CN1315459A - Catalyst system for ether-type olefine polymerization and its preparing process - Google Patents

Abstract

A catalyst system for the ether-type olefin polymerization has a master catalyst which is a solid one prepared by carrying 4-valence Ti compound and ether compound on magnesium halide carrier and a cocatalyst which is an organic compound of metal, and is prepared through mixing magnesium halide, inertial disperser and alcohol and reaction with 4-valence Ti compound and ether compound to obtain solid catalyst. Its advantages include high activity.

Description

A kind of ether olefin polymerization catalytic system and preparation method

This invention relates to catalytic systems for the synthesis of polyolefins. Magnesium halide is used as a carrier to support tetravalent titanium compounds, the cocatalyst is a metal organic compound, and the catalyst system does not need an external electron donor during olefin polymerization.

At present, the high-efficiency carrier catalysts used for olefin polymerization mainly use magnesium halide as a carrier and a complex catalyst system supporting tetravalent titanium. In GB211066 and JP-A-5883006, a magnesium halide is dissolved in alcohol to form a uniform solution, and then the magnesium halide alcohol solution is reacted with low-temperature titanium tetrachloride and an internal electron donor, and a titanium-containing magnesium halide carrier catalyst is obtained while the magnesium halide is precipitated. The internal electron donor is a phthalate compound. However, when this type of catalyst is used for olefin polymerization, it is necessary to add an external electron donor-alkoxy silicon compound to generate polyolefin with high isotacticity, and the polymerization process is complicated. In addition, in the selection of internal and external electron donors, only by selecting appropriate internal and external electron donors can a synergistic effect be achieved to synthesize highly active catalysts and polymerize polyolefins with high isotacticity. The shape and size of the catalyst prepared by this method are difficult to control, and the obtained polymer has poor shape, low apparent density, and the selection of internal and external electron donors is limited.

In addition, the magnesium halide carrier is first activated and made into particles of a certain shape (such as spherical, etc.), and then the formed magnesium halide carrier is reacted with a titanium compound and an internal electron donor to obtain a tetravalent titanium-supported catalyst. The internal electron donor used is still a carboxylate compound, such as dibutyl phthalate and the like. The methods for preparing the molded magnesium halide carrier include spraying method, high-speed stirring method, high-pressure spraying method and other methods to prepare the carrier. For example, in CN1034736C and US4399054, magnesium chloride, ethanol, silicone oil, and mineral oil are heated and dissolved together, and then sprayed at high pressure or stirred at high speed to solidify into microparticles in a cooling medium, and a catalyst is obtained after loading a titanium compound. When this catalyst is used for olefin polymerization, it still needs to add an external electron donor, such as alkoxy silicon compound.

When synthesizing the magnesium halide-supported catalyst, only one electron donor can be used in the synthesis of the catalyst, or an electron donor can be used together with a cocatalyst, and a catalyst with high activity and high stereospecificity can be obtained. This electron donor is an ether compound, and EP0361494 A2 and US4971931 are catalysts prepared by the action of magnesium chloride carrier, titanium tetrachloride and disubstituted propylene glycol. The activation of the magnesium chloride carrier is to prepare a catalyst by mixing a certain proportion of magnesium chloride, diether and chlorinated alkanes by ball milling and activating it, and then carrying out titanium tetrachloride loading. Used in olefin polymerization, the resulting polyolefin has high isotacticity, but the activity is low, and the activity and shape of the catalyst are difficult to control. The resulting polymer also has poor morphology and low apparent density.

The invention overcomes the disadvantages of low catalyst activity in the prior art, needs to add an external electron donor during the polymerization reaction, and complicates the polymerization process, and provides an ether olefin polymerization catalyst system and a preparation method.

