CN115703055A - Feeding method and feeding system of propylene polymerization catalyst, polypropylene and preparation method thereof - Google Patents
Feeding method and feeding system of propylene polymerization catalyst, polypropylene and preparation method thereof Download PDFInfo
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- CN115703055A CN115703055A CN202110945969.6A CN202110945969A CN115703055A CN 115703055 A CN115703055 A CN 115703055A CN 202110945969 A CN202110945969 A CN 202110945969A CN 115703055 A CN115703055 A CN 115703055A
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 171
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims abstract description 91
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002685 polymerization catalyst Substances 0.000 title claims abstract description 35
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 176
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- 238000006243 chemical reaction Methods 0.000 claims description 154
- 150000001336 alkenes Chemical class 0.000 claims description 64
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
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- REIUXOLGHVXAEO-UHFFFAOYSA-N pentadecan-1-ol Chemical compound CCCCCCCCCCCCCCCO REIUXOLGHVXAEO-UHFFFAOYSA-N 0.000 description 2
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- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a feeding method of a propylene polymerization catalyst, which comprises the following steps: 1) Uniformly mixing a propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix; 2) And the catalyst premixed liquid is sequentially metered, conveyed and buffered, and then is introduced into a propylene polymerization reactor to participate in propylene polymerization reaction, wherein the components of the catalyst premixed liquid in the metering, conveying and buffering processes are controlled to be uniform, and the temperature of the catalyst premixed liquid in the buffering process is controlled to be the same as the temperature of the catalyst premixed liquid during the propylene polymerization reaction. The invention also relates to a feeding system of the propylene polymerization catalyst, a preparation method of polypropylene by adopting the feeding method and the prepared polypropylene. According to the feeding method provided by the invention, the stirring is arranged in each link through which the catalyst premixed liquid flows, so that the uniformity of the components is always kept, and therefore, the uniformity of the catalyst components entering a polymerization reactor is ensured, and a feeding pipeline is not blocked.
Description
Technical Field
The invention belongs to the technical field of polymer preparation, and particularly relates to a feeding method and a feeding system of a propylene polymerization catalyst, and a preparation method of polypropylene by using the method and the system.
Background
The catalyst for propylene polymerization is usually prepared by premixing the catalyst with propylene to form a catalyst suspension, and then adding the catalyst suspension into a propylene polymerization reactor to participate in polymerization reaction. However, since the catalyst is a solid powder, a suspension prepared with propylene is liable to settle. In the actual production process, many problems are often caused by the feeding method of the suspension, for example, the feeding amount of the catalyst may fluctuate within a certain range due to the sedimentation of the catalyst, so that the catalyst components entering the reactor at different times are not uniform, the polymerization reaction of propylene is not uniform, and in severe cases, the polymerization reactor is locally overheated to generate agglomeration, which has a great influence on the normal operation of the device; it is also possible that some catalyst fines accumulate in the feed line due to settling of the catalyst, resulting in plugging of the catalyst feed line. Further, the process parameters of the catalyst entering the polymerization reactor are unstable due to the above factors, making the process control of the polymerization reaction difficult, so that in the polymerization reaction of propylene, especially in the preparation of high performance polypropylene with a designable molecular structure, the final molecular structure of the product is not uniformly distributed and has a large difference from the molecular structure of the designed product, thereby affecting the performance and quality of the final product.
In the prior literature reports, many researchers hope to solve the technical problem, for example, one can maintain the components of the suspension uniform by circulating the circulation pump and the circulation line for the metering tank; it has also been known to improve the dispersion of the suspension by designing a metering tank of a particular configuration so that the components of the suspension remain homogeneous; however, these studies can only alleviate the settling of the suspension to a certain extent, which can only ensure the uniformity of the components of the catalyst suspension in the metering tank, but the settling of the catalyst suspension during the transportation of the catalyst suspension into the feeding line is difficult to avoid, the uniformity of the components and the stability of the conditions of the suspension entering the polymerization reactor are not ensured, and the blockage of the pipeline is also difficult to avoid.
Disclosure of Invention
Based on the above, the main object of the present invention is to provide a feeding method and a feeding system for propylene polymerization catalyst, in which the feeding method provided by the present invention makes the catalyst component introduced into the polymerization reactor uniform and the temperature and pressure are consistent with those of the polymerization reactor, and minimizes the influence of the catalyst feeding process on the polymerization reaction, so that the process conditions of the polymerization reaction are controlled, and high performance polypropylene with designable molecular structure is prepared, thereby improving the uniformity and the comprehensive performance of the molecular structure of the product, and simultaneously avoiding the blockage of the feeding pipeline, and improving the market efficiency, so as to be more practical.
