CN112625157A - Catalyst for preparing ultrapure polypropylene and preparation method for preparing ultrapure polypropylene by batch bulk method - Google Patents
Catalyst for preparing ultrapure polypropylene and preparation method for preparing ultrapure polypropylene by batch bulk method Download PDFInfo
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Abstract
The invention provides a catalyst for preparing ultrapure polypropylene and a preparation method for preparing the ultrapure polypropylene by a batch bulk method. The invention provides a catalyst for preparing ultrapure polypropylene, which comprises the following components in part by weight: a main catalyst, a cocatalyst and an external electron donor; the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor; the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalic acid ester. The invention takes titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor as main catalysts of an ultra-pure polypropylene catalytic system, wherein the internal electron donor adopts a specific ternary complex of 1, 3-diether compounds, aromatic diester and phthalate, and the internal electron donor is combined with the titanium tetrachloride and the magnesium dichloride alcoholate to form the main catalyst. The catalytic system containing the main catalyst can effectively improve catalytic activity, reduce ash content of polypropylene and improve isotacticity of polypropylene.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst for preparing ultrapure polypropylene and a preparation method for preparing the ultrapure polypropylene by a batch bulk method.
Background
The polypropylene is a polyolefin resin which develops most rapidly in recent years, and along with the expansion of the application range of the polypropylene, the high-purity polypropylene with low ash content (the general mass fraction is less than 0.0080%) has good application prospect. The ultra-pure polypropylene special for the capacitor has higher requirement on ash content (the mass fraction is lower than 0.0050%), is a special polypropylene material with extremely low ash content and high added value, and becomes an important polymer material special for the capacitor film due to excellent electrical performance and easy processability. Compared with other capacitance membrane materials, the polypropylene is closest to an 'ideal capacitor material', and has the characteristics of extremely low high-frequency loss, high dielectric strength, high insulation resistance, smaller negative temperature coefficient and the like. Based on these excellent characteristics, ultrapure polypropylene is widely used in the sunward industry, including consumer electronics, hybrid vehicle markets, power grid construction markets, new energy, green lighting, railway electrification and electromagnetic ejection from national military aircraft carriers, electromagnetic rail guns, and high-power pulsed lasers. At present, the domestic demand of the ultrapure polypropylene is increased year by year, and the total domestic demand is about 20 ten thousand tons and keeps the annual increase trend of 12.5 percent by 2020.
The production methods of polypropylene are divided into two categories: continuous bulk processes and batch liquid phase bulk processes. Wherein, the production process of the continuous body method is automatically controlled, and the finished product is automatically packaged; the feeding, heating, recycling and other links in the production process of the intermittent bulk method are all manually controlled. The intermittent bulk polypropylene process has the characteristics of short flow, simple equipment, low investment and the like, and becomes a main production method for generating polypropylene.
In the process of polypropylene production technology, a catalytic system and a polymerization process play a vital role in product performance. At present, a Ziegler-Natta catalyst is a mainstream catalyst for synthesizing polypropylene by a liquid-phase bulk method, but the isotacticity of a polypropylene product prepared by adopting a polymerization process is low, and the polypropylene product cannot meet the application occasions of polypropylene with high isotacticity.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst for preparing ultrapure polypropylene and a method for preparing ultrapure polypropylene by a batch bulk method. The catalyst and the preparation method provided by the invention can be used for preparing the ultrapure polypropylene for the capacitor, have higher catalytic activity and improve the isotacticity of the polypropylene.
The invention provides a catalyst for preparing ultrapure polypropylene, which comprises a main catalyst, a cocatalyst and an external electron donor;
the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor;
the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalic acid ester.
Preferably, the 1, 3-diether compound is selected from one or more of 1, 3-dimethyl propylene dimethyl ether, dipropylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane and 4, 4-bis (methoxymethyl) -2-methylhexane.
Preferably, the aromatic diester is ethylene dibenzoate;
the phthalate is dibutyl phthalate;
the magnesium dichloride alcoholate is MgCl2·(EtOH)m(ROH)nWherein m is 2.0-3.8, n is 2.0-5.1, and R is other than ethylAnd C1-C10 alkyl groups other than the above groups.
Preferably, in the internal electron donor, the molar ratio of the 1, 3-diether compound to the aromatic diester to the phthalic acid ester is (20-60) to (1-40) to (0-10);
in the main catalyst, the mass ratio of the titanium element, the magnesium element and the internal electron donor is (1.0-5.2) to (12-25) to (10-30).