An ether olefin polymerization catalytic system of the present invention contains a main catalyst and a co-catalyst. The main catalyst is a solid catalyst composed of a tetravalent titanium compound and an ether compound loaded on a magnesium halide carrier. Wherein the molar ratio of the magnesium halide carrier to the ether compound is 50:1-1:1, preferably 20:1-2:1. The general formula of the compound using magnesium is Mg(OR) _n X _2-n (n=0~2), where R is a C ₁ ~C ₁₀ hydrocarbon group, preferably a C ₂ ~C ₄ hydrocarbon group, such as ethoxy Magnesium, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, etc. The cocatalyst is a group IA-IIIA metal organic compound, the general formula is R _n MeX _3-n , R is hydrogen or C ₁ -C ₂₀ hydrocarbon group, X represents halogen, Me is metal, n=1-3. Such as Al(CH ₃ ) ₃ , Al(C ₂ H ₅ ) ₃ , Al(C ₄ H ₉ ) ₃ , Al(iC ₄ H ₉ ) ₃ , Al(C ₂ H ₅ ) ₂ Cl, Al(C ₂ H ₅ ) Cl ₂ etc., the best being triethylaluminum and triisobutylaluminum. When olefins are polymerized, the molar ratio of the amount of aluminum alkyl to the content of titanium in the catalyst is 10-2000, preferably 40-800. The above-mentioned tetravalent titanium compound is Ti(OR) _n X _4-n (n=0-4), and X is a halogen. R is a C ₁ -C ₁₀ hydrocarbon group, and R may be the same or different, preferably a C ₂ -C ₅ hydrocarbon group. Such as TiCl ₄ , TiBr ₄ , TiI ₄ , Ti(OEt)Cl ₃ , Ti(OEt) ₂ Cl ₂ , Ti(OBu) ₄ , Ti(OiBuO) ₄ , preferably TiCl ₄ .

1．R₁,R₂,R₃,R₄是含C₁～C₁₀的直链或支链烃基、环烃基或氢原子等。R₁,R₂,R₃,R₄可以相同，也可以不同，如氢原子，甲基，乙基，丙基等，最好为氢原子和甲基。2．X₁,X₂,X₃,X₄可以全部是烃氧基，也可以部分是烃氧基，但是至少其中两个必须是烃氧基。如甲氧基，乙氧基，丙氧基，丁氧基，异丁氧基，戊氧基，己氧基，辛氧基，异辛氧基，苯氧基，苄氧基，取代苯氧基，取代苄氧基等，两个必须的烃氧基最好为甲氧基，乙氧基。3．X₁,X₂,X₃,X₄可以部分是烃基，最多只能是其中两个为烃基，如甲基，乙基，丙基，丁基，异丁基，戊基，环戊基，己基，环己基，辛基，异辛基，苯基，苄基，取代苯基，取代苄基等。4．结构式中心碳原子也可作为桥碳原子与烃基相连成环，如脂肪六员环，脂肪七员环，环戊二烯环，茚环，芴环等。The general formula of the ether compounds used in the present invention is:

1. R ₁ , R ₂ , R ₃ , R ₄ are linear or branched hydrocarbon groups, cyclic hydrocarbon groups or hydrogen atoms containing C ₁ to C ₁₀ . R ₁ , R ₂ , R ₃ and R ₄ can be the same or different, such as hydrogen atom, methyl group, ethyl group, propyl group, etc., preferably hydrogen atom and methyl group. 2. X ₁ , X ₂ , X ₃ , and X ₄ can all be alkoxy groups, or part of them can be alkoxy groups, but at least two of them must be alkoxy groups. Such as methoxy, ethoxy, propoxy, butoxy, isobutoxy, pentyloxy, hexyloxy, octyloxy, isooctyloxy, phenoxy, benzyloxy, substituted phenoxy Base, substituted benzyloxy, etc., the two necessary alkoxy groups are preferably methoxy and ethoxy. 3. Part of X ₁ , X ₂ , X ₃ , and X ₄ can be hydrocarbon groups, at most two of them can be hydrocarbon groups, such as methyl, ethyl, propyl, butyl, isobutyl, pentyl, cyclopentyl, Hexyl, cyclohexyl, octyl, isooctyl, phenyl, benzyl, substituted phenyl, substituted benzyl, etc. 4. The central carbon atom of the structural formula can also be used as a bridging carbon atom to connect with a hydrocarbon group to form a ring, such as an aliphatic six-membered ring, aliphatic seven-membered ring, cyclopentadiene ring, indene ring, fluorene ring, etc.

