CN1155605C - Substituted indenyl metal titanium compound and its preparation method and use - Google Patents

Abstract

The invention relates to a substituted indenyl metal titanium compound and a preparation method and use thereof. The present invention adopts the following substitution structure indenyl metal titanium compound: wherein R ¹ , R ² and R ³ are all H, C ₁ ~ C ₄ alkyl, R ¹ , R ² and R ³ cannot be H at the same time, and R ⁴ is C ₆ -C ₁₀ cycloalkyl. Its preparation method is mainly to react the corresponding alcohol solution with alkyllithium or Grignard reagent, then add the corresponding substituted indenyl titanium trichloride solution to react, filter, concentrate and crystallize to obtain the product. The obtained compound has high catalytic activity for the syndiotactic polymerization of styrene, and can prepare polystyrene with high syndiotacticity, which can be used in industrial production.

Description

Substituted indenyl metal titanium compound and its preparation method and use

Technical field

The invention relates to a substituted indenyl metal titanium compound and a preparation method and use thereof.

Background technique

Atactic Polystyrene (aPS), obtained by free radical polymerization of styrene, has the advantages of hardness, transparency, insulation, and easy processing, and has been widely used in packaging, construction, medicine, electronics, automobiles, and daily necessities and other industries. However, due to the randomness of the structure, its softening temperature is about 100°C, which makes it brittle and poor in heat resistance and chemical corrosion resistance.

In 1955, Natta et al. used TiCl ₄ /AlEt ₃ catalytic system to obtain isotactic polystyrene (isotactic Polystyrene, iPS), with a melting point of 240°C and high crystallinity, but its crystallization rate was too slow to achieve industrialization.

Recently, Ishihara et al obtained syndiotactic polystyrene (syndiotactic Polystyrene, sPS) with a homogeneous organometallic catalyst system [(U.S.Pat.4680353 (1987)] composed of titanium compound and methylaluminoxane (MAO), which is a A crystalline material with a melting point of about 270°C. It has the advantages of fast crystallization speed, low specific gravity, low dielectric constant, good heat resistance, and chemical corrosion resistance, so it has broader industrial prospects.

Catalysts used in the literature for the synthesis of syndiotactic polystyrene include titanium halides, tetraalkoxytitaniums, tetraalkyltitaniums, titanates, titanocenes, and the corresponding zirconium compounds.

Among them, the catalytic system composed of semi-sandwich compound (a trichlorotitanium, a trialkyltitanium, a trialkoxytitanium, and various compounds substituted with alocene) and MAO or B(C ₆ F ₅ ) ₃ etc. The catalytic polymerization of styrene monomers has remarkable syndiotactic orientation and high catalytic activity, and there are many corresponding patents.

Contents of Invention

One of the technical problems to be solved by the present invention is to overcome the defect of low catalytic activity of indenyl compounds obtained in the prior art when used in the syndiotactic polymerization of styrene, and provide a new substituted indenyl metal titanium compound. The substituted indenyl metal titanium compound is used in the syndiotactic polymerization process of styrene, has high catalytic activity, and maintains a relatively high syndiotactic degree of polystyrene.

The second technical problem to be solved by the present invention is to solve the preparation method required to obtain the substituted indenyl metal titanium compound.

The third technical problem to be solved by the present invention is to solve the use of substituted indenyl metal titanium compounds.

In order to solve one of the above-mentioned technical problems, the technical scheme adopted in the present invention is as follows: a substituted indenyl metal titanium compound, whose structure has the following general formula:

Wherein R ¹ , R ² and R ³ are all H, C ₁ -C ₄ alkyl, but R ¹ , R ² and R ³ cannot be H at the same time, and R ⁴ is C ₆ -C ₁₀ cycloalkyl.