Preferably, the main catalyst is prepared by the following method:
under the protection of inert gas, dropwise adding titanium tetrachloride into a magnesium dichloride alcohol compound under the reaction condition of-20-0 ℃, stirring and reacting for 1-1.5 h at 80-100 ℃, then sequentially adding aromatic diester, phthalate and 1,3 diether compounds into a reaction system, and then heating to 100-110 ℃ for reacting for 2-3 h to obtain the main catalyst.
Preferably, the cocatalyst is an alkyl aluminum compound; the external electron donor is a siloxane-based external electron donor.
Preferably, the cocatalyst is selected from one or more of triisobutylaluminum, triethylaluminum, diethylaluminum chloride and methylaluminoxane;
the siloxane external electron donor is selected from one or more of diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and diisopropyldimethoxysilane;
the molar ratio of Al in the cocatalyst to Ti in the main catalyst is (5-100) to 1;
the molar ratio of Si in the external electron donor to Ti in the main catalyst is (0.1-100) to 1.
The invention also provides a preparation method for preparing the ultrapure polypropylene by the batch bulk method, which comprises the following steps:
a) adding a catalyst, part of hydrogen and part of propylene monomer into an intermittent bulk reaction system, and carrying out prepolymerization reaction to obtain a prepolymer;
b) adding the rest hydrogen and the rest propylene monomer into the intermittent bulk reaction system, and carrying out polymerization reaction to obtain ultrapure polypropylene;
the catalyst is the catalyst in the technical scheme.
Preferably, the concentration of the total hydrogen amount of the part of hydrogen in the step a) and the residual hydrogen in the step b) in the catalyst is 10-5000 ppm;
the mass ratio of part of hydrogen in the step a) to the total hydrogen is 10-50%;
the mass ratio of part of propylene monomer in the step a) to the total propylene monomer is 10-50%.
Preferably, in the step a), the temperature of the prepolymerization reaction is 0-60 ℃, the time is 0.3-2 h, and the pressure is 1.0-3.0 MPa.
In the step b), the temperature of the polymerization reaction is 65-75 ℃, the time is 1-2.5 h, and the pressure is 2.5-3.5 MPa.
The invention provides a catalyst for preparing ultrapure polypropylene, which comprises a main catalyst, a cocatalyst and an external electron donor; the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor; the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalic acid ester. The invention takes titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor as main catalysts of an ultra-pure polypropylene catalytic system, wherein the internal electron donor adopts a specific ternary complex of 1, 3-diether compounds, aromatic diester and phthalate, and the internal electron donor is combined with the titanium tetrachloride and the magnesium dichloride alcoholate to form the main catalyst. The catalytic system containing the main catalyst can effectively improve catalytic activity, reduce ash content of polypropylene and improve isotacticity of polypropylene.
Experimental results show that the catalyst provided by the invention can be used for preparing ultrapure polypropylene, the catalytic activity can reach more than 12Kg PP/g cat h, the ash content of the product is below 15ppm, and the isotacticity reaches more than 97%.
Detailed Description
The invention provides a catalyst for preparing ultrapure polypropylene, which comprises a main catalyst, a cocatalyst and an external electron donor;
the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor;
the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalic acid ester.
The invention takes titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor as main catalysts of an ultra-pure polypropylene catalytic system, wherein the internal electron donor adopts a specific ternary complex of 1, 3-diether compounds, aromatic diester and phthalate, and the internal electron donor is combined with the titanium tetrachloride and the magnesium dichloride alcoholate to form the main catalyst. The catalyst system containing the main catalyst can effectively improve the catalytic activity, reduce the ash content of polypropylene, prepare the ultra-pure polypropylene and improve the isotacticity of the polypropylene.
According to the invention, the catalyst comprises a main catalyst; the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and an internal electron donor.
In the present invention, the source of the titanium tetrachloride is not particularly limited, and may be a commercially available product.
In the present invention, the magnesium dichloride alcoholate is preferably MgCl2·(EtOH)m(ROH)nNamely the magnesium dichloride-alcohol adduct, wherein m is 2.0 to 3.8, n is 2.0 to 5.1, and R is C1 to C10 alkyl except ethyl. The magnesium dichloride alcoholate of the present invention is not particularly limited in its origin, and can be prepared according to a conventional preparation method well known to those skilled in the art.