The ether compounds used are:1. The substituents _X3 and _X4 of the diether compound are alkyl or aryl. Alkyl diethers are: 2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl- 1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2,2 -Diisobutyl-1,3-dimethoxypropane, 2,2-dipentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxy 2,2-dicyclohexyl-1,3-dimethoxypropane. The aryl diethers are: 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane. 2. The substituents X ₁ , X ₂ , and X ₃ of the triether compound are alkoxy groups, and X ₄ is an alkyl or aryl group. The triether compounds are: 2-benzyl butanetriol trimethyl ether, 2-isobutylbutanetriol trimethyl ether, 2-indenyl butanetriol trimethyl ether, 2-fluorenyl butanetriol trimethyl ether, 2-benzyl -2-benzyloxymethyl-1,3-dimethoxypropane, etc. 3. Tetraethers: pentaerythritol tetramethyl ether, pentaerythritol tetraethyl ether, 2,2-diisopropoxymethyl-1,3-dimethoxypropane, 2-benzyloxymethyl butanetriol trimethyl ether, 2 , 2-dibenzyloxymethyl-1,3-dimethoxypropane, etc.

The ether olefin polymerization catalyst system of the present invention is used for olefin polymerization and copolymerization and has the following characteristics: 1. When the catalytic system of the present invention is used for olefin polymerization, no external electron donor is needed. 2. The catalyst activity is high, and it is 35,000 to 150,000 gPP/gCat. under bulk polymerization conditions. 3. The catalytic system has good adaptability and can be used in liquid-phase bulk polymerization, slurry polymerization and gas-phase polymerization systems, and can also be used for batch or continuous polymerization and copolymerization of olefins. 4. Proper selection of ether compounds makes catalysts and polymers free of aryl groups, which can be used for biological materials and food storage. 5. The catalyst and polymer particles are uniform, the particle size distribution is narrow, and the apparent density of the polymer is large, which can be adjusted within a certain range.

The preparation method of an ether olefin polymerization catalytic system of the present invention is carried out in the following order: 1. Preparation method of magnesium compound alcohol solution 1) Add magnesium halide, inert dispersant and alcohol in sequence into the reaction kettle fully replaced with inert gas. The molar ratio of alcohol to magnesium halide is 1-10, and the best molar ratio is 2-5. Heat and stir, react at 80-150°C for 1-8 hours, preferably at 100-135°C for 2-4 hours. The concentration of magnesium halide in the dispersant is 5-30g/l, preferably 10-20g/l, and cooled to 25°C to obtain magnesium halide alcohol solution. Method 2) Add magnesium halide compound, inert dispersant and alcohol in sequence to the reaction kettle fully replaced with inert gas, the molar ratio of alcohol to magnesium halide is 1-10, and the best molar ratio is 2-5. Heat and stir, react at 80-150°C for 1-8 hours, preferably at 100-135°C for 2-4 hours. The concentration of magnesium halide in the dispersant is 5-30g/l, preferably 10-20g/l. Cool to 20-80°C and add ether compounds, the molar ratio of magnesium halide to ether compounds is 50-0, preferably 20-0, cool to 25°C to obtain magnesium halide alcohol solution. 2. Catalyst preparation method 1) Drop the above-prepared magnesium halide compound alcohol solution into the titanium compound solution at -25-0°C in 0.5-3 hours, stir at this temperature for 1-3 hours, and heat up to 40-40°C. Add ether compounds at 100°C, the molar ratio of magnesium halide to ether compounds is 20:1-2:1. Raise the temperature to 100-135°C for 1-4 hours, filter the solid, then treat it with titanium tetrachloride at 100-135°C for 1-4 hours, filter it, wash it with anhydrous hexane for 1-6 times, and dry it in vacuum to obtain solid catalyst. Method 2) Take magnesium chloride alcoholate MgCl ₂ .xROH (x=0～5, R=C ₂ ～C ₆ ) to form a carrier, slowly add it to titanium tetrachloride at -25～0℃, within 1～4 hours Raise the temperature to 100-140°C. When the temperature rises to 40-100°C, add ether compounds, the molar ratio of magnesium halide to ether compounds is 20:1-2:1, and react at 100-135°C for 2 hours. Add TiCl ₄ to the filtered solid, and react at 100-135°C for 2 hours. After filtering, wash with hexane for 1 to 5 times, and dry in vacuum to obtain a solid catalyst.

The reagents used for synthesizing the above-mentioned catalysts are: alcohols are C ₁ ~C ₁₀ straight chain and branched alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, isoamyl alcohol, Hexanol, heptanol, octanol, isooctyl alcohol, nonanol, decanol, etc., preferably C ₅ -C ₈ branched alkanol. The above-mentioned inert dispersant is C ₇ -C ₃₀ aliphatic hydrocarbon and halogenated aromatic hydrocarbon. Including kerosene, vaseline oil, white oil, chlorobenzene, etc., preferably C ₉ -C ₁₅ aliphatic hydrocarbons.