2-CH₃IndTiCl₂(OPh)，2-CH₃IndTiCl₂(OCH₂Ph)，1-PhCH₂IndTiCl₂(OMe)，1-PhCH₂IndTiCl₂(OEt)，1-PhCH₂IndTiCl₂(OⁿPr)，1-PhCH₂IndTiCl₂(OⁱPr)，1-PhCH₂IndTiCl₂(OⁿBu)，1-PhCH₂IndTiCl₂(OⁱBu)，1-PhCH₂IndTiCl₂(OPh)，1-PhCH₂IndTiCl₂(OCH₂Ph)，2-PhCH₂IndTiCl₂(OMe)，2-PhCH₂IndTiCl₂(OEt)，2-PhCH₂IndTiCl₂(OⁿPr)，2-PhCH₂IndTiCl₂(OⁱPr)，2-PhCH₂IndTiCl₂(OⁿBu)，2-PhCH₂IndTiCl₂(OⁱBu)，2-PhCH₂IndTiCl₂(OPh)，2-PhCH₂IndTiCl₂(OCH₂Ph)，1，2-Me₂IndTiCl₂(OMe)，1，2-Me₂IndTiCl₂(OEt)，1，2-Me₂IndTiCl₂(OⁿPr)，1，2-Me₂IndTiCl₂(OⁱPr)，1，2-Me₂IndTiCl₂(OⁿBu)，1，2-Me₂IndTiCl₂(O¹Bu)，

1，2-Me₂IndTiCl₂(OPh)，1，2-Me₂IndTiCl₂(OCH₂Ph)，1，3-Me₂IndTiCl₂(OMe)，1，3-Me₂IndTiCl₂(OEt)，1，3-Me₂IndTiCl₂(OⁿPr)，1，3-Me₂IndTiCl₂(OⁱPr)，1，3-Me₂IndTiCl₂(OⁿBu)，1，3-Me₂IndTiCl₂(OⁱBu)，

1，3-Me₂IndTiCl₂(OPh)，1，3-Me₂IndTiCl₂(OCH₂Ph)Typical examples are: 1-CH ₃ IndTiCl ₂ (OMe), 1-CH ₃ IndTiCl ₂ (OEt), 1-CH ₃ IndTiCl ₂ ( ^On Pr), 1-CH ₃ IndTiCl ₂ (O ⁱ Pr), 1 -CH ₃ IndTiCl ₂ ( ^On Bu), 1-CH ₃ IndTiCl ₂ (O ^t Bu), 1-CH ₃ IndTiCl ₂ (OPh), 1-CH ₃ IndTiCl ₂ (OCH ₂ Ph), 2-CH ₃ IndTiCl ₂ (OMe), 2-CH ₃ IndTiCl ₂ (OEt) 2-CH ₃ IndTiCl ₂ ( ^On Pr), 2-CH ₃ IndTiCl ₂ (O ⁱ Pr), 2-CH ₃ IndTiCl ₂ ( ^On Bu), 2-CH ₃ IndTiCl ₂ (O ⁱ Bu)

2-CH ₃ IndTiCl ₂ (OPh), 2-CH ₃ IndTiCl ₂ (OCH ₂ Ph), 1-PhCH ₂ IndTiCl ₂ (OMe), 1-PhCH ₂ IndTiCl ₂ (OEt), 1-PhCH ₂ IndTiCl ₂ (O ⁿ Pr), 1-PhCH ₂ IndTiCl ₂ (O ⁱ Pr), 1-PhCH ₂ IndTiCl ₂ ( ^On Bu), 1-PhCH ₂ IndTiCl ₂ (O ⁱ Bu), 1-PhCH ₂ IndTiCl ₂ (OPh), 1-PhCH ₂ IndTiCl ₂ (OCH ₂ Ph), 2-PhCH ₂ IndTiCl ₂ (OMe), 2-PhCH ₂ IndTiCl ₂ (OEt), 2-PhCH ₂ IndTiCl ₂ (O ⁿ Pr), 2-PhCH ₂ IndTiCl ₂ (O ⁱ Pr), 2-PhCH ₂ IndTiCl ₂ ( ^On Bu), 2-PhCH ₂ IndTiCl ₂ (O ⁱ Bu), 2-PhCH ₂ IndTiCl ₂ (OPh), 2-PhCH ₂ IndTiCl ₂ (OCH ₂ Ph), 1,2-Me ₂ IndTiCl ₂ (OMe), 1,2-Me ₂ IndTiCl ₂ (OEt), 1,2- Me ₂ IndTiCl ₂ ( ^On Pr), 1,2-Me ₂ IndTiCl ₂ (O ⁱ Pr), 1,2-Me ₂ IndTiCl ₂ ( ^On Bu), 1,2-Me ₂ IndTiCl ₂ (O ¹ Bu ),