To this end, the present invention provides a process for feeding a propylene polymerization catalyst, comprising the steps of:
1) Uniformly mixing a propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix;
2) And the catalyst premixed liquid is sequentially metered, conveyed and buffered, and then is introduced into a propylene polymerization reactor to participate in propylene polymerization reaction, wherein the components of the catalyst premixed liquid in the metering, conveying and buffering processes are controlled to be uniform, and the temperature of the catalyst premixed liquid in the buffering process is controlled to be the same as the temperature of the catalyst premixed liquid during the propylene polymerization reaction.
The feeding method of the present invention, wherein preferably, the metering process comprises circulating the catalyst premix in a metering tank under stirring and precisely metering by a diaphragm metering pump.
The feeding method of the present invention, wherein preferably, the conveying process employs a pipeline provided with a stirrer.
The feeding method of the present invention, wherein preferably, the buffering process comprises circulating the catalyst premix in the buffer tank under stirring, and then adjusting the temperature of the catalyst premix and the pressure in the buffer tank.
Therefore, the invention also provides a feeding system of the propylene polymerization catalyst, which comprises a batching tank, a metering tank, a diaphragm metering pump, a conveying pipeline and a buffer tank which are connected in sequence, wherein the buffer tank is connected with the propylene polymerization reaction device; preferably, the stirrer arranged in the conveying pipeline is an inclined paddle type stirrer, the inclined paddle type stirrer is composed of two straight blades, and the two blades are reversely turned by 45-60 degrees.
Specifically, a stirrer is arranged on a conveying pipeline connecting the diaphragm metering pump and the buffer tank and used for continuously keeping components of the catalyst premixed liquid uniform in the conveying process.
The feeding system of the present invention, wherein preferably, the metering tanks comprise at least two, and further preferably, the metering tanks are connected in parallel.
The feeding system of the present invention, wherein preferably, a protection valve is arranged between the metering tank and the diaphragm metering pump; further preferably, the diaphragm metering pump is a stroke-adjustable diaphragm metering pump.
In the feeding system of the present invention, preferably, a plurality of stirrers are disposed in the conveying pipeline, and further preferably, the distance between adjacent stirrers is less than 2m.
Therefore, the invention also provides a preparation method of the high-impact high-gloss polypropylene, which comprises the following steps:
1) Introducing the catalyst premixed liquid into a loop reactor by adopting the feeding method to carry out first polymerization with a first olefin monomer;
2) Introducing the catalyst premixed liquid into a horizontal reactor by adopting the feeding method to carry out second polymerization with the product obtained in the step 1) and a second olefin monomer.
The production process of the present invention, wherein it is preferable that the first polymerization comprises a prepolymerization reaction and a liquid-phase bulk polymerization reaction which occur in this order; the reaction temperature of the prepolymerization reaction is 10-40 ℃, the reaction pressure is 2.8-4.1 Mpa, and the reaction time is 3-5 min; the reaction temperature of the liquid-phase bulk polymerization reaction is 60-80 ℃, and the reaction pressure is 2.7-4.0 Mpa.
The production method of the present invention, wherein it is preferable that, during the prepolymerization, the first olefin monomer is propylene; and in the first polymerization process, the mass concentration of the propylene polymerization catalyst in the catalyst premix is more than or equal to 50%.
In the preparation method of the present invention, it is preferable that the propylene polymerization catalyst includes a main catalyst and a cocatalyst; wherein the content of the first and second substances,
the main catalyst comprises a magnesium compound carrier, transition metal halide, alcohol with 2-15 carbon atoms and an electron donor, and the molar ratio of the four is 1: (1-40): (0.01-10): (0.01 to 10);
the cocatalyst comprises an organoaluminum compound; the organic aluminum compound comprises alkyl aluminum and/or alkyl aluminoxane serving as a hydrolysis product of the alkyl aluminum;
the ratio of the transition metal halide to the organoaluminum compound is, in terms of mole ratios, 1: (10 to 500).
In the preparation method of the present invention, preferably, the electron donor is at least one selected from organic phosphorus compounds, organosilanes, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and electron donors shown in formula I:
in the formula I, R 1 、R 6 Each independently selected from C 1 -C 12 Straight chain alkyl group of (1), C 3 -C 12 Branched alkyl of C 3 -C 15 Cycloalkyl of (C) 3 -C 15 Aryl of (2); r is 2 、R 3 、R 4 、R 5 Each independently selected from H atom, halogen, C 1 -C 12 Straight chain alkyl of (1), C 3 -C 12 Branched alkyl of C 3 -C 8 Cycloalkyl of, C 6 -C 15 Aryl of (C) 6 -C 15 Aralkyl of (4); wherein R is 2 And R 3 、R 3 And R 4 、R 4 And R 5 Are independently connected into a ring or not.