The ether olefin polymerization catalyst system of the present invention has specific high activity, no external electron donor is needed during the polymerization reaction, and can be used for gas phase polymerization, slurry polymerization or bulk polymerization of olefins, and can also be used for copolymerization of olefins, which can be pre-polymerized and then polymerized or direct aggregation. Hydrogen is used as the polymer molecular weight modifier, and the polymerization temperature is 20°C to 90°C, preferably 40°C to 80°C.

The method for olefin polymerization of the present invention is as follows: Slurry polymerization: in 250 milliliters of reaction bottles that are vacuum-dried and fully replaced with nitrogen and propylene, add 100 milliliters of hexane treated with anhydrous and oxygen-free treatment, and keep the olefin pressure in the bottle at 770 mmHg, controlled at a certain temperature, add AlR ₃ heptane solution, stir for 5 minutes, add catalyst, polymerize for 1 hour, add 100 ml of acidified ethanol to terminate the reaction, filter with suction, wash with ethanol, and dry in vacuo to obtain a polymer. Bulk polymerization: Add 0.5-0.8 liters of propylene in a 2-liter high-pressure reactor after being fully dried and replaced by nitrogen and propylene. A solution of AlR ₃ in heptane was added and after stirring the catalyst was added. Then add 0.4-0.6 liters of propylene, rapidly raise the temperature to a certain temperature, polymerize at this temperature for 2 hours, release unreacted propylene, and obtain a polymer.

Example

Embodiment 1. Catalyst synthesis: 18 grams of anhydrous magnesium chloride, 80 milliliters of decane, 70 milliliters of kerosene, 30 milliliters of isooctyl alcohol and 20 milliliters of ethanol were successively added into a reaction kettle fully replaced with nitrogen. Heat to 100°C under stirring for 3 hours, after all the solids are dissolved, cool to 25°C, drop into 620ml of titanium tetrachloride and 100ml of chlorobenzene at 0°C within 2 hours. The temperature was raised to 100°C within 2 hours, and when the temperature was raised to 60°C, 4.8 ml of 2,2-dipropyl-1,3-dimethoxypropane was added and reacted at 100°C for 2 hours. After filtration, 100 ml of chlorobenzene and 450 ml of titanium tetrachloride were added and reacted at 120° C. for 2 hours. After suction filtration, wash five times with 100 ml of hexane at 55° C., and wash once with 100 ml of hexane at 25° C. After suction filtration and vacuum drying, 23.4 g of a solid catalyst with a titanium content of 3.06% was obtained. Olefin polymerization: After fully exchanging the 250ml three-necked flask with nitrogen and three times with propylene, add 100ml of heptane treated with anhydrous and anaerobic treatment. Under stirring, at a temperature of 70° C., a heptane solution (3.6 mmol/ml) of triethylaluminum was added, and then the above-mentioned catalyst was added. Under the condition that the pressure of propylene is 770mmHg, carry out the polymerization reaction for 1 hour, add acidified ethanol to terminate the reaction, wash the polymer with ethanol, and dry in vacuum to obtain the polymer. The operating conditions and polymer properties are listed in Table 1.

Example 2 Catalyst synthesis: 22 grams of anhydrous magnesium chloride, 210 ml of kerosene and 45 ml of ethanol were successively added into a reaction kettle fully replaced with nitrogen. Heat to 100°C for 2.5 hours under stirring. After the solid is dissolved, cool to 40°C and add 5.5 ml of 2,2-diisobutyl-1,3-dimethoxypropane, react for another hour, and cool to 25°C. Drop into 785 ml of titanium tetrachloride at -22°C within 1.5 hours. Heat up to 120°C within 2 hours, react for 3 hours, wash five times with 120 ml of hexane at 55°C, and wash once with 100 ml of hexane at room temperature. After suction filtration and vacuum drying, 26.7 g of a solid catalyst with a titanium content of 2.33% was obtained. Olefin polymerization: the method for propylene polymerization is the same as in Example 1, and the operating conditions and polymer properties are listed in Table 1.