1,2-Me ₂ IndTiCl ₂ (OPh), 1,2-Me ₂ IndTiCl ₂ (OCH ₂ Ph), 1,3-Me ₂ IndTiCl ₂ (OMe), 1,3-Me ₂ IndTiCl ₂ (OEt), 1,3-Me ₂ IndTiCl ₂ ( ^On Pr), 1,3-Me ₂ IndTiCl ₂ (O ⁱ Pr), 1,3-Me ₂ IndTiCl ₂ (On ^Bu ), 1,3-Me ₂ IndTiCl ₂ (O ⁱ Bu),

1,3-Me ₂ IndTiCl ₂ (OPh), 1,3-Me ₂ IndTiCl ₂ (OCH ₂ Ph)

In order to solve the above-mentioned technical problem 2, the technical scheme adopted by the present invention is as follows: a preparation method of a substituted indenyl metal titanium compound, firstly, a solution of a dehydrated C ₆ -C ₁₀ cycloalkyl alcohol is mixed with an alkyllithium Or Na, K, Grignard reagent reaction, and then add indenyl titanium trichloride solution containing 1, 2, and 3 positions respectively substituted by R ¹ , R ² and R ³ , wherein substituted indenyl titanium trichloride and C The molar ratio of ₆ -C ₁₀ cycloalkyl alcohol is 1:0.8-1.5, the molar ratio of C ₆ -C ₁₀ cycloalkyl alcohol and alkyl lithium or Na, K, and Grignard reagent is 1:0.8-1.5 , under the protection of an inert atmosphere, the dropwise temperature is -78 ~ 0 ° C, the reaction temperature after the drop is 10 ~ 100 ° C, and the reaction time is 1 ~ 30 hours. Then, it is filtered, concentrated, and reconstituted with an organic solvent. Crystallization, the product substituted indenyl metal titanium compound.

In the above preparation method, the molar ratio of the substituted indenyl titanium trichloride to the C ₆ -C ₁₀ cycloalkyl alcohol preferably ranges from 1:1 to 1.2, and the C ₆ -C ₁₀ cycloalkyl alcohol to the alkyllithium or Na , K, the molar ratio of the Grignard reagent is 1:1～1.2, the preferred scheme of alkyllithium is n-butyllithium, the preferred range of dropping temperature is -60～-30°C, and the preferred range of reaction temperature is 25～35°C, The reaction time preferably ranges from 8 to 16 hours. The organic solvent is selected from dichloromethane, tetrahydrofuran, toluene, n-hexane or petroleum ether and mixtures thereof. The gas used in the inert atmosphere can be argon or nitrogen.

In order to solve the third technical problem above, the technical scheme adopted in the present invention is as follows: the substituted indenyl metal titanium compound is used to catalyze the syndiotactic polymerization of styrene.

The catalytic system of the substituted indenyl metal titanium compound used in the syndiotactic polymerization of styrene of the present invention is composed of the above-mentioned substituted indenyl metal titanium compound and a cocatalyst.

The molar ratio of styrene monomer to titanium in the catalyst is 1000:1 to 500000:1, preferably 5000:1 to 300000:1.

The cocatalyst is MAO (methylaluminoxane) or boron compound BX ₁ X ₂ X ₃ or its salt, wherein X ₁ , X ₂ , X ₃ can be the same or different, and X ₁ , X ₂ and X ₃ are all It is a C ₁ -C ₂₀ fluorohydrocarbon substituent.

The catalytic system composed of catalyst and cocatalyst may also include alkylaluminum or alkylaluminum hydrogen compound, the alkyl group is C ₁ -C ₆ , such as trimethylaluminum, triethylaluminum, triisobutylaluminum, di Ethyl aluminum hydride, diisobutyl aluminum hydride, etc. The molar ratio of alkylaluminum or alkylaluminum hydrogen to titanium is 0-2000:1, preferably 0-500:1.

The polymerization reaction is in solvent state or bulk polymerization, in the former case, the solvent is aliphatic hydrocarbon or aromatic hydrocarbon, preferably toluene, and the volume ratio of solvent to monomer is 0～10:1.

The polymerization temperature is 20-100°C.

The polymerization time is 0.5 to 10 hours, preferably 0.5 to 2 hours.

