,, (СНз) з CgH, (сНз) з51СНа;

 R, - (CHj) 5Si, (C2GG5) s51.

The proposed gigaso-derivatives of chaefehvalent vanadium are significantly more stable than the known compounds of the type V R, the temperature of the onset of their thermal decomposition is within the range of 89-179 C.

Alkoxyproiodine tetravalent vanadium in combination with a halogen-containing almine-organic compound04, such as diethylaluminum-chloro. RIDOM (DEAH) can be used as a catalyst for the polymerization of ethylene

in an inert hydrocarbon solvent, such as n-heptane. The optimal concentrations of vanadium-organic compounds (BOC) used are 0.02-0.08 g / l, the molar ratios of DEAC and BOC are 30: 1-50: 1, the polymerization temperature (tf, e) is 20-50 ° C

pressure (rpol.

Synthesis of the proposed BOC can be carried out by one of three methods.

By alcoholysis of the corresponding type Compounds with alcohols at temperatures from -78 ° C to + 20 ° C.

R Vt2ROH R-V (DR) .H42RH

1 i

(., CH, .c /, -, R-tc.Hg, (cps) ze - () 51X

.: - ;. "By the exchange interaction of compounds of the (Ro) 2VCeiC type with Grignard reagent at temperatures from to.

tiO

(Ro), v№, + iuce

VCa t2ROL

(Ro) vce ,, + iRMgx -H R ,, V (OR,) + 2Mgxce

(R- (CH) -., HgXCH) ,, Br)

By the exchange interaction of tetraalkoxy derivatives of vanadium type (with Grignard reagent at temperatures from -78 ° C to + 20 ° C:

((0) 4V + 2RMgX R2V (OR9, j- 2RMg)

, ("(SNS)):, and

Example 1. The preparation and use of bis-pentafluorophenyl in anadium-di-thrc-butoxide (CeF5) 2V (OtC4H9) 2

6.4 g (0.0089 mol) of tetra (pentafluorophenyl) vanadium (taken in the form of a solution in 50 ml of diethyl ether, with 1.3 g (0.0178 mol)) are mixed in a vacuumized glass ampoule at minus 78 ° C. a) tert-butyl alcohol (tC. HdON); extract as a solution in 20 ml of diethyl ether. The temperature of the reaction mixture is then raised to room temperature.

(+ 20 ° C) and incubated for 2 hours (the color of the reaction mass changes from faint to green), after which the solvent is completely removed, the solid residue is washed with peral ether and dried in vacuo at, the yield of bis-pentafluoro-fevane vanadium tert-butoxide

((CeO) 7 (OtCj (Hg) 2) is 4.0

(8.71 from theoretical),

The content of vanadium. In the synthesized compound according to the results of chemical analysis is

9.65 wt.% (Theoretically calculated

For the compound obtained is paramagnetic. The constants of its EPR spectrum are: the line width (A) is equal to 52,710.3 rstehd (E), the value of the d-factor (gi) is equal to

1.9717. The temperature of the onset of thermal decomposition (CgFg), V (ОССд Нд), determined using differential thermal analysis (DTA) at a heating rate of 7 K / min, is 179 ° C.

 Conducting polymerization. 6.3 mg (CgFg) jV () and 47.3 mg AG ()} CE (di-ethyl aluminum chloride is used as a 30% solution in n-heptane) sealed separately in

 glass ampoules (molar ratio of aluminum to vanadium 33: 1), placed in a 150 ml stainless steel reactor, free the reactor from air and traces of moisture, introduces

5 him with 100 ml of purified n-heptane and keep the temperature up to. Then ethylene is fed into the reactor up to a total pressure of 1 atm by switching on a mixing device that breaks

0 ampoules with components of the catalytic system. Polymerization is started, during which the temperature and pressure of ethylene in the reaction zone are automatically kept constant. 100 minutes after the start of the polymerization, the reactor is freed from ethylene, the polymer is recovered and the catalyst is washed with water and ethyl alcohol. The weight of the washed PE after drying is

0 1.46 g, equivalent to yield

232 g of PE with 1 g of BOC or 2401 g of PE with 1 g of V. The characteristic viscosity of PE, determined at 135 ° C. In decal5 () is 7.9 dl / g, and the corresponding average molecular weight ( Mv) 890500.