Example 3 Catalyst synthesis: 11.5 grams of anhydrous magnesium chloride, 135 ml of white petrolatum, and 55 ml of isooctyl alcohol were successively added to a reaction kettle fully replaced with nitrogen. Heat to 135°C under stirring for 2 hours to react. After the solid dissolves, cool to 25°C and drop into 525 ml of titanium tetrachloride at -25°C within 2 hours. The temperature was raised to 135° C. within 2.5 hours, and when the temperature was raised to 40° C., 5.6 g of 2-fluorenylbutanetriol trimethyl ether was added. React at 135°C for 3 hours, wash five times with 65 ml of hexane at 65°C, and wash once with 60 ml of hexane at room temperature. After suction filtration and vacuum drying, 14.3 g of a solid catalyst with a titanium content of 3.18% was obtained. Olefin polymerization: The method of propylene polymerization is the same as that of Example 1, but the solvent of polymerization is toluene, and triisobutylaluminum is used as co-catalyst (3.6mmol/ml). The operating conditions and polymer properties are listed in Table 1.

Embodiment 4～5. The synthesis of the catalyst and the olefin polymerization method are the same as in Example 3, but the ethers used in Examples 4 to 5 are respectively 2,2-dibutyl-1,3-dimethoxypropane, 2,2-dipentyl- 1,3-Dimethoxypropane. The operating conditions and polymer properties are listed in Table 1. Example 6 Catalyst Synthesis: 3 l grams of anhydrous magnesium chloride, 330 ml of kerosene and 70 ml of isooctyl alcohol were successively added into a reactor fully replaced with nitrogen. It was heated to 125° C. for 2.5 hours under stirring and reacted for 2.5 hours. After the solid was dissolved, 4.2 g of 2,2-dibenzyl-1,3-methoxypropane was added and reacted for another 30 minutes. Cool to 25°C and drop into 985ml of titanium tetrachloride at -22°C within 2.5 hours. The temperature was raised to 120°C within 2.5 hours, and when the temperature was raised to 60°C, 9.3 g of 2,2-dibenzyl-1,3-dimethoxypropane was added and reacted at 120°C for 2 hours. After suction filtration, 950 ml of TiCl ₄ was added and reacted at 120° C. for 2 hours. After suction filtration, wash five times with 150 ml hexane at 55° C., and wash once with 150 ml hexane at room temperature. After suction filtration and vacuum drying, 36.8 g of a solid catalyst with a titanium content of 3.77% was obtained. Olefin polymerization: the method for propylene polymerization is the same as in Example 1, and the operating conditions and polymer properties are listed in Table 1.

Example 7 Catalyst synthesis: 14.5 g of MgCl ₂ .2.5C ₂ H ₅ OH formed carrier was slowly added to 385 ml of titanium tetrachloride at -22°C. The temperature was raised to 120°C within 2.5 hours, and when the temperature was raised to 60°C, 1.8 g of pentaerythritol tetramethyl ether was added and reacted at 120°C for 2.5 hours. After suction filtration, 350 ml of TiCl ₄ was added and reacted at 115°C for 2 hours. After suction filtration, it was washed five times with 50 ml of hexane at 65°C and once at room temperature with 50 ml of hexane. After suction filtration and vacuum drying, 7.8 g of a solid catalyst with a titanium content of 2.77% was obtained. Olefin polymerization: the method for propylene polymerization is the same as in Example 2, and the operating conditions and polymer properties are listed in Table 1.

Example 8 Catalyst synthesis: Take 16.7 g of MgCl ₂ .2.1C ₂ H ₅ OH shaped support and slowly add it to 415 ml of titanium tetrachloride at 0°C. The temperature was raised to 100°C within 2 hours, and when the temperature was raised to 40°C, 2.8 g of 2-benzylbutanetriol trimethyl ether was added and reacted at 100°C for 2 hours. After filtration, 410 ml of TiCl ₄ was added, the temperature was raised to 100°C, 4.2 g of 2-benzylbutanetriol trimethyl ether was added, and the reaction was carried out at 120°C for 2 hours. After suction filtration, it was washed five times with 55 ml of hexane at 60° C. and once with 55 ml of hexane at room temperature. After suction filtration and vacuum drying, 9.7 g of a solid catalyst with a titanium content of 3.22% was obtained. Olefin polymerization: the method for propylene polymerization is the same as in Example 2, and the operating conditions and polymer properties are listed in Table 1.