In the preparation method of the invention, preferably, in the liquid-phase bulk polymerization process, the first olefin monomer is propylene or an olefin mixture, the olefin mixture is composed of propylene with a molar percentage of not less than 96% and other olefins with a molar percentage of not more than 4%, and the other olefins are ethylene and/or butylene.
In the production method of the present invention, it is preferable that the catalyst is used in an amount of 0.02 to 0.10% by mass based on the mass of the liquid-phase propylene in the first olefin monomer in the liquid-phase bulk polymerization.
In the preparation method of the present invention, it is preferable that the liquid-phase bulk polymerization reaction employs a polymerization reaction loop, the polymerization reaction loop includes a plurality of polymerization loop units connected in parallel, and the polymerization loop unit includes a plurality of annular reaction tubes connected in series.
In the preparation method of the present invention, it is preferable that the polymerization reaction loop is connected in series with the horizontal reactor.
In the preparation method of the present invention, it is preferable that the second olefin monomer is at least two of ethylene, propylene and butene; more preferably, the mol percentage content of the ethylene in the second olefin monomer is less than or equal to 60 percent.
In the preparation method of the present invention, preferably, the reaction temperature of the second polymerization is 60 to 80 ℃ and the reaction pressure is 2.0 to 3.0Mpa, and more preferably, the reaction temperature of the second polymerization is 65 to 75 ℃ and the reaction pressure is 2.4 to 2.5Mpa.
In the preparation method of the present invention, it is preferable that the amount of the catalyst in the catalyst premix in the second polymerization process is 0.02 to 0.10% by mass of the second olefin monomer.
In the preparation method of the present invention, it is preferable that the first polymerization further comprises a step of adding a first auxiliary agent, the first auxiliary agent including a molecular weight modifier; the second polymerization further comprises the step of adding a second coagent, the second coagent comprising a molecular weight regulator.
According to the preparation method provided by the invention, preferably, a transverse stirring shaft is arranged in the horizontal reactor, and a plurality of stirring paddles are arranged on the transverse stirring shaft.
In the preparation method of the present invention, preferably, the horizontal reactor is internally divided into a gasification separation zone and a gas phase polymerization reaction zone along the feeding direction; a clapboard is arranged between the gasification separation zone and the gas-phase polymerization reaction zone; and a gap is arranged between one end of the partition plate and the side wall of the horizontal reactor.
Therefore, the invention also provides the high-impact high-gloss polypropylene prepared by the method, which is characterized in that the normal temperature impact strength is more than or equal to 60KJ/m according to the test of ASTM D256 standard 2 (ii) a The low-temperature impact strength is more than or equal to 50KJ/m 2 (ii) a Measured according to the GB/T8807 standard, the glossiness of the paint is not less than85％。
By means of the technical scheme, the feeding method and the feeding system of the propylene polymerization catalyst, the preparation method of the polypropylene by using the method and the system, and the polypropylene prepared by the preparation method at least have the following advantages:
1. the invention provides a feeding method of a propylene polymerization catalyst, which comprises the steps of firstly, uniformly mixing the propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix; aiming at the technical problems that the components of the catalyst premixed liquid are uneven and a feeding pipeline is blocked due to the fact that the catalyst premixed liquid is easy to settle, the components are kept uniform all the time by arranging stirring in each link through which the catalyst premixed liquid flows, and therefore the catalyst entering a polymerization reactor is even in components and cannot block the feeding pipeline;
2. the feeding system of the propylene polymerization catalyst provided by the invention has the advantages that the intermittent catalyst ingredients can continuously feed materials to a polymerization reactor by designing the metering tanks connected in parallel; the stirrer with the pipeline structure is arranged on the conveying pipeline, so that the catalyst is prevented from depositing in the feeding pipeline to block the pipeline, production faults are reduced, and the production efficiency is improved;
3. according to the feeding system of the propylene polymerization catalyst, the buffer tank is designed, so that the catalyst introduced into the polymerization reactor is uniform in components, and the temperature and the pressure are consistent with those in the polymerization reactor, the influence of a feeding process on the polymerization reaction process condition is minimized, and the preparation of high-performance polypropylene with a designable molecular structure is guaranteed;
4. according to the feeding system of the propylene polymerization catalyst, the diaphragm metering pump is arranged on the pipeline for accurate metering, so that the quantity of the catalyst fed into the polymerization reactor is accurate, the influence of a feeding process on the polymerization reaction process condition is minimized, and the preparation of high-performance polypropylene with a designable molecular structure is guaranteed;
5. according to the preparation method of the polypropylene, the high-impact high-gloss polypropylene is prepared by jointly using the loop reactor to perform propylene liquid-phase bulk polymerization and the horizontal reactor to perform propylene impact-resistant copolymerization, so that the defects of the prior art are overcome, the polypropylene with good impact resistance and high gloss is obtained, and the application range of the polypropylene is widened;
6. according to the preparation method of the polypropylene, the structure of a target molecule can be designed, and the proportion of olefin monomers can be adjusted in a wider range, so that the polypropylene with high ethylene content is obtained;
7. according to the preparation method of the polypropylene, the size and the molecular weight distribution of the homopolymer or the random copolymer are accurately controlled through reaction in the loop reactor; and then the materials in the horizontal reactor are axially, backmixed and radially and fully backmixed, so that the residence time of each reaction material in the reactor is basically consistent, the consistency of the molecular structure of the reaction materials is controlled, and the performance stability of the product is improved.