Tests have proved that the catalytic system composed of the substituted indenyl metal titanium compound of the present invention has very high catalytic activity, especially for the polymerization of styrene monomers, and can obtain up to 95.3% high-syndiotactic polystyrene. The highest activity is 1.32×10 ⁷ g polystyrene/(mole titanium·mole styrene·hour), which reduces the residual metal content in the polymer, reduces production cost, improves production efficiency, and achieves better results.

The present invention will be further elaborated below by embodiment:

Detailed ways

【Example 1】

Under argon protection, in 2.5 milliliters (4.73 millimoles) n-hexane solution of n-butyllithium, slowly add dropwise 0.218 grams (4.73 millimoles) of ethanol's n-hexane solution (5.7 milliliters), the lithium salt solution that reaction generates is cold To -40°C, slowly add 1.340 g (4.73 mmol) of 1-CH ₃ IndTiCl ₃ dichloromethane solution (20 ml) dropwise, drop it in 1 hour, naturally rise to 30°C, stir for 10 hours, filter, clear The liquid was pumped to dryness, and the obtained solid was recrystallized with dichloromethane and n-hexane to obtain 0.615 g of 1-CH ₃ IndTiCl ₂ (OEt) red crystals, the yield was 44.4%, and mp=97-100°C. The analysis test results are as follows

Molecular formula: C ₁₂ H ₁₄ Cl ₂ OTi;

MS (EI): 292 (11, M ⁺ ).

¹ H NMR (CDCl ₃ , δ): 7.75-7.72 (m, 2H, IndH ₂ ), 7.47-7.40 (m, 2H, IndH ₂ ), 6.70 (d, 1H, J=2.9, IndH), 6.58 (d , 1H, J=2.9, IndH), 3.35 (q, 2H, J=6.9, OCH ₂ CH ₃ ), 2.64 (s, 3H, IndH ₃ ), 1.34 (t, 3H, J=6.9, OCH ₂ CH ₃ ).

E.A.: Measured, C: 49.18% H: 4.82%

Computing, C: 49.11% H: 4.81%

[Example 2]

All operations were the same as in Example 1, except that methanol was used instead of ethanol, and finally 1-CH ₃ IndTiCl ₂ (OMe) red crystals were obtained with a yield of 73.6% and mp=110-115°C. The analysis test results are as follows

Molecular formula: C ₁₁ H ₁₂ Cl ₂ OTi;

MS (EI): 278 (6, M ⁺ ).

¹ H NMR (CDCl ₃ , δ): 7.76-7.68 (m, 2H, IndH ₂ ), 7.47-7.44 (m, 2H, IndH ₂ ), 6.72 (d, 1H, J=3.3, IndH), 6.61 (d , 1H, J=3.3, IndH), 4.36 (s, 3H, OCH ₃ ), 2.64 (s, 3H, IndH ₃ )

E.A.: Measured, C: 52.37% H: 5.65%

Computing, C: 52.14% H: 5.70%

[Example 3]

All operations were the same as in Example 1, except that isopropanol was used instead of ethanol, and finally 1-CH ₃ IndTiCl ₂ (O ⁱ Pr) red crystals were obtained with a yield of 32.3% and mp=59-61°C. The analysis test results are as follows

Molecular formula: C ₁₃ H ₁₆ Cl ₂ OTi;

MS (EI): 306 (6, M ⁺ ).

¹ H NMR (CDCl ₃ , δ): 7.75-7.73 (m, 2H, IndH ₂ ), 7.45-7.41 (m, 2H, IndH ₂ ), 6.68 (d, 1H, J=3.3, IndH), 6.57 (d , 1H, J=3.3, IndH), 4.97(m, 1H, J=6.1, OCH(CH ₃ ) ₂ ), 2.63(s, 3H, IndH ₃ ), 1.31(d, 6H, J=6.1, OCH( CH ₃ ) ₂ )

E.A.: Measured, C: 50.87% H: 5.25%

Computing, C: 50.71% H: 5.30%

【Example 4】

红色晶体，产率为37.3％，m.p.＝84～86℃。分析测试结果如下All operations are the same as in Example 1, except that ethanol is replaced with cyclohexyl, and finally

Red crystals, yield 37.3%, mp=84-86°C. The analysis test results are as follows

Molecular formula: C ₁₆ H ₂₀ Cl ₂ OTi;

MS (EI): 346 (1, M ⁺ ).