Table 1. Polymerization condition and polymerization result of embodiment 1～8 No. Titanium content Catalyst amount AlR ₃ activity M _w Melting point Isotacticity (%) (g) (ml) (gPP/gCat.) (°C) (%) Example 1 3.06 0.1220 2.2 187.3 30.33 160.2 94.7 Example 2 2.33 0.1087 3.0 276.7 12.16 163.7 97.6 例3 3.18 0.1479 4.1 264.4 16.58 161.5 95.8例4 3.02 0.1316 1.2 220.2 35.66 162.4 96.2例5 3.32 0.1268 3.7 234.6 22.79 162.9 96.0例6 3.77 0.1388 3.1 271.8 18.64 164.2 97.3例7 2.77 0.1306 4.2 215.3 10.03 161.6 96.1例8 3.22 0.1472 2.8 258.4 27.35 163.8 97.2 Polymerization conditions: 70°C, 60 minutes, AlR ₃ concentration 3.6mmol/ml, M _w ×10 ⁴ , solvent is heptane or toluene

The synthesis of embodiment 9～14 catalyst and olefin polymerization method are the same as embodiment 2, but the ether that adopts from embodiment 9～14 is respectively 2,2-diethyl-1,3-dimethoxypropane, 2, 2-dicyclopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxy propane, 2-isobutylbutanetriol trimethyl ether, 2-indenylbutanetriol trimethyl ether. Operating conditions and polymer properties are listed in Table 2

Table 2. Polymerization condition and polymerization result of embodiment 9～14 No. Titanium Content Catalyst Amount AlEt3 Activity _Mw Melting Point Isotacticity (%) (g) (ml) (gPP/gCat.) (°C) (%) 例9 3.17 0.0849 1.5 203.4 34.66 159.7 95.0例10 2.43 0.0759 1.6 325.7 18.93 164.1 97.3例11 4.62 0.1005 1.4 311.6 36.75 162.6 95.2例12 2.86 0.08631 2.9 286.6 12.66 162.2 96.0例13 3.20 0.0775 1.5 291.2 29.87 162.3 95.9例14 3.04 0.0995 1.8 306.8 26.36 163.4 96.8 Polymerization conditions: 70°C, 60 minutes, AlEt ₃ concentration 3.6mmol/ml, M _w ×10 ⁴ , solvent is toluene

The synthesis of embodiment 15～18 catalyst and olefin polymerization method are the same as embodiment 6, but the ether that adopts from embodiment 15～18 is respectively 2-benzyloxymethyl butanetriol trimethyl ether, 2,2-dibenzyloxymethyl Base-1,3-dimethoxypropane, pentaerythritol tetraethyl ether, 2,2-diisopropoxymethyl-1,3-dimethoxypropane. Operating conditions and polymer properties are listed in Table 3

table 3. Polymerization condition and polymerization result of embodiment 15～18 No. Titanium Content Catalyst Amount AlEt3 Activity _Mw Melting Point Isotacticity (%) (g) (ml) (gPP/gCat.) (°C) (%) Example 15 3.27 0.1442 2.8 236.5 18.62 161.4 95.6 Example 16 2.83 0.1052 1.7 241.6 14.35 161.1 96.0 Example 17 3.46 0.1270 3.8 263.3 9.47 162.0 95.1 Cases 18 3.09 0.1357 2.54.8 12.69 164.5 Polymerization conditions: 70°C, 60 minutes, AlEt ₃ concentration 3.6mmol/ml, M _w ×10 ⁴ , solvent is heptane

The synthesis of the catalyst of Examples 19 to 23 is the same as in Example 2, but the ethers used in Examples 19 to 23 are 2,2-dibutyl-1,3-dimethoxypropane, 2,2-dipentyl- 1,3-dimethoxypropane, 2-benzylbutanetriol trimethyl ether, 2,2-dibenzyloxymethyl-1,3-dimethoxypropane and 2,2-diisobutyl- 1,3-Dimethoxypropane. Olefin polymerization: In a 2-liter high-pressure reactor, after fully drying, replace with nitrogen three times, and then fully replace with propylene, add 0.5 liter of propylene, and add a heptane solution of triethylaluminum (0.9 mmol/ml). Then add 0.5 liter of propylene, rapidly raise the temperature to 70°C, polymerize at this temperature for 2 hours, release unreacted propylene, and obtain a polymer. The operating conditions and polymer properties are listed in Table 4.