Drawings
FIG. 1 is a schematic process flow diagram of a process for feeding a propylene polymerization catalyst of the present invention;
FIG. 2 is a schematic view of the structure of a feed system for a propylene polymerization catalyst of the present invention.
Wherein, 1, a batching tank, 2, a metering tank, 3, a diaphragm metering pump, 4, a stirrer in a pipeline, 5, a buffer tank, 6 and a polymerization reactor;
21. a first metering tank, 22, a second metering tank.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and experimental methods without specific conditions noted in the following examples are generally performed under conventional conditions.
The invention provides a feeding method of a propylene polymerization catalyst, which comprises the following steps as shown in the attached figure 1:
s1, catalyst proportioning: uniformly mixing a propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix;
s2, catalyst metering: stirring and circulating the catalyst premixed liquid in a metering tank, accurately metering by a diaphragm metering pump, and conveying to a buffer tank;
s3, buffering of catalyst feed: stirring and circulating the catalyst premixed liquid in a buffer tank, and adjusting the temperature of the premixed liquid and the pressure in the buffer tank;
s4 propylene polymerization reaction: and introducing the catalyst premixed solution after the stable condition of the buffer tank into a polymerization reactor for propylene polymerization.
Uniformly mixing a propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix; and then the catalyst premixed liquid is fed into a propylene polymerization reactor to participate in propylene polymerization reaction after being metered, conveyed and buffered in sequence, wherein the components of the metered, conveyed and buffered premixed liquid are controlled to be uniform, the ranges of the buffered pressure and the buffered premixed liquid temperature as well as the pressure and the temperature of the propylene polymerization reaction are controlled to be the same, the premixed liquid is fed into the propylene polymerization reactor to participate in the propylene polymerization reaction after being metered, conveyed and buffered in sequence, wherein the components of the metered, conveyed and buffered premixed liquid are controlled to be uniform, and the temperature of the buffered premixed liquid is controlled to be the same as the temperature range of the propylene polymerization reaction.
In order to avoid the problems caused by catalyst sedimentation, the technical scheme of the invention improves the feeding method of the propylene polymerization catalyst, and the propylene polymerization catalyst and liquid-phase propylene are uniformly mixed to obtain a catalyst premix; and then, continuously stirring the catalyst premixed liquid in a metering tank, a conveying pipeline and a buffer tank to keep the premixed liquid in a state of uniform components, and simultaneously controlling the temperature condition of the buffer tank to be consistent with the process condition of the first procedure of the polymerization reactor, thereby reducing the influence of catalyst feeding on the polymerization reaction process condition, realizing the stable control of the polymerization reaction condition and controlling the molecular structure and the performance of a polymerization product.
Preferably, the metering comprises circulating the catalyst premix solution in a metering tank under agitation and accurately metering by a diaphragm metering pump.
The diaphragm metering pump replaces a piston with a specially designed and processed flexible diaphragm, and reciprocating motion is realized under the action of a driving mechanism to complete the suction-discharge process. Due to the isolation of the diaphragm, it is structurally possible to achieve isolation between the fluid being metered and the driving lubrication mechanism.
Preferably, the pipeline used for conveying is provided with a stirrer with a pipeline structure.
The stirrer with the pipeline structure can force liquid and gas media to convect and mix uniformly, and is composed of two straight blades, so that the generated radial liquid flow velocity is low. The two blades of the pitched blade agitator are turned 45 ° or 60 ° in opposite directions, thus creating an axial flow.
Preferably, the buffering comprises stirring and circulating the catalyst premix in a buffer tank and adjusting the temperature of the premix and the pressure in the buffer tank.