In the invention, the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalate. The invention adopts the three specific components to form the internal electron donor, and the three components play a synergistic action, wherein the aromatic diester and the phthalic acid ester influence the crystallization form of magnesium dichloride in the preparation process of the catalyst, so that the structure and the form of a magnesium dichloride microcrystal carrier are changed, the specific surface area and the catalytic activity of the final carrier can be increased by the compounded aromatic diester and the phthalic acid ester, meanwhile, the 1, 3-diether compound has a stronger coordination effect with a titanium metal center, the diether internal electron donor is tightly combined with the titanium metal center under the action of an alkyl aluminum cocatalyst, the probability of forming a random active center is reduced by matching the influence of the aromatic diester and the phthalic acid ester on the magnesium dichloride microcrystal, therefore, the three substances are compounded as the internal electron donor and are combined with titanium tetrachloride and a magnesium dichloride alcohol compound, the isotacticity of polypropylene can be improved, the ash content is reduced, and the using amount of the alkyl aluminum cocatalyst is reduced.
Wherein:
the 1, 3-diether compound is preferably one or more of 1, 3-dimethyl propylene dimethyl ether, dipropylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane and 4, 4-dimethyloxymethyl-2-methylhexane; more preferably one or more of 1, 3-dimethyl propylene dimethyl ether, dipropylene glycol dimethyl ether and 2-isopropyl-2 isobutyl-1, 3 dimethoxypropane; most preferred is 1, 3-dimethylpropyldimethyl ether.
The aromatic diester is preferably ethylene dibenzoate.
The phthalate is preferably dibutyl phthalate.
In the invention, the molar ratio of the 1, 3-diether compound to the aromatic diester to the phthalic acid ester is preferably (20-60) to (1-40) to (0-10), more preferably (30-60) to (1-20) to (0-10), and most preferably (30-50) to (1-20) to (0-10), wherein the dosage of the phthalic acid ester is not 0. The catalytic activity and the product isotacticity can be effectively improved only by the above proportion, wherein if the proportion of the diether compound is too high, the steric hindrance of monomer insertion is increased, although the stereoselectivity is higher, the catalytic activity is reduced, if the proportion is too low, the stereoselectivity is difficult to ensure, the aromatic diester and the phthalate are key factors determining the catalytic activity, if the proportion is too high or too low, the crystallization and the form change of the magnesium dichloride as a carrier are caused, the good specific surface area and the proper catalyst form are difficult to ensure, and the catalytic effect is influenced.
In the invention, the mass ratio of the titanium element, the magnesium element and the internal electron donor in the main catalyst is preferably (1.0-5.2) to (12-25) to (10-30), the optimal matching can be achieved under the above ratio, the catalytic effect is improved, and if the ratio is broken, the relationship among catalytic activity, product isotacticity and the use amount of the alkyl aluminum cocatalyst is difficult to coordinate, and the index requirements of high activity, high isotacticity and low ash content are difficult to meet at the same time.
In the present invention, the main catalyst is preferably prepared by the following method:
under the protection of inert gas, dropwise adding titanium tetrachloride into a magnesium dichloride alcohol compound under the reaction condition of-20-0 ℃, stirring and reacting for 1-1.5 h at 80-100 ℃, then sequentially and respectively adding aromatic diester, phthalate and 1,3 diether compounds into a reaction system, and then heating to 100-110 ℃ for reacting for 2-3 h. After the reaction is finished, washing the obtained solid powder with hexane for 3 times, filtering and pumping to obtain yellow solid powder, namely the main catalyst.
According to the invention, the catalyst also comprises a cocatalyst and an external electron donor.
In the present invention, the cocatalyst is preferably an alkylaluminum compound. The alkyl aluminum compound is preferably one or more of triisobutyl aluminum, triethyl aluminum, diethyl aluminum chloride and methylaluminoxane; more preferably one or more of triisobutylaluminum, triethylaluminum and methylaluminoxane; further preferred is triisobutylaluminum and/or triethylaluminum. In the present invention, the source of the cocatalyst is not particularly limited, and may be any commercially available one.
In the invention, the molar ratio of Al in the alkyl aluminum compound cocatalyst to Ti in the main catalyst is preferably (5-100) to 1, more preferably (5-70) to 1, and most preferably (5-45) to 1.