) ¹ H NMR (CDCl ₃ , δ): 7.76-7.73 (m, 2H, IndH ₂ ), 7.48-7.42 (m, 2H, IndH ₂ ), 6.68 (d, 1H, J=3.3, IndH), 6.58 (d , 1H, J=3.3, IndH), 4.75(m, 1H, ), 2.63(s, 3H, IndH ₃ ), 1.90～1.28(m, 10H,

)

E.A.: Measured, C: 55.36% H: 5.81%

Computing, C: 55.26% H: 5.92%

【Example 5】

Polymerizations were carried out in a baked argon-filled ampule three times. 2 mL of styrene, 4 mL of toluene, 6 mL of 1.72 mol/L MAO in toluene, and 0.05 mL of 0.05 mol/L 1-CH ₃ IndTiCl ₂ (O ⁱ Pr ) in toluene were sequentially injected into the ampoule placed in an oil bath whose temperature was previously constant to 50°C for polymerization for 1 hour. Terminate the polymerization reaction with ethanol containing 10% HCl. After filtering and washing, the obtained polymer is vacuum-dried to constant weight at 100° C. to obtain 0.3169 g of polystyrene, with a yield of 17.5% and a catalytic activity of 7.29×10 ⁶ g PS/(mole Ti mole S·hour), wherein PS is polystyrene, and S is styrene.

It was extracted in butanone for 2 hours to remove atactic polystyrene, and the measured syndiotactic polystyrene content was 95.2%.

The resulting polymer had a melting point of 271°C.

[Example 6]

2 mL of styrene, 4 mL of toluene, 6 mL of MAO in toluene at a concentration of 1.72 mol/L, and 0.05 mL of MAO at a concentration of 0.05 mol/L The toluene solution was sequentially injected into the ampoule, and polymerized in an oil bath at 50°C for 1 hour. Terminate the polymerization reaction with ethanol containing 10% HCl, after filtering and washing, the obtained polymer is vacuum-dried to constant weight at 100°C to obtain 0.3359 g of polystyrene, with a yield of 18.5% and a catalytic activity of 7.72×10 ⁶ g PS/(mole Ti·mole S·hour).

The measured syndiotactic polystyrene content was 94.8%.

The resulting polymer had a melting point of 271°C.

[Comparative Example 1]

2 mL styrene, 4 mL toluene, 6 mL MAO toluene solution with a concentration of 1.72 mol/L, and 0.05 mL 1-CH ₃ IndTiCl ₃ toluene solution with a concentration of 0.05 mol/L were sequentially injected into the ampoule, at 50 °C polymerized in an oil bath for 1 hour. Terminate the polymerization reaction with ethanol containing 10% HCl, after filtering and washing, the obtained polymer is vacuum-dried to constant weight at 100°C to obtain 0.1277 g of polystyrene, the yield is 7.1%, and the catalytic activity is 2.94×10 ⁶ g PS/(mole Ti·mole S·hour).

The measured syndiotactic polystyrene content was 93.2%.

The resulting polymer had a melting point of 271°C.

[Example 7]

11 ml of styrene, 0.9 ml of a toluene solution of MAO with a concentration of 1.72 mol/L, and 0.1 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OEt) with a concentration of 0.05 mol/L were sequentially injected into the ampoule, at 50°C Polymerized in an oil bath for 1 hour to obtain 1.3588 g of polystyrene, with a yield of 13.6%, and a catalytic activity of 2.84×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 95.3%.

【Comparative Example 2】

11 mL of styrene, 0.9 mL of MAO in toluene with a concentration of 1.72 mol/L, and 0.1 mL of 1-CH ₃ IndTiCl ₃ in toluene with a concentration of 0.05 mol/L were sequentially injected into the ampoule and placed in an oil bath at 50 °C. Medium polymerization for 1 hour yielded 0.6523 g of polystyrene with a yield of 6.6% and a catalytic activity of 1.36×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 93.2%.

