CN116948067B - Catalyst for propylene polymerization and propylene polymerization or copolymerization reaction method - Google Patents
Catalyst for propylene polymerization and propylene polymerization or copolymerization reaction methodInfo
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- CN116948067B CN116948067B CN202210378701.3A CN202210378701A CN116948067B CN 116948067 B CN116948067 B CN 116948067B CN 202210378701 A CN202210378701 A CN 202210378701A CN 116948067 B CN116948067 B CN 116948067B
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Abstract
本发明公开了一种用于丙烯聚合的催化剂及丙烯聚合或共聚合反应方法，该催化剂包括：含钛的主催化剂A、助催化剂B；主催化剂A包括卤化镁的醇合物载体、卤化钛和内给电子体，内给电子体为具有通式(Ⅰ)所式的分子骨架为噻吩结构的双膦化合物：其中，R1、R2、R3和R4相同或不相同，且各自独立地选自氢原子、C1～C20的直链或支链烷基、C3～C20的环烷基、C6～C20的芳基、C7～C20的芳烷基和C7～C20的烷氧基芳基。本发明的催化剂在高温聚合条件下表现出较高的催化活性，同时解决了制备高温聚合物等规指数偏低的问题。This invention discloses a catalyst for propylene polymerization and a method for propylene polymerization or copolymerization. The catalyst comprises: a titanium-containing main catalyst A and a co-catalyst B; the main catalyst A comprises a magnesium halide alkoxide support, titanium halide, and an internal electron donor, wherein the internal electron donor is a bisphosphine compound having a thiophene structure with the general formula (I). In this invention, R1 , R2 , R3 , and R4 may be the same or different, and each is independently selected from hydrogen atoms, C1-C20 straight-chain or branched alkyl groups, C3-C20 cycloalkyl groups, C6-C20 aryl groups, C7-C20 aralkyl groups, and C7-C20 alkoxyaryl groups. The catalyst of this invention exhibits high catalytic activity under high-temperature polymerization conditions, while simultaneously solving the problem of low isotactic index in the preparation of high-temperature polymers.
Description
Technical Field
The invention relates to a catalyst for olefin polymerization, in particular to a catalyst for propylene polymerization and a propylene polymerization or copolymerization reaction method.
Background
The internal electron donor compound, which is one of the important components of Ziegler-Natta catalyst, plays a critical role in improving the performance of the catalyst, and can not only improve the orientation capability of the catalyst, but also improve the activity of the catalyst. For example, the invention of common 1, 3-diether electron donor compounds can obviously improve the catalytic activity of the catalyst, the isotactic index of the polymer and the like. The structure of the different 1, 3-diether electron donor compounds and the properties of the catalysts obtained therefrom are reported as ：CN1473809、CN1376722、CN1298887、CN1268957、CN1143651、CN1141303、CN1141285、CN1066723;EP0728770、EP0728724、EP0361493、US5095153、US5068213、US4978648 et al.
Chinese patent CN101560272a discloses a catalyst for olefin polymerization, wherein the internal electron donor is diaryl acid-2, 4-pentanediol ester, and the catalyst prepared from 2- (2-thiophenecarboxylic acid) -4- (p-isopropylbenzoic acid) pentanediol ester has higher activity, reaching 58.4KgPP/gcat, but the isotactic index of the polymer prepared from the catalyst is lower.
Chinese patent CN105985469a discloses a polymerization catalyst of biphosphine compound of biphenyl structure as an internal electron donor, which has better activity in propylene polymerization than catalysts containing monophosphate or biphosphite, and gives polypropylene with wider molecular weight distribution. The general formula of the internal electron donor is:
However, the highest polymerization activity of the catalyst is 32.5KgPP/gTi, and the polymerization activity is still lower than that of a general catalyst in the market.
At present, a high-efficiency carrier type Ziegler-Natta (Z-N) catalyst commonly used in olefin polymerization generally adopts aluminum alkyl (such as Et 3 AL and the like) as a cocatalyst, propylene polymerization is carried out at a temperature of 65-80 ℃, high polymerization activity can be obtained, and the obtained polymer has high isotactic index, but the polymerization activity of the catalyst and the isotactic index, molecular weight and the like of the polymer are drastically reduced after the polymerization temperature is continuously increased. Because the main function of the aluminum alkyl is to alkylate the active center, but the alkylation is also carried out, the polymerization temperature is raised, the reduction reaction is promoted, more active center Ti 3+ is reduced to Ti 2+, the deactivation of the active center of the catalyst is accelerated, the polymerization reaction speed is reduced, the polymerization activity of the system is reduced, the generated oligomer is increased, and the isotactic index of the finally obtained polymer is lower.
Aluminoxane is not an effective cocatalyst for magnesium halide supported Ziegler-Natta catalysts, but increasing the polymerization temperature of propylene, and the addition of aluminoxane to the polymerization system can increase the polymerization activity of the catalyst, but the polymerization activity is still not ideal. For example, chinese patent CN1887918a discloses a catalyst, in which a mixture of aluminoxane and alkyl aluminum is introduced as a cocatalyst in the polymerization process, and the catalyst system still has higher activity and stereotacticity at a polymerization temperature of 100 ℃ of propylene, but the activity of propylene polymerization at high temperature is still lower, the isotactic index of the polymer is up to 95%, and both the activity and stereotacticity of the catalyst are still to be further improved.
The modification of methylaluminoxane and the effect of the modification on the polymerization catalytic activity of ethylene in the Japanese patent application, chemical research, 2004,15 (1) 24-26, and the authors utilize the effect of BCl 3 and Methylaluminoxane (MAO) to prepare modified methylaluminoxane (BMAO), examine the performance of a metallocene catalyst system Cp 2ZrCl2/BMAO in catalyzing the polymerization of ethylene, and compared with MAO, the polymerization activity can be properly increased and the MAO dosage can be reduced by using BMAO as a cocatalyst. However, a large amount of toluene is used as a solvent in preparation BMAO, which is not beneficial to post-treatment and environmental protection of the product.