The present invention also provides a feeding system of propylene polymerization catalyst, as shown in fig. 2, which comprises:
the preparation device comprises a dosing tank 1, a reaction kettle and a reaction kettle, wherein a stirrer is arranged in the dosing tank 1 and is used for uniformly mixing a propylene polymerization catalyst and liquid-phase propylene to obtain a catalyst premix;
a metering tank 2, the inlet of which is connected with the outlet of the batching tank 1; a stirrer is arranged in the metering tank 2 and is used for continuously keeping the components of the catalyst premixed liquid uniform;
a diaphragm metering pump 3, the inlet of which is connected with the outlet of the metering tank 2, for metering the catalyst premixed liquid;
the inlet of the buffer tank 5 is connected with the outlet of the diaphragm metering pump 3, and the outlet is connected with the polymerization reactor 6; a stirrer, a temperature controller and a pressure regulator are arranged in the buffer tank 5; the stirrer is used for continuously keeping the components of the catalyst premix uniform; the temperature controller and the pressure regulator are respectively used for regulating the temperature of the catalyst premixed liquid and the pressure in the buffer tank;
and the stirrer 4 with a pipeline structure is arranged in a conveying pipeline connected between the diaphragm metering pump 3 and the buffer tank 5 and is used for continuously keeping the components of the catalyst premixed liquid uniform in the conveying process.
Preferably, metering tank 2 includes at least two metering tanks connected in parallel with each other, as shown in FIG. 2, and metering tank 2 includes two first metering tank 21 and second metering tank 22 connected in parallel with each other.
Preferably, a protective valve is arranged between the metering tank 2 and the diaphragm metering pump 3.
Preferably, the diaphragm metering pump 3 is a stroke-adjustable diaphragm metering pump.
Preferably, a plurality of stirrers 4 are arranged in the conveying pipeline; the distance between two adjacent stirrers 4 is less than 2m.
Pipeline structure's agitator, its agitating unit is including running through the (mixing) shaft that sets up in the hybrid pipeline, demountable installation has impeller on the (mixing) shaft, the one end of (mixing) shaft stretches out hybrid pipeline is connected with drive arrangement. The two mixing pipelines are longitudinally arranged in parallel, the bottom ends of the two mixing pipelines are respectively provided with an expansion pipe fitting, and a communication elbow is arranged between the bottom ends of the two expansion pipe fittings; the pipe diameter of the expansion pipe fitting is larger than the pipe diameters of the mixing pipeline and the communication elbow. The driving device comprises a driving motor, and the driving motor is installed above the mixing pipeline through a support.
The invention also provides a preparation method of the high-impact high-gloss polypropylene, which comprises the following steps:
1) Obtaining a catalyst premix according to the feeding method;
2) Introducing the catalyst premixed liquid into a loop reactor according to the feeding method to perform first polymerization with a first olefin monomer;
3) And (3) introducing the catalyst premixed solution into a horizontal reactor according to the feeding method to perform second polymerization with the product obtained in the step 2) and a second olefin monomer.
In said loop reactor, liquid phase bulk polymerization of said first olefin monomer occurs; a first auxiliary agent may be added at the time of the first polymerization; the first auxiliary means various auxiliaries required in the first polymerization, for example, including a molecular weight regulator and the like; in the horizontal reactor, the second olefin monomer and the product obtained in the step 2) undergo gas-phase copolymerization to generate a propylene copolymer; a second auxiliary agent can be added during the second polymerization; the second auxiliary means various auxiliary agents required at the time of second polymerization, for example, including a molecular weight regulator and the like.
In the polymerization process, the characteristics of materials in different stages before and after the polymerization process are different greatly, the requirements on reaction conditions are different, for example, the viscosity of a material system in the early stage of the polymerization is low, the heat is more released, the flow is easy, the conditions are often opposite in the later stage of the polymerization, and the low molecular substances generated can be removed while the reaction is carried out, so that a horizontal reactor can achieve a better effect.
Preferably, the first polymerization comprises a prepolymerization reaction and a liquid-phase bulk polymerization reaction which occur in this order.
The loop reactor comprises a prepolymerization loop and a liquid-phase bulk polymerization loop which are connected in series. Firstly, propylene and a catalyst are introduced into the prepolymerization loop to carry out prepolymerization reaction to obtain slurry containing the catalyst with a certain polymerization degree, so that the reaction control capability of subsequent liquid-phase bulk polymerization can be adjusted.
And introducing the slurry containing the catalyst obtained by the prepolymerization reaction, the first olefin monomer and the first auxiliary agent with the formula design into the polymerization reaction loop to carry out liquid-phase bulk polymerization reaction to obtain the polymer slurry with a certain polymerization degree.
Preferably, in the prepolymerization, the first olefin monomer is propylene; the mass concentration of the catalyst component is more than or equal to 50 percent.
Preferably, the reaction temperature of the prepolymerization reaction is 10-40 ℃, the reaction pressure is 2.8-4.1 Mpa, and the reaction time is 3-5 min.
Preferably, the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein the main catalyst comprises a magnesium compound carrier, transition metal halide, alcohol with 2-15 carbon atoms and an electron donor; the molar ratio of the magnesium compound carrier, the transition metal halide, the alcohol with the carbon atom number of 2-15 and the electron donor is 1: (1-40): (0.01-10): (0.01 to 10); the cocatalyst comprises an organoaluminum compound; the dosage of the transition metal halide and the cocatalyst organic aluminum compound in the main catalyst is 1: (10 to 500).