[Embodiment 8]

11 ml of styrene, 0.9 ml of a toluene solution of MAO with a concentration of 1.72 mol/L, and 0.1 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OEt) with a concentration of 0.05 mol/L were sequentially injected into the ampoule, at 70°C Polymerized in an oil bath for 1 hour to obtain 1.6691 g of polystyrene, the yield was 16.8%, and the catalytic activity was 3.49×10 ⁶ g PS/(mol Ti·mol S·hour).

The syndiotactic polystyrene content was measured to be 87.5%.

[Comparative Example 3]

11 mL of styrene, 0.9 mL of MAO in toluene with a concentration of 1.72 mol/L, and 0.1 mL of 1- _CH3IndTiCl3 with a concentration of 0.05 mol/L in _toluene were sequentially injected into the ampoule and placed in an oil bath at 70 °C. Medium polymerization for 1 hour yielded 0.9920 g of polystyrene with a yield of 10.0% and a catalytic activity of 2.07×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 93.2%.

[Example 9]

11 ml of styrene, 0.9 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.1 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OMe) with a concentration of 0.05 mol/L were injected into the ampoule in sequence. Polymerized in an oil bath for 1 hour to obtain 1.6515 g of polystyrene, the yield was 16.6%, and the catalytic activity was 3.45×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 91.5%.

The resulting polymer had a melting point of 270°C.

【Example 10】

11 ml of styrene, 0.9 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.1 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OMe) with a concentration of 0.05 mol/L were injected into the ampoule in sequence. Polymerized in an oil bath for 1 hour to obtain 1.6332 g of polystyrene with a yield of 16.4% and a catalytic activity of 3.41×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 95.3%.

The resulting polymer had a melting point of 268°C.

[Example 11]

11 ml of styrene, 0.9 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.1 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OMe) with a concentration of 0.05 mol/L were injected into the ampoule in sequence, at 90°C Polymerized in an oil bath for 1 hour to obtain 1.8034 g of polystyrene with a yield of 18.1%, and a catalytic activity of 3.77×10 ⁶ g PS/(mol Ti·mol S·hour).

The measured syndiotactic polystyrene content was 92.1%.

The resulting polymer had a melting point of 268°C.

[Comparative Example 4]

11 mL of styrene, 0.9 mL of MAO in toluene with a concentration of 1.72 mol/L, and 0.1 mL of 1-CH ₃ IndTiCl ₃ in toluene with a concentration of 0.05 mol/L were sequentially injected into the ampoule and placed in an oil bath at 90 °C. Medium polymerization for 1 hour yielded 0.7006 g of polystyrene with a yield of 7.0% and a catalytic activity of 1.46×10 ⁶ g PS/(mol Ti·mol S·hour).

The syndiotactic polystyrene content was measured to be 87.0%.

[Example 12]

11 ml of styrene, 0.9 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.1 ml of 1-CH ₃ IndTiCl ₂ (O ⁱ Pr) toluene solution with a concentration of 0.05 mol/L were injected into the ampoule in sequence, Polymerized in an oil bath at 50° C. for 1 hour to obtain 0.6229 g of polystyrene with a yield of 6.3% and a catalytic activity of 1.32×10 ⁶ g PS/(mole Ti mole S·hour).

The measured syndiotactic polystyrene content was 94.8%.

[Example 13]

的甲苯溶液依次注射入安培瓶中，在90℃的油浴中聚合1小时，得1.6069克聚苯乙烯，产率为16.1％，催化活性为3.36×10⁶克PS/(摩尔Ti·摩尔S·小时)。11 ml of styrene, 0.9 ml of MAO in toluene at a concentration of 1.72 mol/L, and 0.1 ml of 0.05 mol/L

The toluene solution was injected into the ampoule successively, and polymerized in an oil bath at 90° C. for 1 hour to obtain 1.6069 grams of polystyrene, with a yield of 16.1%, and a catalytic activity of 3.36×10 ⁶ grams of PS/(mole Ti mole S ·Hour).

The measured syndiotactic polystyrene content was 91.4%.

[Example 14]

11 milliliters of styrene, 0.9 milliliters of MAO toluene solution with a concentration of 1.72 mol/L, and 0.1 milliliters of 1-CH ₃ IndTiCl ₂ (O ^t Bu) toluene solution with a concentration of 0.05 mol/liter were injected into the ampoule in sequence, Polymerization in an oil bath at 70°C for 1 hour yielded 0.7215 g of polystyrene with a yield of 15.2% and a catalytic activity of 1.51×10 ⁶ g PS/(mole Ti·mol S·hour).