Chinese patent CN1421468a discloses that by controlling the process conditions and the prepolymerization multiple in the prepolymerization process, the conventional Z-N catalyst is suitable for polymerization of propylene at a higher temperature (> 85 ℃) and provides a method for polymerizing or copolymerizing propylene at a high temperature and a catalyst prepolymer suitable for the method, but the prepolymerization multiple control means mentioned in the method embodiment is more complex, and the isotactic index of the obtained polymer is still lower than that of the polymer prepared at 70 ℃.
Chinese patent CN1621421a discloses that the catalyst component is introduced into a mixture of aluminoxane prepared by reacting trialkylaluminum with water to achieve high temperature polymerization of propylene, but the preparation method is also complicated in process, and both the high temperature polymerization activity and the isotactic index of the polymer are to be further improved.
There are various disadvantages of the catalyst or the high temperature polymerization method in the prior art, so that it is necessary to provide a new catalyst and a high temperature polymerization method to overcome the disadvantages of the prior art.
Disclosure of Invention
The invention aims to provide a catalyst for propylene polymerization, which comprises a biphosphine compound containing a thiophene molecular skeleton and a functional group. Another object of the present invention is to provide a propylene polymerization or copolymerization reaction method, wherein the catalyst of the present invention can exhibit higher catalytic activity when used for propylene polymerization or copolymerization reaction under high temperature polymerization conditions, and solve the problem of lower isotactic index when preparing high temperature polymers.
To achieve the above object, the present invention provides a catalyst for propylene polymerization comprising a titanium-containing procatalyst a and a cocatalyst B, wherein:
the main catalyst A is a titanium catalyst supported by a magnesium halide alkoxide carrier and comprises a magnesium halide alkoxide carrier, titanium halide and an internal electron donor, wherein the internal electron donor is a biphosphine compound with a molecular skeleton of a general formula (I) as a thiophene structure:
Wherein R 1、R2、R3 and R 4 are the same or different and are each independently selected from a hydrogen atom, a C1-C20 linear or branched alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group and a C7-C20 alkoxyaryl group, P is phosphorus, S is sulfur, and the cocatalyst B is a mixture of aluminoxane modified by Lewis acid and an alkylaluminum compound.
The present invention is not particularly limited to the magnesium halide alkoxide carrier selected from at least one of a magnesium chloride ethanol adduct carrier, a magnesium bromide ethanol adduct carrier, a magnesium chloride isopropanol adduct carrier, a magnesium chloride n-butanol adduct carrier, a magnesium chloroethoxychloride methanolate adduct carrier, preferably a magnesium chloride ethanol adduct carrier.
The present invention is not particularly limited to titanium halide, which is a liquid compound completely soluble in a nonpolar solvent at an application temperature, and is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, and titanium trichloride, preferably titanium tetrachloride.
The catalyst for propylene polymerization of the present invention is selected from 3, 4-bis (dimethylphosphino) -thiophene, 3, 4-bis (diethylphosphino) -thiophene, 3, 4-bis (di-n-propylphosphino) -thiophene, 3, 4-bis (diisopropylphosphino) -thiophene, 3, 4-bis (di-n-butylphosphino) -thiophene, 3, 4-bis (diisobutylphosphino) -thiophene, 3, 4-bis (di-n-pentylphosphino) -thiophene, 3, 4-bis (dicyclopentylphosphino) -thiophene, 3, 4-bis (di-n-hexylphosphino) -thiophene, 3, 4-bis (dicyclohexylphosphino) -thiophene, 3, 4-bis (diphenylphosphino) -thiophene, 3, 4-bis (di-p-tolylphosphino) -thiophene, 3, 4-bis (di-m-tolylphosphino) -thiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -thiophene, 3, 4-bis (di-m-methoxyphenylphosphino) -thiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -thiophene, 3, 4-bis (dimethylphosphino) -2-methylthiophene, 3, 4-bis (diethylphosphino) -2-methylthiophene, 3, 4-bis (di-n-propylphosphino) -2-methylthiophene, 3, 4-bis (diisopropylphosphino) 2-methyl-thiophene, 3, 4-bis (di-n-butylphosphino) -2-methylthiophene, 3, 4-bis (diisobutylphosphino) -2-methylthiophene, 3, 4-bis (di-n-pentylphosphino) -2-methylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-methylthiophene, 3, 4-bis (di-n-hexylphosphino) -2-methylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-methylthiophene, 3, 4-bis (diphenylphosphino) -2-methylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-methylthiophene, 3, 4-bis (di-m-tolylphosphino) -2-methylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (di-m-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (di-o-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (dimethylphosphino) -2-ethylthiophene, 3, 4-bis (diethylphosphino) -2-ethylthiophene, 3, 4-bis (di-n-propylphosphino) -2-ethylthiophene, 3, 4-bis (diisobutylphosphino) -2-ethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-ethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-ethylthiophene, 3, 4-bis (diphenylphosphino) -2-ethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-ethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2-ethylthiophene, 3, 4-bis (dimethylphosphino) -2-isopropylthiophene, 3, 4-bis (diethylphosphino) -2-isopropylthiophene, 3, 4-bis (di-n-propylphosphino) -2-isopropylthiophene, 3, 4-bis (diisobutylphosphino) -2-isopropylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-isopropylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-isopropylthiophene, 3, 4-bis (diphenylphosphino) -2-isopropylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-isopropylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-isopropylthiophene, 3, 4-bis (dimethylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diethylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-n-propylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diisobutylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diphenylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dimethylphosphino) -2-phenylthiophene, 3, 4-bis (diethylphosphino) -2-phenylthiophene, 3, 4-bis (di-n-propylphosphino) -2-phenylthiophene, 3, 4-bis (diisobutylphosphino) -2-phenylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-phenylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-phenylthiophene, 3, 4-bis (diphenylphosphino) -2-phenylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-phenylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-phenylthiophene, 3, 4-bis (dimethylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diethylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-n-propylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diisobutylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dicyclopentylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dicyclohexylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diphenylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-p-tolylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dimethylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diethylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diethylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diethylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-diphenylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diethylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-di-p-tolylthiophene, At least one of 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-di-p-tolylthiophene.