In the present invention, the external electron donor is preferably a siloxane-based external electron donor. The siloxane external electron donor is preferably one or more of diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and diisopropyldimethoxysilane; more preferably diphenyldimethoxysilane and/or cyclohexylmethyldimethoxysilane.
In the present invention, the molar ratio of Si in the siloxane-based external electron donor to Ti in the main catalyst is preferably (0.1 to 100) to 1, more preferably (5 to 50) to 1, and most preferably (5 to 30) to 1.
The catalyst provided by the invention takes titanium tetrachloride, magnesium dichloride alcoholate and an internal electron donor as a main catalyst of an ultra-pure polypropylene catalytic system, wherein the internal electron donor is a specific ternary complex of 1, 3-diether compounds, aromatic diester and phthalate, and the internal electron donor is combined with the titanium tetrachloride and the magnesium dichloride alcoholate to form the main catalyst. The catalyst system containing the main catalyst can effectively improve the catalytic activity, reduce the ash content of polypropylene, prepare the ultra-pure polypropylene and improve the isotacticity of the polypropylene.
Experimental results show that the catalyst provided by the invention can be used for preparing ultrapure polypropylene, the catalytic activity can reach more than 12Kg PP/g cat h, the ash content of the product is below 15ppm, and the isotacticity reaches more than 97%.
The invention also provides a preparation method for preparing the ultrapure polypropylene by the batch bulk method, which comprises the following steps:
a) adding a catalyst, part of hydrogen and part of propylene monomer into an intermittent bulk reaction system, and carrying out prepolymerization reaction to obtain a prepolymer;
b) adding the rest hydrogen and the rest propylene monomer into the intermittent bulk reaction system, and carrying out polymerization reaction to obtain ultrapure polypropylene;
the catalyst is the catalyst in the technical scheme.
With respect to step a):
in the invention, the mass ratio of the partial hydrogen to the total hydrogen is preferably 10-50%; in some embodiments of the invention, the mass ratio is 30%, 40% or 50%. Hydrogen is also a key index influencing catalytic activity and later-stage product melt index, high catalytic activity is difficult to realize if the amount of hydrogen input in the early stage is too low, and local violent heat release is caused if the amount of hydrogen input in the early stage is too high, so that the process is difficult to control. In the invention, the concentration of the total hydrogen in the catalyst is preferably 10-5000 ppm, and more preferably 10-500 ppm.
In the invention, the mass ratio of the partial propylene monomer to the total propylene monomer is preferably 10-50%; in some embodiments of the invention, the mass ratio is 30%, 40% or 50%. In the present invention, the mass ratio of the catalyst to the total propylene monomer is preferably 0.00075% to 0.003%.
In the invention, the temperature of the prepolymerization reaction is preferably 0-60 ℃, more preferably 20-50 ℃, and most preferably 40-50 ℃. The temperature rise rate of the prepolymerization reaction is preferably 1-5 ℃/min, and more preferably 5 ℃/min. The pressure of the prepolymerization reaction is preferably 1.0-3.0 MPa, more preferably 1.5-2.7 MPa, and most preferably 2.0-2.5 MPa. The time of the prepolymerization reaction is preferably 0.3-2 h, more preferably 0.5-1.2 h, and most preferably 0.8-1.2 h. After the prepolymerization reaction, a prepolymer is generated.
With respect to step b):
after the prepolymerization reaction in the step a), adding the residual hydrogen and the residual propylene monomer into the reaction system, and continuing the polymerization reaction. In the invention, the polymerization reaction temperature is preferably 65-75 ℃, and more preferably 70 ℃. In the present invention, the rate of temperature rise in the polymerization reaction is preferably < 5 ℃/min, more preferably 3 ℃/min. The pressure of the polymerization reaction is preferably 2.5-3.5 MPa. The time of the polymerization reaction is preferably 1-2.5 h. The ultrapure polypropylene is obtained by the polymerization reaction.
The preparation method provided by the invention adopts the sectional program temperature control mode, can ensure that a catalytic system can exert optimal catalytic activity and polymer morphology, and meanwhile, the polymerization method is beneficial to regulation and control of the melt index and molecular weight distribution of the polymer.