Example 2 Under the conditions of Example 1, 6.0 mg (CgF5) 2V (OtC.Hg) and 45.1 mg are loaded into the reactor.

0 At, () C (the molar ratio A6 / V is 33: 1) and is supported. temperature The PE yield is 1.31 g, or 218 g PE / g BOC, or 2263 g PE / g V.

5 Example 3. Under the conditions of Example 1, 6.4 mg (CgFg) V (OtC4Hg) 2 and 52.6 mg AE () C (AP / V molar ratio is 36: 1) are charged to the reactor and the temperature is raised to

0 500 ° C. The yield of PE is 1.21 g.

or 188 g PED VOS, or 1960 g PE / g V.

Example 4, B. The conditions of example 1 are added to the reactor, p is charged with 2.1 mg (CgF5) 2V (OtC4H9) 2 and 18.9 mg Ae () C 5 (the molar ratio AP / V is equal to

39: 1) H serves ethylene to a total pressure of 4 at. The PE yield is 1.62 g, or 171 g PE / g BOC, or. 7994 g PE / g V.

l Example 5. The preparation and use of dimesitylvanadium-tert-butoxide {(CHgjg CgHj VCOtC Hq).

In a vacuum glass ampoule, at -78s, 2.4 g (0.0070 mol) of tetra-tert-butoxyvan di (, V, taken as a solution in 50 ml of diethyl ether, with 14.0 ml of 1.0 N) are mixed. a solution of mesityl magnesium bromide ((CH)) in diethyl ether (0.0140 mol).

The temperature of the reaction mixture, while stirring, is slowly raised to room temperature (20 ° C), and the mixture is kept for 6 hours, after which the yellowish-green solution is drained from the precipitate of mania salae, the solvent is removed in vacuo, and dimesythylvanadiidi-tert is extracted from petroleum ether -butoxide i (CH,) gH, j, V (OtCdHg). After drying the substance obtained in vacuo, 2.5 g of a viscous black-green liquid, crystallizing from -5 to, are obtained. The yield of dimethyl titanium diide-tert-butoxide is 80% of the theoretical value.

The content of vanadium in the synthesized compound according to the results of chemical analysis is 11.37%, carbon 71, 50%, hydrogen 9.15% (theoretically calculated for the contents of V, C, H, respectively, equal to 11.72%, and 9.20%) . The ESR spectrum constants of the obtained compound are A -56.91 O, gi 1.9669. The temperature of the onset of thermal decomposition {(CH3), V (OtC4Hg), determined by the DTA method, as in Example 1, is.

Conducting polymerization. Under the conditions of Example 1, I load 6.2 mg {(C H,) s, V into the reactor. and 7bg, 7 mg AB (C5H5) iCf (AP / V molar ratio is 46: 1). The yield of PE is 3.31 g, or 540 g of PE. / H wok, or 4770 g of PE / g V. PE is characterized by the values r1 | | and Mu, respectively, 23.4 dl / g and 3531300.

Example 6. Under the conditions of example 1, 6.5 mg (CH (CH) () 76.8 mg A {Cif) (the AI / V molar ratio is 44: 1) is charged to the reactor and the temperature is raised to 50 ° C. The yield of PE is 1.96 g, or 301 g of PE / g of wax, or 2652 g of PE / g of V.

PRI me R 7. Obtaining and using bis-trimethylsilylmethylvanadium di-tert-butoxide (CH) iCH2 V () -.

1.7 ml (0.0164 mol) of tetrachloride vanadium CD-D dissolved in 7t ml of diethyl ether, placed in a three-necked flask purged with argon, and cool its contents to 78 ° C. Then to the contents of the flask while stirring slowly add 41 ml of 0.8 n. solution of tert-butoxy acid (), (0,0328 mol) in petroleum ether. To the received di-tert-butoksivanadiy

DICHLORIDE ((t SdNDO) ,, VCe) with

 slowly add 54.5 ml

0.6 n. of trimethylsilylmethylmagnesium chloride solution {(СН,) e31СН2МдСг)