Preferably, the internal electron donor is selected from at least one of 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dimethylphosphino) -2-isopropylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dimethylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dimethylphosphino) -2- (4-ethylphenyl) thiophene.
The catalyst for propylene polymerization comprises the following components in percentage by weight:
the invention is not particularly limited to the preparation method of the main catalyst A, and a method can be adopted in which magnesium halide and partial titanium halide are mixed, an internal electron donor of a biphosphine compound containing a thiophene molecular skeleton and a functional group is added, the mixture is filtered after heating treatment, and the residual titanium halide is added, heated, filtered, washed and dried to prepare a catalyst product. The preparation method comprises the following steps of (1) adding spherical magnesium halide alkoxide particles into titanium halide liquid at the temperature of-50-20 ℃ for reaction for 10 minutes to 5 hours, wherein the molar ratio of magnesium to titanium is 1:5-1:100, (2) heating to 0-90 ℃, adding an internal electron donor compound, wherein the molar ratio of magnesium to the internal electron donor compound is 2:1-20:1, (3) heating to 100-140 ℃ for reaction for 1-6 hours, (4) adding titanium halide liquid with the same amount as that in the step 1 after filtration, reacting for 1-4 hours at the temperature of 110-130 ℃, and then filtering, washing and drying to obtain the supported main catalyst A.
According to the catalyst for propylene polymerization, the ratio of the Lewis acid modified aluminoxane to the alkyl aluminum compound is 1:1-50, preferably 1:1-10, calculated by the molar ratio of aluminum to aluminum.
The catalyst for propylene polymerization of the present invention has the following general formula:
Wherein Y is C 1-C12 alkyl, Y 2 is 2Y groups, a is an integer of 4-30, al is aluminum, and O is oxygen. The aluminoxane is, for example but not limited to, at least one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, preferably the aluminoxane is methylaluminoxane.
The catalyst for propylene polymerization according to the present invention is modified with a Lewis acid such as, but not limited to, BF 3、BCl3、BBr3、AlCl3、ZnCl2 or the like, preferably BF 3. Wherein the molar ratio of the Lewis acid to the aluminoxane is 1:1-500, preferably 1:1-50.
The present invention is not particularly limited to the method of modifying aluminoxane with a Lewis acid, and the method of modifying aluminoxane is, for example, but not limited to, vacuum-pumping a dry polymerization bottle-nitrogen-substitution three times, adding a certain amount of toluene solution of aluminoxane to the bottle, and adding a Lewis acid to the bottle to react for a certain period of time to obtain a Lewis acid-modified aluminoxane.
The general formula of the aluminum alkyl compound is AlZ nX(3-n), wherein Z is alkyl, aryl or aralkyl of C 1～C20, X is halogen, preferably chlorine, n is an integer of 0-3, and Al is aluminum. The alkyl aluminum compound is, for example, but not limited to, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride and diisobutylaluminum monochloride, preferably triethylaluminum or triisobutylaluminum.
The catalyst for propylene polymerization also contains an organic electron donor C, wherein the organic electron donor C is an alkoxy silane compound and is at least one selected from cyclohexyl methyl dimethoxy silane (CHMMS), dicyclopentyl dimethoxy silane, diisopropyl dimethoxy silane, diisobutyl dimethoxy silane, dimethoxy dimethyl silane, diethoxy dimethyl silane or dimethoxy diphenyl silane, and cyclohexyl methyl dimethoxy silane is preferable.
The catalyst for propylene polymerization is characterized in that the molar ratio of titanium to aluminum to silicon is 1:5-1000:0-500, and the molar ratio of titanium to aluminum to silicon in the catalyst is preferably 1:10-50:0-5 when the catalyst is applied to propylene polymerization.
The invention also provides a propylene polymerization or copolymerization reaction method, which is characterized in that the catalyst is adopted.
The propylene polymerization or copolymerization reaction method of the invention comprises the following steps:
(1) Carrying out pre-complexing reaction on a main catalyst A and a cocatalyst B for 0-20 min at the temperature of-10-60 ℃ to obtain a pre-complexing catalyst system;
(2) Carrying out prepolymerization reaction on propylene for 5-30 min in the presence of the pre-complex catalyst system in the step (1) at the temperature of 0-60 ℃ to obtain a prepolymer;
(3) And (3) under the condition of 85-120 ℃, propylene is polymerized or copolymerized in the presence of the prepolymer in the step (2) in a liquid phase or gas phase medium. In the propylene polymerization or copolymerization reaction method, in the step (1), the pre-complexing temperature is 0-30 ℃ and the pre-complexing time is 5-10 min.
In the propylene polymerization or copolymerization reaction method, in the step (2), the temperature of the prepolymerization reaction is 40-50 ℃, and the time of the prepolymerization reaction is 10-20 min.
In the propylene polymerization or copolymerization reaction method, in the step (3), the polymerization temperature is 93-110 ℃, and the polymerization reaction time is 1 hour.
The propylene polymerization or copolymerization process of the present invention is operated in the liquid phase of the monomer or monomers in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas-liquid phase.