The catalyst system and the preparation method provided by the invention have the following beneficial effects:
(1) the catalyst provided by the invention has the characteristics of high catalytic activity, long catalytic life, low cocatalyst consumption and the like, internal electron donor of the ternary complex forms stable coordination with a metal center, and the probability of forming a random active center by complexing the cocatalyst with the cocatalyst is reduced, so that a polypropylene product has high isotacticity which can reach more than 97%.
(2) The invention adopts a sectional program temperature control mode, can ensure that a catalytic system can exert optimal catalytic activity and polymer morphology, and simultaneously, the polymerization method is beneficial to the regulation and control of the melt index and molecular weight distribution of the polymer.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is dropwise added into magnesium dichloride alcoholate (R is C8 alkyl, m is 2.2, and n is 3.4) under the reaction condition of-20 ℃, the mixture is stirred and reacted for 1.5 hours at 80 ℃, then ethylene dibenzoate, dibutyl phthalate and dipropylene glycol dimethyl ether are added into a reaction system according to the sequence and the molar ratio of 0.1: 1, and then the temperature is raised to 100 ℃ for reaction for 2 hours. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 12.6 wt%, Ti: 2.4 wt%.
And (3) a cocatalyst: triethyl aluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 53: 1.
External electron donor: cyclohexyl methyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 29: 1.
Hydrogen gas: the concentration in the catalyst system was 50 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.0015%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 30% of the total amount of hydrogen, and the adding amount of the propylene monomer is 30% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 40 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.2MPa, and the prepolymerization reaction is carried out for 1 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Example 2
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is added dropwise into magnesium dichloride alcoholate (R is C6 alkyl, m is 2.4, n is 3.8) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1.5h at 100 ℃, then, ethylene dibenzoate, dibutyl phthalate and 2-isopropyl-2 isobutyl-1, 3 dimethoxypropane are added into the reaction system according to the sequence and the molar ratio of 0.1: 1, and then, the temperature is raised to 110 ℃ for reaction for 2 h. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 14.6 wt%, Ti: 3.1 wt%.
And (3) a cocatalyst: triethyl aluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 23: 1.
External electron donor: cyclohexyl methyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 14: 1.
Hydrogen gas: the concentration in the catalyst system was 70 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.0015%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 30% of the total amount of hydrogen, and the adding amount of the propylene monomer is 30% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 45 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.5MPa, and the prepolymerization reaction is carried out for 1.5 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.5MPa, and continuously finishing the polymerization reaction.
Example 3
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is added dropwise into magnesium dichloride alcoholate (R is C10 alkyl, m is 2.1, n is 4.5) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1.5h at 80 ℃, then ethylene dibenzoate, dibutyl phthalate and 2-isopropyl-2 isobutyl-1, 3 dimethoxypropane are added into the reaction system according to the sequence and the molar ratio of 0.1: 1, and then the temperature is raised to 110 ℃ for reaction for 2 h. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 17.8 wt%, Ti: 2.6 wt%.
And (3) a cocatalyst: triisobutylaluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 36: 1.
External electron donor: diphenyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 8: 1.
Hydrogen gas: the concentration in the catalyst system was 50 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.00075%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 50% of the total amount of hydrogen, and the adding amount of the propylene monomer is 50% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 40 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.3MPa, and the prepolymerization reaction is carried out for 0.8 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 2.5MPa, and continuously finishing the polymerization reaction.
Example 4
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is added into magnesium dichloride alcoholate (R is C8 alkyl, m is 3.1, n is 4.2) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1h at 90 ℃, then ethylene dibenzoate, dibutyl phthalate and dipropylene glycol dimethyl ether are added into the reaction system according to the sequence and the molar ratio of 0.5: 0.1: 1, and then the temperature is raised to 100 ℃ for reaction for 3 h. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 13.5 wt%, Ti: 3.5 wt%.
And (3) a cocatalyst: triisobutylaluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 34: 1.
External electron donor: diphenyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 14: 1.
Hydrogen gas: the concentration in the catalyst system was 100 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.0015%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 40% of the total amount of hydrogen, and the adding amount of the propylene monomer is 40% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 50 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.5MPa, and the prepolymerization reaction is carried out for 0.8 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Example 5
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is added into magnesium dichloride alcoholate (R is C6 alkyl, m is 2.4, n is 4.1) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1.5h at 90 ℃, then ethylene dibenzoate, dibutyl phthalate and dipropylene glycol dimethyl ether are added into the reaction system according to the sequence and the molar ratio of 1: 0.2: 1, and then the temperature is raised to 100 ℃ for reaction for 3 h. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 15.6 wt%, Ti: 2.7 wt%.