Preferably, the electron donor is at least one selected from organic phosphorus compounds, organosilanes, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and electron donors with the following structures:
in the formula, R 1 、R 6 Each independently selected from C 1 -C 12 Straight chain alkyl of (1), C 3 -C 12 Branched alkyl of C 3 -C 15 Cycloalkyl of, C 3 -C 15 Aryl of (a); r 2 、R 3 、R 4 、R 5 Each independently selected from H atom, halogen, C 1 -C 12 Straight chain alkyl group of (1), C 3 -C 12 Branched alkyl of C 3 -C 8 Cycloalkyl of, C 6 -C 15 Aryl of, C 6 -C 15 Aralkyl of (4); wherein R is 2 And R 3 、R 3 And R 4 、R 4 And R 5 Are independently connected into a ring or not connected into a ring.
Preferably, the organoaluminum compound comprises an alkylaluminum and/or a hydrolysate of an alkylaluminoxane.
The catalyst is used for homopolymerization or olefin copolymerization of olefin monomers, and the olefin monomers can be any one or more of ethylene, alpha-olefin of C3-C20 or polar olefin monomers of C3-C20.
Specifically, the olefin polymerization catalyst adopted in the technical scheme of the invention can effectively catalyze ethylene homopolymerization, propylene homopolymerization, ethylene and alpha-olefin copolymerization, propylene and alpha-olefin copolymerization, ethylene and polar olefin monomer copolymerization or propylene and polar olefin monomer copolymerization, and the catalyst has high catalytic activity. Among them, the α -olefin is a C3 to C20 olefin, and preferably propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene, α -methylstyrene and norbornene.
Preferably, in the liquid phase bulk polymerization, the first olefin is propylene; or the first olefin monomer consists of propylene with a molar percentage of more than or equal to 96 percent and ethylene and/or butylene with a molar percentage of less than or equal to 4 percent.
The liquid-phase bulk polymerization may be homopolymerization or copolymerization. The actual production can be determined by the formula design according to the product performance requirements to be produced. Mixing the raw material slurry, liquid-phase propylene and hydrogen to obtain a liquid-phase polymerization raw material; feeding the liquid-phase polymerization raw material into a polymerization reaction loop reactor to carry out propylene liquid-phase bulk homopolymerization to obtain polypropylene slurry; and continuously inputting the polypropylene slurry into a horizontal gas-phase polymerization reactor, and carrying out gas-phase homopolymerization on propylene in the polypropylene slurry to obtain a product containing a propylene homopolymer. Or sending the liquid-phase polymerization raw material into a polymerization reaction loop reactor to carry out liquid-phase random copolymerization with ethylene to obtain copolymer slurry; wherein the ethylene feed is less than 5% by mass of the liquid phase propylene (since ethylene is a non-condensable gas, and at high contents in the loop reactor, it may be difficult to fuse with propylene into a homogeneous phase, and there is also a large safety risk); and continuously inputting the copolymer slurry into a gas-phase polymerization reactor, and carrying out gas-phase random copolymerization or gas-phase impact copolymerization on the ethylene and the propylene in the copolymer slurry to obtain a product containing a propylene-ethylene random copolymer or an impact ethylene-propylene copolymer, wherein the specific reaction can be carried out, and the feeding proportion and the process parameters can be designed according to the actual production requirement to obtain the polymer with the target structure. The product containing propylene homopolymer or the product containing propylene ethylene random/impact copolymer obtained by the technical scheme of the invention is subjected to gas-solid separation, the separated solid is dried to obtain polypropylene or propylene ethylene copolymer, and the separated gas is subjected to propylene and hydrogen recovery.
When the first olefin monomer is propylene alone, the product obtained by polymerization in the loop reactor is a polypropylene homopolymer. When the first olefin monomer is a mixture of propylene and ethylene, the product obtained by polymerization in the loop reactor is an ethylene-propylene random copolymer. Since ethylene is a non-condensable gas, when the amount of ethylene added is large, there are problems of pressure load in the reactor, and high reaction heat in the polymerization of ethylene, which results in that the content of ethylene in the loop reactor cannot be large, or the reaction conditions of the polymerization reaction system cannot be controlled easily.
Preferably, in the liquid-phase bulk polymerization reaction, the catalyst is used in an amount of 0.02 to 0.10% by mass based on the mass of the liquid-phase propylene.
The amount of the catalyst can be determined according to actual production needs and the structure and performance of the target polymer.
Preferably, the amount of the catalyst is 0.02 to 0.03%, 0.03 to 0.04%, 0.04 to 0.05%, 0.05 to 0.06%, 0.06 to 0.07%, 0.07 to 0.08%, 0.08 to 0.09%, and 0.09 to 0.10% by mass of the liquid phase propylene.