The catalyst provided by the invention uses the biphosphine compound containing a thiophene structure, and the lone pair electrons of the phosphorus atom and the sulfur atom in the biphosphine compound can stabilize the central metal titanium, so that the catalyst has higher activity in propylene polymerization, the phosphorus atom and the sulfur atom in the biphosphine compound containing the thiophene structure provide two different chemical environments, and meanwhile, the problem of low isotactic index of a polymer prepared at a high temperature is solved by virtue of the space structure provided by the thiophene skeleton. The catalyst disclosed by the invention can be used for high-temperature propylene polymerization or copolymerization reaction, and has higher catalytic activity in propylene high-temperature polymerization, wherein the catalytic activity of the catalyst in polymerization or copolymerization of olefin at a high temperature of 85-120 ℃ is 2 times or more than that of the catalyst at a common polymerization temperature of 65-80 ℃.
According to the invention, the aluminum alkoxide as a cocatalyst is modified by the Lewis acid, the aluminum alkoxide and the Lewis acid form a complex, and the electron-withdrawing property of the Lewis acid causes the electron cloud of the aluminum alkoxide to deviate to the Lewis acid, so that the electron effect enhances the electropositivity of the aluminum atom and improves the acidity of the cocatalyst, thereby enhancing the electropositivity of the titanium catalyst, improving the alkylation capacity of an active center, reducing the excessive reduction of the titanium in the active center, stabilizing the active center and improving the activity of the catalyst. In addition, because the aluminoxane modified by Lewis acid removes free trimethylaluminum in the aluminoxane, the stereoselectivity of the catalyst system is improved, and the problem of low isotactic index of the prepared high-temperature polymer is solved.
Detailed Description
The following describes the present invention in detail, the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the scope of protection of the present invention is not limited to the following examples, in which the experimental methods of specific conditions are not noted, and generally according to conventional conditions.
Test method
The polymer isotactic index is measured by heptane extraction (heptane boiling extraction for 6 hours), i.e., 1 gram of a dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, and the ratio of the polymer weight (g) obtained by drying the residue to constant weight to 1 is the isotactic index.
Synthesis of internal electron donor
The invention is not particularly limited to a preparation method of an internal electron donor, and for convenience of explanation, taking 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene as an example, the preparation method of the internal electron donor can adopt the following steps:
Adding 1.0g of 2, 5-dimethylthiophene and 1.9g of NaOAc into 50mL of CH 2Cl2 for reaction at normal temperature and in a dark place for 5min, then cooling to 0 ℃, gradually dropwise adding 0.96mL of Br 2 at the same time, heating to room temperature after the completion of the dropwise addition, reacting for 2h, adding 10% of Na 2S2O3 solution, separating liquid, extracting aqueous phase with CH 2Cl2, merging organic phases, washing with water, drying the organic phases with anhydrous MgSO 4, and separating by using petroleum ether as eluent by column chromatography to obtain colorless solid 3, 4-dibromo-2, 5-dimethylthiophene with 1.87g and 75% yield.
Adding 6g of 3, 4-dibromo-2, 5-dimethylthiophene into 70mLTHF under the nitrogen atmosphere, cooling to-78 ℃, slowly dripping 18.8mL of n-hexane solution of n-butyllithium, maintaining the temperature to-78 ℃, stirring for 1h, adding 8.41mL of diphenyl phosphine chloride, heating to room temperature, reacting for 5h, quenching the reaction with water, extracting an organic phase with CH 2Cl2, drying, steaming off the organic solvent, and obtaining 7.42g of white solid through column chromatography, wherein the yield is 69%. 31P NMR(CDCl3 120 MHz) delta-21.45.
The internal electron donors used in the examples below were synthesized according to this method.
Example 1
1. Preparation of the procatalyst 5.0 g of microspherical magnesium chloride alkoxide particles (homemade, average particle size 50 μm, specific surface 150-230m 2/g, molar ratio of alcohol to magnesium chloride content 2.85:1, molecular formula: mgCl 2·2.85CH3CH2 OH) were added to 140mL titanium tetrachloride liquid at-20 ℃ C. Under anhydrous and anaerobic conditions, reacted for 1 hour, then gradually warmed to 60 ℃ C., 1.2g of 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene was added, gradually warmed to 120 ℃ C., reacted for 2 hours, filtered, and titanium tetrachloride 140mL was added, reacted at 120 ℃ C. For 1 hour and filtered. Washing 5 times with 100mL of hexane at 60℃and once with 50mL of hexane at room temperature gave the main catalyst after drying in vacuo.
2. Preparation of the Co-catalyst, namely, a dried 50mL polymerization bottle is vacuumized and replaced by nitrogen for three times, 20mL MAO (0.5 mol/L MAO toluene solution) produced by Shanghai Yabao is added into the polymerization bottle under the protection of nitrogen, 10mL of BF 3 diethyl ether solution (0.5 mol/L BF 3 diethyl ether solution) is dropwise added, the molar ratio of BF 3 to MAO is 1:2, and after a certain period of reaction, a complex solution of BF 3 and MAO is obtained and is recorded as BMAO for standby.
3. The preparation method comprises the steps of (1) pre-complexing a catalyst system at a high temperature (more than or equal to 93 ℃), adding 30mg of a main catalyst into a glass bottle with 100mL of glass at normal temperature under the protection of nitrogen, adding 1.25mL of triethylaluminum (1 mol/L of hexane solution), 2.5mL BMAO of mixed solution and 0.1mL of cyclohexylmethyl dimethoxy silane, pre-complexing the catalyst system in the glass bottle for 5min, (2) pre-polymerizing, carrying out a pre-polymerizing reaction, carrying out vacuum drying treatment on 10L of the catalyst system in a high-temperature polymerization kettle with nitrogen and propylene fully replaced by the gas, firstly adding 0.5kg of propylene, then adding the pre-complexed catalyst system under the protection of nitrogen, continuously adding 1.5kg of propylene, keeping stirring, carrying out pre-polymerizing for 10min at the temperature of 10 ℃, carrying out high-temperature polymerization, quickly raising the temperature of the polymerization kettle to 93 ℃ after the pre-polymerizing reaction is finished, and discharging unreacted propylene to obtain the high-temperature polymer.