And (3) a cocatalyst: triisobutylaluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 45: 1.
External electron donor: diphenyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 12: 1.
Hydrogen gas: the concentration in the catalyst system was 50 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.00080%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 50% of the total amount of hydrogen, and the adding amount of the propylene monomer is 50% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 50 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.5MPa, and the prepolymerization reaction is carried out for 0.8 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Example 6
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is dropwise added into magnesium dichloride alcoholate (R is C8 alkyl, m is 2.2, and n is 4.5) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1.5 hours at 90 ℃, then ethylene dibenzoate, dibutyl phthalate and 1, 3-dimethyl propylene dimethyl ether are added into the reaction system according to the sequence and the molar ratio of 1: 0.2: 1, and then the temperature is raised to 110 ℃ at the speed of 3 ℃/min for 3 hours. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 18.2 wt%, Ti: 3.2 wt%.
And (3) a cocatalyst: triethyl aluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 27: 1.
External electron donor: cyclohexyl methyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 10: 1.
Hydrogen gas: the concentration in the catalyst system was 200 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.00075%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 40% of the total amount of hydrogen, and the adding amount of the propylene monomer is 40% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 50 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.5MPa, and the prepolymerization reaction is carried out for 1 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Example 7
S1 catalyst system
Under the protection of nitrogen, titanium tetrachloride is dropwise added into magnesium dichloride alcoholate (R is C8 alkyl, m is 2.5, and n is 4.6) under the reaction condition of 0 ℃, the mixture is stirred and reacted for 1.5h at 100 ℃, then ethylene dibenzoate, dibutyl phthalate and 1, 3-dimethyl propylene dimethyl ether are added into the reaction system according to the sequence and the molar ratio of 1: 0.2: 1, and then the temperature is raised to 110 ℃ at the speed of 3 ℃/min for 3 h. After the reaction is finished, washing the solid powder with hexane for 3 times, filtering and draining to obtain the main catalyst. In the main catalyst obtained: mg: 15.6 wt%, Ti: 3.0 wt%.
And (3) a cocatalyst: triethyl aluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 20: 1.
External electron donor: cyclohexyl methyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 8: 1.
Hydrogen gas: the concentration in the catalyst system was 200 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.00075%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 40% of the total amount of hydrogen, and the adding amount of the propylene monomer is 40% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 50 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.5MPa, and the prepolymerization reaction is carried out for 1 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Comparative example 1
S1 catalyst system
Main catalyst: the sunward catalyst plant commercializes the polypropylene catalyst CS-1.
And (3) a cocatalyst: triethyl aluminum; the molar ratio of Al in the cocatalyst to Ti in the main catalyst is 60: 1.
External electron donor: cyclohexyl methyldimethoxysilane; the molar ratio of Si in the external electron donor to Ti in the main catalyst is 30: 1.
Hydrogen gas: the concentration in the catalyst system was 100 ppm.
The mass ratio of the catalyst to the total propylene monomer was 0.00075%.
S2 preparation of polypropylene
Adding the components of the catalyst system and a propylene monomer into an intermittent bulk reaction system respectively, wherein the adding amount of hydrogen is 80% of the total amount of hydrogen, and the adding amount of the propylene monomer is 80% of the total amount of the propylene monomer; the temperature of the reaction system is increased to 50 ℃ at the heating rate of 5 ℃/min, the reaction pressure is controlled to be 2.7MPa, and the prepolymerization reaction is carried out for 1 h.
After the prepolymerization reaction is finished, adding the residual hydrogen and the residual propylene monomer into the system, raising the temperature of the reaction system to 70 ℃ at the heating rate of 3 ℃/min, controlling the reaction pressure to be 3.0MPa, and continuously finishing the polymerization reaction.
Example 8
(1) The catalytic activity of the preparation processes of examples 1 to 7 and comparative example 1 and the technical indexes of the obtained polypropylene product were tested, and the results are shown in table 1.
TABLE 1 technical indices of polypropylenes obtained in examples 1 to 7 and comparative example 1
The test results in Table 1 show that the catalytic activity of the catalyst and the preparation method of the invention is obviously improved, and the catalyst reaches more than 12Kg PP/g cat h, the ash content of the product is below 15ppm, and the isotacticity reaches more than 97%.