Table 4. Polymerization condition and polymerization result of embodiment 19～23 No. Titanium Content Catalyst Amount AlEt3 Activity _Mw Melting Point Isotacticity (%) (g) (ml) (gPP/gCat.) (°C) (%) 例19 3.42 0.0052 0.7 7.36 14.32 163.6 96.7例20 2.98 0.0047 0.5 6.95 15.86 162.5 96.2例21 4.46 0.0049 1.0 8.72 8.67 164.0 97.4例22 4.19 0.0038 0.8 9.46 10.32 163.7 98.2例23 4.05 0.0044 0.9 12.8 11.87 164.2 98.6 Polymerization conditions: 70°C, 2 hours, AlEt ₃ concentration 0.9mmol/ml, activity × 10 ⁴ , M _w × 10 ⁴

Claims (11)

1. catalyst system for ether-type olefine polymerization, contain Primary Catalysts and promotor, it is characterized in that a kind of solid catalyst that described Primary Catalysts is made up of magnesium chloride support load titanium tetrachloride and ether compound, wherein the mole proportioning of magnesium chloride and ether compound is 50: 1～1: 1, promotor is triethyl aluminum and triisobutyl aluminium, and the structural formula of above-mentioned ether compound is:

X ₁, X ₂, X ₃And X ₄Be-oxyl or alkyl.

2. a kind of catalyst system for ether-type olefine polymerization according to claim 1 is characterized in that described ether compound is a diether compounds, three ether compounds or tetraether compound.

3. ether compound according to claim 2 is characterized in that the substituent X of described diether compounds ₁=X ₂Be methoxyl group, X ₃And X ₄Be alkyl, diether compounds is: 2, and 2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal or 2,2-phenylbenzene-1,3-Propanal dimethyl acetal.

4. ether compound according to claim 2 is characterized in that the substituent X of described three ether compounds ₁=X ₂=X ₃Be methoxyl group, X ₄Be alkyl, three ether compounds are: 2-benzyl trihydroxybutane three methyl ethers, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers or 2-fluorenyl trihydroxybutane three methyl ethers.

5. ether compound according to claim 2 is characterized in that the substituent X of described tetraether compound ₁, X ₂, X ₃And X ₄Be-oxyl, the tetraether compound is: tetramethylolmethane tetramethyl ether, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, 3-Propanal dimethyl acetal, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal or 2-benzyloxy trihydroxybutane three methyl ethers.

6. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 1, it is characterized in that carrying out in the following order: (1) is with magnesium chloride, inertia dispersion agent decane or kerosene and alcohol mix, heated and stirred, in 80～150 ℃ of reactions 1～8 hour, be cooled to 20～80 ℃ and add ether compound, be cooled to 25 ℃, obtain the magnesium chloride alcoholic solution, alcohol is 1～10 with the mol ratio of magnesium chloride, magnesium chloride and ether compound mol ratio are 50～0, the concentration of magnesium chloride in dispersion agent is 5-30g/l, and (2) with above-mentioned magnesium chloride alcoholic solution, joins in-25～0 ℃ the titanium tetrachloride solution, stirred 1～3 hour, add ether compound at 40～100 ℃, the mol ratio of magnesium chloride and ether compound 20: 1～2: 1 is warming up to 100～135 ℃ of reactions 1～4 hour, solid after filtering was handled 1～4 hour in 100～135 ℃ with titanium tetrachloride again, filter washing, the dry solid catalyst that gets.

7. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 1, it is characterized in that magnesium chloride alcohol adduct shaping carrier, join in-25～0 ℃ the titanium tetrachloride, in the time of 40-100 ℃, add ether compound, the mol ratio of magnesium chloride and ether compound 20: 1～2: 1 100～135 ℃ of reactions 2 hours, adds TiCl in the solid after overanxious ₄,, filter washing, the dry solid catalyst that gets 100～135 ℃ of reactions 2 hours.

8. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 6, the mol ratio that it is characterized in that above-mentioned alcohol and magnesium chloride is 2～5.

9. according to the preparation method of claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described diether compounds is: 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal or 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal.

10. according to the preparation method of claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described three ether compounds are: 2-benzyl trihydroxybutane three methyl ethers, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers or 2-fluorenyl trihydroxybutane three methyl ethers.

11. preparation method according to claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described tetraether compound is: tetramethylolmethane tetramethyl ether, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, 3-Propanal dimethyl acetal, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal or 2-benzyloxy trihydroxybutane three methyl ethers.