The polymerization results are shown in Table 1.
Example 2
The preparation of the main catalyst and the cocatalyst was the same as in example 1, except that the prepolymerization temperature was increased to 25℃in the polymerization prepolymerization of propylene at high temperature (. Gtoreq.93 ℃).
The polymerization results are shown in Table 1.
Example 3
The preparation of the main catalyst and the cocatalyst was the same as in example 1, except that the prepolymerization temperature was increased to 45℃in the polymerization prepolymerization of propylene at high temperature (. Gtoreq.93 ℃).
The polymerization results are shown in Table 1.
Example 4
The preparation of the main catalyst and the cocatalyst was the same as in example 1, except that the polymerization prepolymerization temperature of propylene was increased to 60℃at a high temperature (. Gtoreq.93 ℃).
The polymerization results are shown in Table 1.
Example 5
The preparation of the main catalyst and the cocatalyst is the same as in example 1, except that the polymerization prepolymerization temperature of propylene at high temperature (more than or equal to 93 ℃) is increased to 45 ℃ and the prepolymerization time is increased to 15min.
The polymerization results are shown in Table 1.
Example 6
The preparation of the main catalyst and the cocatalyst is the same as in example 1, except that the polymerization prepolymerization temperature of propylene at high temperature (more than or equal to 93 ℃) is increased to 45 ℃ and the prepolymerization time is increased to 20min.
The polymerization results are shown in Table 1.
Example 7
The preparation of the main catalyst and the cocatalyst, and the polymerization and prepolymerization temperature and prepolymerization time of propylene at high temperature (more than or equal to 93 ℃) are the same as those of example 5, except that triethylaluminum (1 mol/L hexane solution) is added in an amount of 3.5mL and BMAO solution is added in an amount of 1.5mL in the pre-complexation stage of the catalyst system.
The polymerization results are shown in Table 1.
Example 8
The preparation of the main catalyst and the cocatalyst, and the polymerization and prepolymerization of propylene at high temperature (93 ℃ or more) were carried out in the same manner as in example 5, except that triethylaluminum (1 mol/L hexane solution) was added in an amount of 5mL and BMAO solution was added in an amount of 1mL in the stage of pre-complexation of the catalyst system.
The polymerization results are shown in Table 1.
Example 9
The preparation of the main catalyst and the cocatalyst, and the polymerization and prepolymerization temperature and prepolymerization time of propylene at high temperature (more than or equal to 93 ℃) were the same as those of example 5, except that triethylaluminum (1 mol/L hexane solution) was added in an amount of 12.5mL and BMAO solution in an amount of 0.5mL during the pre-complexation stage of the catalyst system.
The polymerization results are shown in Table 1.
Example 10
The preparation of the main catalyst and the cocatalyst, and the polymerization and prepolymerization temperature and prepolymerization time of propylene at high temperature (more than or equal to 93 ℃) are the same as those of example 5, except that in the preparation process of the catalyst, the carrier is replaced by the magnesium chloride ethanol adduct.
The polymerization results are shown in Table 1.
Example 11
The preparation of the main catalyst and the cocatalyst, and the polymerization and prepolymerization temperature and prepolymerization time of propylene at high temperature (more than or equal to 93 ℃) are the same as those of example 5, except that triisobutylaluminum (1 mol/L hexane solution) is added in the catalyst system in the pre-complexation stage in an amount of 2.5mL and BMAO solution in an amount of 2.5mL.
The polymerization results are shown in Table 1.
Example 12
The preparation of the main catalyst, the polymerization and prepolymerization of propylene at high temperature (not less than 93 ℃) for the same time as in example 5, except that 1mLBF 3 of diethyl ether solution (0.5 mol/L of BF 3 diethyl ether solution) was added during the preparation of the cocatalyst, and the molar ratio of BF 3 to MAO was 1:20.
The polymerization results are shown in Table 1.
Example 13
The preparation of the main catalyst, the polymerization and prepolymerization of propylene at high temperature (93 ℃ C. Or more) and the prepolymerization time were the same as those of example 5, except that 20mL of BF 3 diethyl ether solution (0.5 mol/L of BF 3 diethyl ether solution) was added during the preparation of the cocatalyst, and the molar ratio of BF 3 to MAO was 1:1.
The polymerization results are shown in Table 1.
Example 14
The preparation of the main catalyst and the cocatalyst was the same as in example 1;
The preparation method comprises the steps of (1) pre-complexing a catalyst system at a high temperature (more than or equal to 93 ℃) and carrying out a pre-polymerization reaction, wherein 0.5kg of propylene is firstly added into 10L of a high-temperature polymerization kettle which is subjected to vacuum drying treatment and is fully replaced by nitrogen and propylene gas, the pre-complexing catalyst system is added under the protection of nitrogen, stirring is kept, and the polymerization is carried out for 15min at 45 ℃, and (3) carrying out high-temperature polymerization, after the pre-polymerization reaction is finished, the temperature of the polymerization kettle is quickly increased to 93 ℃, and a mixed gas of ethylene and propylene (wherein the volume fraction of the ethylene is 3%) is introduced, and after the polymerization is carried out for 1 hour, the ethylene-propylene mixture which is not reacted is discharged, so as to obtain the high-temperature polymer.
The polymerization results are shown in Table 1.
Example 15
Preparation of procatalyst and cocatalyst the preparation method of the procatalyst and cocatalyst is the same as in example 1 except that 3, 4-bis (dimethylphosphino) -2, 5-dimethylthiophene is replaced with 3, 4-bis (diphenylphosphino) -2-isopropylthiophene during the preparation of the procatalyst.
Propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 5.
The polymerization results are shown in Table 1.
Example 16
Preparation of procatalyst and cocatalyst the preparation method of the procatalyst and cocatalyst was the same as in example 1 except that 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene was used in place of 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene in the preparation of the procatalyst.
Propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 5.
The polymerization results are shown in Table 1.
Example 17
Preparation of the procatalyst and cocatalyst the same procedure as in example 16.
Ethylene propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 14.
The polymerization results are shown in Table 1.
Example 18
Preparation of a procatalyst, cocatalyst and propylene high temperature polymerization the same as in example 16 except that BF 3 modified methylaluminoxane in the cocatalyst preparation was replaced with BF 3 modified ethylaluminoxane.
The polymerization results are shown in Table 1.
Example 19
Preparation of the Main catalyst and Co-catalyst propylene high temperature polymerization example 16 was followed except that BF 3 modified methylaluminoxane in the preparation of Co-catalyst was replaced with BF 3 modified isopropylaluminoxane.
The polymerization results are shown in Table 1.
Example 20
Preparation of the Main catalyst and Co-catalyst propylene high temperature polymerization the same as in example 16, except that diethylaluminum chloride was used in place of triethylaluminum.
The polymerization results are shown in Table 1.
Example 21
The preparation of the main catalyst and the cocatalyst was the same as in example 16, except that cyclohexylmethyldimethoxysilane was not added during the high-temperature polymerization, and the other polymerization methods were the same as in example 16.
The polymerization results are shown in Table 1.
Example 22
Preparation of the Main catalyst and Co-catalyst, high temperature polymerization of propylene As in example 16, except that the amount of cyclohexylmethyldimethoxysilane added was increased from 0.1mL to 0.2mL.
The polymerization results are shown in Table 1.
Example 23
Preparation of the Main catalyst and Co-catalyst, high temperature polymerization of propylene the same as in example 16 was carried out except that the organic electron donor compound was replaced by dicyclopentyl dimethoxy silane instead of cyclohexylmethyl dimethoxy silane.
The polymerization results are shown in Table 1.
Example 24
Preparation of procatalyst and cocatalyst propylene high temperature polymerization the same as in example 16 except that AlCl 3 modified MAO was used instead of BF 3 modified MAO.
The polymerization results are shown in Table 1.
Example 25
Preparation of procatalyst, cocatalyst and propylene high temperature polymerization the same as in example 16 except that the high temperature polymerization temperature was replaced by 85 ℃ instead of 93 ℃.
The polymerization results are shown in Table 1.
Example 26
Preparation of procatalyst, cocatalyst and propylene high temperature polymerization the same as in example 16 except that the high temperature polymerization temperature was replaced by 120 ℃ for 93 ℃.
The polymerization results are shown in Table 1.
Comparative example 1
1. Preparation of procatalyst and cocatalyst
The procedure of example 1 was followed except that phthalate was used in place of 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene in the preparation of the procatalyst.
2. High temperature (93 ℃) polymerization of propylene in a polymerization kettle which is treated by vacuum drying and is fully replaced by nitrogen and propylene gas, 0.5kg of propylene is firstly added, 5mL of triethylaluminum (1 mol/L hexane solution) and 0.1mL of cyclohexylmethyl dimethoxy silane are added, 30mg of polypropylene catalyst (comparative example 1) are added, 1.5kg of propylene is continuously added, the temperature of the polymerization kettle is quickly raised to 93 ℃, polymerization is carried out for 1 hour, and unreacted propylene is discharged, thus obtaining 93 ℃ for preparing the polymer.
The polymerization results are shown in Table 1.
Comparative example 2
1. Preparation of procatalyst and cocatalyst
As in example 1.
2. High temperature (93 ℃ or more) polymerization of propylene
In a high temperature polymerization vessel which had been subjected to 10L of vacuum drying treatment and had been sufficiently replaced with nitrogen and propylene gas, 0.5kg of propylene was first added, 2.5mL of triethylaluminum (1 mol/L in hexane), 2.5mL BMAO mL of cyclohexylmethyldimethoxysilane and 0.1mL of cyclohexylmethyldimethoxysilane were further added, 30mg of polypropylene catalyst was further added, and 1.5kg of propylene was prepolymerized at 45℃for 15 minutes, the temperature of the polymerization vessel was rapidly raised to 93℃and the polymerization was carried out for 1 hour, and unreacted propylene was vented to give a high temperature polymer, and the polymerization-related data were shown in Table 1.
The polymerization results are shown in Table 1.
Comparative example 3
1. Preparation of procatalyst and cocatalyst
The preparation method of the main catalyst and the cocatalyst were the same as in example 1, except that 9, 9-bis (methoxymethyl) fluorene (synthetic method referred to CN 02127846.6) was used instead of 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene in the preparation process of the main catalyst.
2. Propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 1.
The polymerization results are shown in Table 1.
Comparative example 4
1. Preparation of procatalyst and cocatalyst
The preparation method of the main catalyst and the cocatalyst is the same as that of comparative example 3.
2. Polymerization of propylene (93 ℃ or more)
(1) Pre-complexation of catalyst systems
Under the protection of nitrogen, adding 30mg of a main catalyst into a glass bottle with 100mL of normal temperature, adding 2.5mL of triethylaluminum (1 mol/L hexane solution), 2.5mL of MAO (10% toluene solution) and 0.1mL of cyclohexylmethyl dimethoxy silane, and pre-complexing the catalyst system in the glass bottle for 5min;
(2) High temperature (93 ℃ or more) polymerization of propylene
And (3) performing propylene high-temperature polymerization by using the catalyst obtained in the step (1). And (2) adding 0.5kg of propylene into 10L of high-temperature polymerization kettle which is subjected to vacuum drying treatment and is fully replaced by nitrogen and propylene gas, adding the pre-complexed catalyst system obtained in the step (1), continuously adding 1.5kg of propylene, pre-polymerizing for 15min at 45 ℃, quickly raising the temperature of the polymerization kettle to 93 ℃, carrying out polymerization reaction for 1 hour, and emptying unreacted propylene to obtain the high-temperature polymer.