(2) The polypropylene samples obtained in examples 3,6 to 7 and the polypropylene sample in comparative example 2 were tested for the physical and chemical properties such as molecular weight, molecular weight distribution, density, crystallization temperature and melting point, and the results are shown in table 2. Meanwhile, the mechanical properties of the polypropylene samples were tested, and the results are shown in table 3. Wherein the polypropylene sample of comparative example 2 was Nordic chemical HC318 BF.
TABLE 2 physical and chemical Properties of the polypropylenes obtained in examples 1 to 7 and comparative example 1
TABLE 3 mechanical Properties of the polypropylenes obtained in examples 1 to 7 and comparative example 1
As can be seen from tables 2-3, the polypropylene prepared by the invention has better comprehensive mechanical properties.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The catalyst for preparing the ultra-pure polypropylene is characterized by comprising a main catalyst, a cocatalyst and an external electron donor;
the main catalyst comprises: titanium tetrachloride, magnesium dichloride alcoholate and internal electron donor;
the internal electron donor is a ternary complex of a 1, 3-diether compound, an aromatic diester and phthalic acid ester.
2. The catalyst according to claim 1, wherein the 1, 3-diether compound is one or more selected from the group consisting of 1, 3-dimethylpropyldimethyl ether, dipropylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1, 3-dimethoxypropane and 4, 4-dimethyloxymethyl-2-methylhexane.
3. The catalyst of claim 1, wherein the aromatic diester is ethylene dibenzoate;
the phthalate is dibutyl phthalate;
the magnesium dichloride alcoholate is MgCl2·(EtOH)m(ROH)nWherein m is 2.0 to 3.8, n is 2.0 to 5.1, and R is a C1 to C10 alkyl group other than ethyl.
4. The catalyst of claim 1, wherein in the internal electron donor, the molar ratio of the 1, 3-diether compound to the aromatic diester to the phthalate is (20-60) to (1-40) to (0-10);
in the main catalyst, the mass ratio of the titanium element, the magnesium element and the internal electron donor is (1.0-5.2) to (12-25) to (10-30).
5. The catalyst of claim 1, wherein the procatalyst is prepared by the method of:
under the protection of inert gas, dropwise adding titanium tetrachloride into a magnesium dichloride alcohol compound under the reaction condition of-20-0 ℃, stirring and reacting for 1-1.5 h at 80-100 ℃, then sequentially adding aromatic diester, phthalate and 1,3 diether compounds into a reaction system, and then heating to 100-110 ℃ for reacting for 2-3 h to obtain the main catalyst.
6. The catalyst of claim 1 wherein the cocatalyst is an alkyl aluminum compound; the external electron donor is a siloxane-based external electron donor.
7. The catalyst of claim 6, wherein the cocatalyst is selected from one or more of triisobutylaluminum, triethylaluminum, diethylaluminum chloride and methylalumoxane;
the siloxane external electron donor is selected from one or more of diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and diisopropyldimethoxysilane;
the molar ratio of Al in the cocatalyst to Ti in the main catalyst is (5-100) to 1;
the molar ratio of Si in the external electron donor to Ti in the main catalyst is (0.1-100) to 1.
8. A method for preparing ultrapure polypropylene by a batch bulk method is characterized by comprising the following steps:
a) adding a catalyst, part of hydrogen and part of propylene monomer into an intermittent bulk reaction system, and carrying out prepolymerization reaction to obtain a prepolymer;
b) adding the rest hydrogen and the rest propylene monomer into the intermittent bulk reaction system, and carrying out polymerization reaction to obtain ultrapure polypropylene;
the catalyst is the catalyst according to any one of claims 1 to 7.
9. The preparation method according to claim 8, wherein the total hydrogen content of the partial hydrogen in the step a) and the residual hydrogen in the step b) is 10-5000 ppm in the catalyst;
the mass ratio of part of hydrogen in the step a) to the total hydrogen is 10-50%;
the mass ratio of part of propylene monomer in the step a) to the total propylene monomer is 10-50%.
10. The preparation method according to claim 8, wherein in the step a), the temperature of the prepolymerization reaction is 0-60 ℃, the time is 0.3-2 h, and the pressure is 1.0-3.0 MPa;
in the step b), the temperature of the polymerization reaction is 65-75 ℃, the time is 1-2.5 h, and the pressure is 2.5-3.5 MPa.
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