Preferably, the first polymerization in step 2) further comprises the step of adding a first auxiliary agent; the first auxiliary agent comprises a molecular weight regulator.
The molecular weight regulator is hydrogen, which is also called chain transfer agent. In the actual production process, the process of adjusting the melt index of the polymer by using hydrogen without using a degradation agent enables the molecular weight of the polymer to be small and the melt index to be increased. Hydrogen is used as a chain transfer agent of the polymerization reaction, and is dissolved in liquid-phase propylene to enter the two loop reactors for chain transfer reaction, so that the melt index of a polymer product is obviously improved, and the product has the characteristics of no toxicity and no odor.
In the liquid-phase bulk polymerization, the concentration of hydrogen can be adjusted within a wide range depending on the molecular weight of the polymer to be produced. The hydrogen concentration is less than or equal to 20 percent by volume; the hydrogen concentration is less than or equal to 10 percent; the hydrogen concentration is less than or equal to 5 percent; the concentration of hydrogen is less than or equal to 1 percent; the hydrogen concentration is less than or equal to 0.8 percent; the hydrogen concentration is less than or equal to 0.6 percent; the hydrogen concentration is less than or equal to 0.4 percent; the hydrogen concentration is less than or equal to 0.2 percent.
Preferably, the reaction temperature of the liquid-phase bulk polymerization reaction is 60-80 ℃, and the reaction pressure is 2.7-4.0 MPa.
The polymerization in the loop reactor is liquid phase polymerization, and the polymerization temperature is basically kept at about 70 ℃. Because of the low vaporization temperature of the olefin monomer, it is necessary to maintain a certain pressure at the reaction temperature to make the reaction system a liquid phase medium. The loop reactor is adopted for homopolymerization or random copolymerization, on one hand, the concentration of the monomer can be improved in a liquid phase medium, so that the polymerization activity of the catalyst is improved; on the other hand, the loop reactor has small pipe diameter, large specific surface area and fast heat transfer, is particularly suitable for the conduction of reaction heat generated by polymerization reaction, is beneficial to the stable maintenance of the reaction system condition and has good reaction controllability for high exothermic reaction. In the liquid-phase bulk polymerization, the liquid is reacted in a loop in a circulating and reciprocating way, which is a process of fully mixing materials, and the reaction materials are fully contacted, so that the reaction of the materials is more thorough, and therefore, the homopolymerization or random copolymerization in the step has high conversion rate, and the effect of greatly increasing the yield can be achieved.
The liquid phase bulk polymerization is carried out in liquid phase propylene by taking hydrogen as a molecular weight regulator. To produce a homopolymer of propylene or a copolymer of propylene and ethylene, a C4 and C4 or higher alpha-olefin. The polymerization conditions of the liquid-phase bulk polymerization are as follows: the polymerization pressure is 2.2-6.5 Mpa, and the polymerization temperature is 55-95 ℃. The polymerization pressure is preferably 2.7 to 4.0MPa, and the polymerization temperature is preferably 60 to 80 ℃. The hydrogen concentration is determined according to the molecular weight of the polymer to be produced by the liquid-phase bulk polymerization.
In actual production, the molecular weight of the polymer produced by liquid-phase bulk polymerization is generally smaller than that of the polymer produced by gas-phase bulk polymerization. The polymer generated by liquid-phase bulk polymerization accounts for 20-90% of the total polymer.
Preferably, said loop reactor comprises a polymerization loop in which liquid phase bulk polymerization takes place, comprising a polymerization loop unit; the polymerization loop unit comprises one or more loop pipes connected in series.
The one or more serially connected annular tubes form a polymeric loop unit.
In one embodiment of the present invention, the polymerization loop may be a single loop or may be two or more loops connected in series, and the reaction conditions in each loop are designed according to actual needs and can be independently controlled to control the structure and molecular weight of the polymer. The monomer and catalyst conditions in each annular tube can be the same or different, and the prepared product can be a homopolymer of a single olefin monomer or a random copolymer of a plurality of olefin monomers; the obtained product may be a unimodal polymer, a bimodal polymer or a multimodal polymer.
Preferably, said polymerization reaction loop comprises several polymerization loop units connected in parallel.
The loop reactor comprises a prepolymerization loop and a polymerization reaction loop, wherein each loop adopts a series connection and parallel connection mixed connection mode, and can be flexibly designed through different technical purposes in actual production.