The polymerization results are shown in Table 1.
Comparative example 5
1. Preparation of the catalyst
The catalyst was prepared in the same manner as in the preparation method disclosed in chinese patent CN101560272a, wherein the internal electron donor was 2- (2-thiophenecarboxylic acid) -4- (p-isopropylbenzoic acid) pentanediol ester as disclosed in example 9 of CN101560272 a.
2. Propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 5.
The polymerization results are shown in Table 1.
Comparative example 6
1. Preparation of the catalyst
The preparation of the catalyst is the same as that disclosed in Chinese patent CN105985469A, wherein the internal electron donor adopts 6,6' -diethoxy-2, 2' -di (diphenylphosphine) -1,1' -biphenyl.
2. Propylene is polymerized at high temperature (. Gtoreq.93 ℃) as in example 5.
The polymerization results are shown in Table 1.
Comparative example 7
1. Preparation of the procatalyst
The procatalyst was prepared as in example 1.
2. Propylene is polymerized at a high temperature (more than or equal to 93 ℃) in the same way as in the example 1, except that the cocatalyst is a mixed solution of triethylaluminum and MAO, wherein BF 3 is not added for MAO modification.
The polymerization results are shown in Table 1.
TABLE 1 catalyst propylene polymerization test results and high temperature Polymer Properties
The results of the examples and the comparative examples show that the invention uses the biphosphine compound containing thiophene structure as the main catalyst, uses the mixture of aluminoxane modified by Lewis acid and alkyl aluminum as the composite catalyst promoter, and has higher catalytic activity under the conditions of high-temperature propylene homopolymerization and ethylene propylene copolymerization, the propylene high-temperature homopolymerization activity reaches 69.1/KgPP/gCat h, the ethylene propylene high-temperature copolymerization activity reaches 72.2/KgPP/gCat h, and the prepared high-temperature polymer has higher isotactic index, thus solving the problem of lower isotactic index of the prepared high-temperature polymer.
The above examples are exemplary examples listed for the purpose of describing the technical solution of the present invention in detail, the present invention is subject to the protection scope of the claims and the summary of the invention, and is not limited by the embodiments, and the simple substitution or modification of the present invention is still within the protection scope of the present invention.
Claims (17)
1. A catalyst for propylene polymerization comprising:
a main catalyst A containing titanium, a cocatalyst B and an organic electron donor C;
carrying out a pre-complexing reaction on the main catalyst A, the cocatalyst B and the organic electron donor C to obtain a pre-complexing catalyst system;
The main catalyst A comprises an alkoxide carrier of magnesium chloride, titanium halide and an internal electron donor, and is characterized in that the internal electron donor is a biphosphine compound with a molecular skeleton of a formula shown in a general formula (I) and a thiophene structure:
general formula (I);
wherein R 1、R2、R3 and R 4 are the same or different and are each independently selected from a hydrogen atom, a C1-C20 linear or branched alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group and a C7-C20 alkoxyaryl group;
The cocatalyst B is a mixture of an alkyl aluminum compound and alumoxane modified by a Lewis acid, the ratio of the alkyl aluminum compound to the alumoxane modified by the Lewis acid is 1-50:1 in terms of the molar ratio of aluminum to aluminum, and the Lewis acid is selected from at least one of BF 3、BCl3、BBr3、AlCl3、ZnCl2.
2. The catalyst according to claim 1, wherein the internal electron donor is selected from the group consisting of 3, 4-bis (dimethylphosphino) -thiophene, 3, 4-bis (diethylphosphino) -thiophene, 3, 4-bis (di-n-propylphosphino) -thiophene, 3, 4-bis (diisopropylphosphino) -thiophene, 3, 4-bis (di-n-butylphosphino) -thiophene, 3, 4-bis (diisobutylphosphino) -thiophene, 3, 4-bis (di-n-pentylphosphino) -thiophene, 3, 4-bis (dicyclopentylphosphino) -thiophene, 3, 4-bis (di-n-hexylphosphino) -thiophene, 3, 4-bis (dicyclohexylphosphino) -thiophene, 3, 4-bis (diphenylphosphino) -thiophene, 3, 4-bis (di-p-tolylphosphino) -thiophene, 3, 4-bis (di-m-tolylphosphino) -thiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -thiophene, 3, 4-bis (di-m-methoxyphenylphosphino) -thiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -thiophene, 3, 4-bis (dimethylphosphino) -2-methylthiophene, 3, 4-bis (diethylphosphino) -2-methylthiophene, 3, 4-bis (di-n-propylphosphino) -2-methylthiophene, 3, 4-bis (diisopropylphosphino) 2-methyl-thiophene, 3, 4-bis (di-n-butylphosphino) -2-methylthiophene, 3, 4-bis (diisobutylphosphino) -2-methylthiophene, 3, 4-bis (di-n-pentylphosphino) -2-methylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-methylthiophene, 3, 4-bis (di-n-hexylphosphino) -2-methylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-methylthiophene, 3, 4-bis (diphenylphosphino) -2-methylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-methylthiophene, 3, 4-bis (di-m-tolylphosphino) -2-methylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (di-m-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (di-o-methoxyphenyl phosphino) -2-methylthiophene, 3, 4-bis (dimethylphosphino) -2-ethylthiophene, 3, 4-bis (diethylphosphino) -2-ethylthiophene, 3, 4-bis (di-n-propylphosphino) -2-ethylthiophene, 3, 4-bis (diisobutylphosphino) -2-ethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-ethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-ethylthiophene, 3, 4-bis (diphenylphosphino) -2-ethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-ethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2-ethylthiophene, 3, 4-bis (dimethylphosphino) -2-isopropylthiophene, 3, 4-bis (diethylphosphino) -2-isopropylthiophene, 3, 4-bis (di-n-propylphosphino) -2-isopropylthiophene, 3, 4-bis (diisobutylphosphino) -2-isopropylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-isopropylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-isopropylthiophene, 3, 4-bis (diphenylphosphino) -2-isopropylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-isopropylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-isopropylthiophene, 3, 4-bis (dimethylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diethylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-n-propylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diisobutylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-cyclopentylthiophene, 