(0.0328 mol) in diethyl ether. Then, with continuous stirring, the temperature of the reaction mixture in the flask is raised to room temperature (2 ° C). The solution is separated from the precipitate, the solvent is removed in vacuo, from the oily residue is distilled off at a residual pressure of 0.1 mm Hg. 1.2 g of blue-green bis-trimethylsilylmethyl-vavadium di-tert-butoxide -

(CHgl SiCH J VCotC.Hg). The product yield is 20%. The content of vanadium in the synthesized compound determined by a chemical method is 14.06%, carbon is 52.01%, hydrogen is 10.45%, (the content of V, C, H theoretically calculated for C gHH OSigVO is, respectively,%: 13.45; 51.75 and 10.78). The constants of the EPR spectrum of the designated compound are -53.4tO, 4 Oe, gj 1.9666, the onset temperature of the teloYeLa decomposition determined by the method as in Example 1 is 148 ° C.

I Conduct polymerization. In Example 1, I load into the reactor

2.3 mg ((CH) s31CH5 | 2 VCOtC4H5) a 34.0 mg AP. () Cf (r-ratio Ap / V is 45: 1). The yield of PE, coc1) is 1.34 g, or 583 g PZ / g.

woC, or 4147 g PE / g V, its IVfl is equal to 7.3 dl / g, and MC t31600,

Example 8. In ycjio3H5Jx, primer 1 in the reactor was 3.4 mg UCH-5) jSiCH2U OBCdH9) g and 42.9 mg A8 (C2Hs) 2CB (molar ratio At / V is 38: 1) and raise the temperature to. The yield of PE is 0.82 g, or 241 g of PE / g BFB, or 1715 g of PE / g V.

Pr and me p 9, Preparation and use of dibeneylvanadium-bi, c-triethylsiloxide (CgH9CHci), VlOSi (CaH3) 3.2 ..

16.0 g (0.0385 mol) of tetrabenzyl vanadium ((C HgCHuUV), dissolved in 100 ml of DIETHYL ester, are placed in a three-necked flask, purged with argon, and its contents are cooled to. Then 10 g are added to the flask with stirring, 10 g (0 , 0770 mol) of triethylsilanol ((: 4H5) z51OH) dissolved in 30 ml of diethyl ether and raise the temperature of the reaction mixture to room temperature (20 ° C). The color of the reaction mixture changes from green to red-violet. After removal from the reaction the mass of the solvent in vacuum get 17 g of oily liquid. The yield of dibenes ilvanady trietilsiloksida-bis ((SeN5SN) (S7N5) is 90% of the theoretical. Designated chemical method vanadium content in the synthesized compound

7 is 10.10% (theoretically calculated for CjgH Si2VO. 10.30%), the constants of its EPR spectrum are: A., V -47.710.5 Oe, gi 1.9637, the temperature of the onset of thermal decomposition, determined by the DTA method as in example 1, is 89 ° C. Conduction, polymerization. Under the conditions of Example 1, 6.4 mg of (CgH5CH2) 2V {OSi (C2H6bL and 47.8 mg Ae ((molar ratio At / V is 31: 1)) are charged to the reactor. The PE yield is 1.64 g, or 256 g of PE / g boil, or 2540 g of PE / g V, its hydride exceeds 40 dl / g, and v 1,000,000. Example 10, Under the conditions of Example 1, 7.6 mg (CsH5CH2), jV is charged to the reactor {OSi (C2H6) 3}, j And 63.3 MG Ar (C2Hb) HSu (A2 / V molar ratio is 35: 1) and increase the temperature to. BE PE = 0.64 g, or 84 g PE / g BOS, or 833 PE / g V. Example 11, Preparation and use of bis-trimethylsilylmethylvanadium-bis-trimethylsiloxide (UCH j iCHjbVtOSKCH), 1.7 ml (0,0164 mol) of vanadium tetrachloride (VCBji) / The solution is placed in a 100 ml diethyl ether solution, placed in a three-necked flask, purged with argon, and its content is cooled to -78 ° C. Then the contents of the flask are sprinkled with small amounts of 3.7 g (0.0328 mol) of hpflHg: 1: Shl: ganatry ((СНз)). To 1 g of the obtained bis-methyl silanadium dichloride bis-methyl (((СН,),,) 54.5 ml of 0.6 and. Are slowly added. of trimethylsilylmethylmagnesium chloride ((,. A5CE, doped with ether, then the temperature of the reaction mixture was raised to room temperature (20 ° С) with continuous stirring