The syndiotactic polystyrene content was measured to be 92.5%.

[Example 15]

11 ml of styrene, 0.45 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.05 ml of a toluene solution of 1-CH ₃ IndTiCl ₂ (OMe) with a concentration of 0.05 mol/L were injected into the ampoule in sequence. Polymerized in an oil bath for 1 hour to obtain 2.7110 g of polystyrene with a yield of 27.2%, and a catalytic activity of 1.13×10 ⁷ g PS/(mol Ti·mol S·hour).

The syndiotactic polystyrene content was measured to be 86.2%.

[Example 16]

11 ml of styrene, 0.45 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.05 ml of 1-CH ₃ IndTiCl ₂ (OEt) toluene solution with a concentration of 0.05 mol/L were sequentially injected into the ampoule, and heated at 50°C Polymerized in an oil bath for 1 hour to obtain 3.1681 g of polystyrene with a yield of 31.8%, and a catalytic activity of 1.32×10 ⁷ g PS/(mol Ti·mol S·hour).

The syndiotactic polystyrene content was measured to be 83.4%.

The resulting polymer had a melting point of 266°C.

[Example 17]

11 ml of styrene, 0.45 ml of MAO toluene solution with a concentration of 1.72 mol/L, and 0.05 ml of 1-CH ₃ IndTiCl ₂ (OEt) toluene solution with a concentration of 0.05 mol/L were injected into the ampoule in sequence, and heated at 90°C Polymerize 1 hour in the oil bath of 2.3977 gram polystyrenes, productive rate is 24.1%, catalytic activity is 1.00 * ¹⁰ gram PS/(mole Ti mole S hours), record syndiotactic polystyrene content as 89.4%.

Claims (8)

1. A substituted indenyl metal titanium compound, the structure of which has the following general formula:

Wherein R ¹ , R ² and R ³ are all H, C ₁ -C ₄ alkyl, but R ¹ , R ² and R ³ cannot be H at the same time, and R ⁴ is C ₆ -C ₁₀ cycloalkyl. 2. According to the preparation method of the substituted indenyl metal titanium compound as claimed in claim 1, the solution of the dehydrated C ₆ -C ₁₀ cycloalkyl alcohol is reacted with alkyllithium or Na, K, Grignard reagent, Then add the solution containing indenyl titanium trichloride substituted by R ¹ , R 2 and R ³ respectively at positions 1, ^2, and 3, wherein the mixture of indenyl titanium trichloride and C ₆ ~ C ₁₀ cycloalkyl alcohol The molar ratio is 1:0.8~1.5, C ₆ ~C ₁₀ cycloalkyl alcohol and alkyl lithium or Na, K, the molar ratio of Grignard reagent is 1:0.8~1.5, under the protection of inert atmosphere, drop The temperature is -78～0℃, the reaction temperature after dropping is 10～100℃, and the reaction time is 1～30 hours. Then, it is filtered, concentrated, and recrystallized with an organic solvent to obtain the product substituted indenyl metal titanium compound . 3. The preparation method of the substituted indenyl metal titanium compound according to claim 2, characterized in that the molar ratio of the substituted indenyl titanium trichloride to the C ₆ -C ₁₀ cycloalkyl alcohol is 1:1-1.2. 4. The method for preparing substituted indenyl metal titanium compounds according to claim 2, characterized in that the molar ratio of C ₆ -C ₁₀ cycloalkyl alcohol to alkyl lithium or Na, K, Grignard reagent is 1:1 ~1.2. 5. The preparation method of the substituted indenyl metal titanium compound according to claim 2, characterized in that the dropping temperature is -60~-30°C, the reaction temperature is 25~35°C, and the reaction time is 8~16 hours. 6. The preparation method of the substituted indenyl metal titanium compound according to claim 2, characterized in that the organic solvent is selected from dichloromethane, tetrahydrofuran, toluene, n-hexane or petroleum ether and mixtures thereof. 7. The preparation method of the substituted indenyl metal titanium compound according to claim 2, characterized in that the alkyllithium is n-butyllithium. 8. The use of the substituted indenyl metal titanium compound according to claim 1 for catalyzing the syndiotactic polymerization of styrene.