3, 4-bis (diphenylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-cyclopentylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2-cyclopentylthiophene, 3, 4-bis (dimethylphosphino) -2-phenylthiophene, 3, 4-bis (diethylphosphino) -2-phenylthiophene, 3, 4-bis (di-n-propylphosphino) -2-phenylthiophene, 3, 4-bis (diisobutylphosphino) -2-phenylthiophene, 3, 4-bis (dicyclopentylphosphino) -2-phenylthiophene, 3, 4-bis (dicyclohexylphosphino) -2-phenylthiophene, 3, 4-bis (diphenylphosphino) -2-phenylthiophene, 3, 4-bis (di-p-tolylphosphino) -2-phenylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2-phenylthiophene, 3, 4-bis (dimethylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diethylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-n-propylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diisobutylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dicyclopentylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dicyclohexylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (diphenylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-p-tolylphosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2- (4-methoxyphenyl) thiophene, 3, 4-bis (dimethylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diethylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-dimethylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diethylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diethylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-diethylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-diisopropylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diethylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (di-p-methoxyphenylphosphino) -2, 5-di-n-butylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diethylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-dicyclohexylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diethylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-diphenylthiophene, 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-diphenylthiophene, 3, 4-bis (dimethylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diethylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (di-n-propylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diisobutylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (dicyclopentylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (dicyclohexylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (diphenylphosphino) -2, 5-di-p-tolylthiophene, 3, 4-bis (di-p-tolylphosphino) -2, 5-di-p-tolylthiophene, At least one of 3, 4-bis (di-p-methoxyphenyl phosphino) -2, 5-di-p-tolylthiophene.
3. The catalyst according to claim 1, wherein the main catalyst a comprises the following components in percentage by weight:
1-10% of internal electron donor
Titanium 1-15%
10-25% Of magnesium
Halogen accounting for 40-60 percent.
4. The catalyst according to claim 1, wherein the ratio of the alkyl aluminum compound to the Lewis acid modified alumoxane is 1 to 10:1 in terms of molar ratio of aluminum to aluminum.
5. The catalyst of claim 1, wherein the aluminoxane has the general formula:
Wherein Y is C 1-C12 alkyl, Y 2 is 2Y groups, al is aluminum, O is oxygen, a is an integer of 4-30, and the aluminoxane is at least one of methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylluminoxane and butylaluminoxane.
6. The catalyst according to claim 5, wherein, the aluminoxane is methylaluminoxane.
7. The catalyst of claim 1, wherein the molar ratio of Lewis acid to aluminoxane is 1:1-500.
8. The catalyst of claim 1, wherein the molar ratio of Lewis acid to aluminoxane is 1:1-50.
9. The catalyst of claim 1 wherein the Lewis acid is BF 3.
10. The catalyst according to claim 1, wherein the alkyl aluminum compound has a general formula of AlZ nX（3-n）, wherein Al is aluminum, Z is an alkyl, aryl or aralkyl group of C 1～C20, X is halogen, n is an integer of 0 to 3, and the alkyl aluminum compound is at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum monochloride and diisobutylaluminum monochloride.
11. The catalyst according to claim 10, wherein the alkyl aluminum compound is triethylaluminum or triisobutylaluminum.
12. The catalyst according to any one of claims 1 to 11, wherein the organic electron donor C is an alkoxysilane compound, selected from the group consisting of cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane diisopropyl dimethoxy silane, diisobutyl dimethoxy silane diisopropyl dimethoxy silane diisobutyldimethoxy silane.
13. The catalyst according to claim 1, wherein the organic electron donor C is cyclohexylmethyldimethoxysilane.
14. The catalyst according to claim 1, wherein the ratio of the main catalyst A, the cocatalyst B and the organic electron donor C is 1:5-1000:0-500 in terms of the molar ratio of titanium to aluminum to silicon.
15. The catalyst according to claim 1, wherein the ratio of the main catalyst A, the cocatalyst B and the organic electron donor C is 1:10-50:0-5 in terms of the molar ratio of titanium to aluminum to silicon.
16. A process for the polymerization or copolymerization of propylene, characterized in that it employs a catalyst according to any one of claims 1 to 15.
17. The reaction method according to claim 16, comprising the steps of:
(1) Carrying out pre-complexing reaction on a main catalyst A, a cocatalyst B and an organic electron donor C for 1-20 min at a temperature of-10-60 ℃ to obtain a pre-complexing catalyst system;
(2) Carrying out prepolymerization reaction on propylene for 5-30 min in the presence of the pre-complex catalyst system in the step (1) at the temperature of 0-60 ℃ to obtain a prepolymer;
(3) And (3) under the condition of 80-120 ℃, propylene is polymerized or copolymerized in the presence of the prepolymer in the step (2) in a liquid phase or gas phase medium.
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| CN109535289A (en) * | 2017-09-22 | 2019-03-29 | 中国石油化工股份有限公司 | Early transition metal compound and preparation method and catalyst for olefines polymerizing composition and application and the method for preparing olefin polymer |
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| DE19806918A1 (en) * | 1998-02-19 | 1999-08-26 | Aventis Res & Tech Gmbh & Co | Catalyst system for the production of olefin polymers, especially polypropylene |
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| CN109535289A (en) * | 2017-09-22 | 2019-03-29 | 中国石油化工股份有限公司 | Early transition metal compound and preparation method and catalyst for olefines polymerizing composition and application and the method for preparing olefin polymer |
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