eight

Then the solution is separated from the precipitate, the solvent is removed in vacuum, the residue is distilled off at a residual pressure of 0.1 mm Hg. 1.2 g of blue-green bis-trimethylsilylmethyl vanadium-bis-trimethylsiloxide (1 (СНз) з81СН,), V {OSi (CH,), i). The yield of the obtained product is 18% of the theoretical. The chemical content of vanadium in the synthesized compound determined by chemical method is 13.10% (theoretically calculated for C, H4pSi4VO / i 12.67%), its EPR spectral constants are -53, liO, 5 Oe, gi 1.9627, the onset temperature of the thermal decomposition, determined by DTA, as in Example 1, is 105 ° C. Under the conditions of Example 1, 4.9 mg | (CH3) H 31 CH, | 2 VtOSKCHj)} and -60.5 mg M ((the molar ratio Af / V is 40: 1) are loaded into the reactor. The PE output is 2.21 g , or 451 g PE / g, BOC, or g PE / g V, it, paBria 7.0 dl / g, and Mv 691300. Example 12. In the conditions of example 1, 5.8 g {(СНа) are charged to the reactor H81SN ,,} g VlOSi (CH) 2 67.1 mg AU (CiRf,) C4. (At / V molar ratio is 38: 1) and the temperature is raised to. The PE yield is 1.48 g, or 255 g PE / g BOC, or 1948 g PE / g V. The main physicochemical characteristics are synthesized; gx of new alkoxy derivatives of the fourth valence vanadium type R2V (OR) 4 are given in Table 1, data on ktivnosti catalytic systems based on Vanadium in the alkoxy derivatives of ethylene polymerization are given in Table 2 (AU cocatalyst (CjHg) CE, solvent: n-heptane (0.1 L), Rtsal 1 atm).

Seele-Nepe- 176 56,9tO, 6 1,9669 71.50

on regog71777

oil-net image

ma

liquid -,

bone:

tzo (MejSiCH4) iV (OtB4) Blue-100 148 green-on P at 0, liiM liquid-bone (CjHjCHjjjVtoeiCtjjj Red-Hep-89-fiole-regogram and re-bone (MesSlCH5t) aV (OSiMej aCHHe-100 ° 105 zele-at Р V per 0.1 mm. LCD-.ND bone Note. - Example experiment. From the given examples and tables, it can be seen that the synthesized new ones (alkoxy derivatives of tetravalent V. anadi are thermostable compounds (temperature the onset of thermal decomposition is in

Continuation of the table, 1 53, 4tO, 4 1.9666 52, Ot w-47.7tO, 5 1.9637 53.110.5, 1.9627 4 was carried out at a pressure of 4 atm., 60 cases 89-179 ° C), which allows you to work with them (for example, their packaging) and store them at room temperature. In combination with diethyl alkaline chloride, assumed BOC form active catalytic ethylene polymerization systems that allow PE to be obtained in the range of 2400-4770 g / g V at atmospheric pressure during the polymerization time of 100 minutes, and the resulting PE is highly molecular, and the average molecular weight is real mass in the range of less than 7,, 10.

For comparison, it should be noted that the domestic production process of low pressure PE production based on the use of the catalytic system titanium tetrachloride - diethyl aluminum chloride, is characterized by a polymer yield of about 900-1000 g PE / g T / for a contact time of 2 hours at a total pressure of 4 at or yield in the order of 250 g PE / g T; in terms of atmospheric pressure. Another important advantage offered by alkoxy compounds of tetravalent vanadium compared to a number of other transition metal compounds is their relatively low lability with respect to air, in the presence of which they decompose without explosion.

if this does not release any aggressive substances (titanium tetrachloride, for example, air is rapidly hydrolyzed, hydrogen chloride is released, causing chemical burns and damage to the respiratory tract).

Claims (2)

1. Razuvaev G.A. et al. Vanadium tetrachloride reaction with alkyl lithium. Izv. USSR Academy of Sciences, chemical series; 1968, p. 2620. 2.-Raevuev G.A. et al., Phenyl derivatives of vanadium, DAN SSSR, 1967, 172, p. 1337.