The loop reactor is divided into two areas, one area is a prepolymerization area, and the other area is a liquid-phase bulk polymerization reaction area; the loop pipes between the two zones are connected in series, and the slurry after prepolymerization in the prepolymerization zone is conveyed to the polymerization reaction zone through a pipeline for liquid-phase bulk polymerization. Wherein the prepolymerization zone comprises a loop into which the first olefin monomer and the catalyst are fed to carry out prepolymerization; the liquid-phase bulk polymerization zone comprises a loop, wherein the prepolymerization product, the first olefin monomer and the first auxiliary agent are introduced into the loop to continue the bulk homopolymerization polymerization reaction to obtain the propylene homopolymer or the ethylene-propylene random copolymer.
In one embodiment of the invention the loop reactor is made up of a number of loops including a prepolymerization loop and several polymerization loop units connected in parallel. The reaction conditions of each polymerization loop unit are independently designed and controlled, and polymers with various polymerization structures and molecular weights can be designed and manufactured according to actual needs.
In the technical scheme of the invention, the olefin is subjected to liquid-phase bulk polymerizationA loop reactor is adopted, a loop is a fully mixed flow, and a plurality of loops are connected in series to be similar to a plurality of stirred tanks connected in series. Compared with kettle type bulk polymerization, the loop has large heat transfer area and high conversion per pass; in the loop bulk polymerization, polymer particles are suspended in propylene liquid, and the polymer and the propylene have good heat transfer; the reaction heat is removed by adopting a cooling jacket, the heat transfer area per unit volume is large, the heat transfer coefficient is large, and generally, the overall heat transfer coefficient of the loop reactor can be as high as 1600 w/(m) 2 Deg.c); the polymer slurry in the loop reactor has a high concentration, and is generally>50 percent (mass fraction), the single-pass conversion rate of the reactor is high, and the single-pass conversion rate of homopolymerized propylene can reach 50 to 65 percent. Further, the loop has the advantage of enhancing the mass transfer effect, in addition to improving the heat transfer capacity of the system. The slurry in the loop reactor is circulated at a high speed by an axial flow pump, and the flow velocity of the fluid can reach 7m/s; if the recycle ratio is high enough, the flow in the loop can be close to perfect thorough mixing, and the distribution of comonomer, catalyst, etc. is more uniform throughout the reactor; on one hand, the isotacticity of the polymer can be improved, and on the other hand, the polymerization reaction conditions are easy to control and can be controlled to be very accurate, so that the product quality is stable, hot spots are not easy to generate, the wall is not easy to stick, and the energy consumption of the axial flow pump is lower; in a stirring kettle, particularly a large stirring kettle, a system always has dead zones, the structure of the manufactured polymer is not uniform, and the performance is unstable; furthermore, the fluid in the loop pipe should be close to the fluid of a piston type, and the short circuit of the catalyst can be greatly reduced and the residence time of the catalyst can be improved under the conveying of the axial flow pump, and the fluid in the tank reactor is in a full mixing type, so that the short circuit of the catalyst can be easily caused.
Preferably, said polymerization reaction loop is connected in series with said horizontal reactor.
The discharge of the loop reactor is directly introduced into the horizontal reactor, the monomer is not required to be gasified by steam, and the liquid-phase monomer is gasified by the heat of gas-phase polymerization reaction, so that the steam consumption is reduced. The conversion per pass of the reaction is high and can reach more than 80 percent, and the circulating amount of the monomer is small.
The preparation method of the polypropylene is a continuous process. The homopolymer or random copolymer obtained from the loop reactor can be fed into the horizontal reactor for further copolymerization without flashing or the like.
The horizontal reactor is a continuous reactor, materials are continuously input from one end of the reactor, products are continuously output from the other end of the reactor until a certain conversion rate is reached, chemical reaction is completed in the flow, and the concentration is gradually reduced and the reaction rate is gradually reduced along with the movement of the materials in the reactor. The horizontal reactor can be provided with a plurality of stirring paddles, and each stirring paddle is separated by a partition plate, so that the flowing condition of materials in the reactor is similar to that of a multistage series stirring reactor, thereby reducing the number of equipment and the installation height.
The horizontal reactor has the following special requirements besides the requirement of a common reactor: firstly, materials can be fully back-mixed in the radial direction in the reactor, and have no back-mixing in the axial direction, and the materials are close to plug flow as much as possible; secondly, according to the theory of polymerization kinetics, in order to achieve the predetermined degree of polymerization, small molecules generated in the system are removed as much as possible, so that the reaction materials are spread in the reactor as much as possible to form a large-area film, thereby increasing the evaporation surface area and continuously updating the evaporation surface area.
In the prior art, most of gas-phase polymerization reactors commonly used in combination with a loop are gas-phase fluidized bed reactors, and fluidized beds belong to fully mixed reactors, so that the difference of the residence time of various materials in the reactors is large, and the difference between polymer powder individuals in the reactors is relatively large. When producing copolymer products, some materials have a very short residence time, so that their content in the comonomer is very low; theoretically, 100% of the homopolymer particles may be present in the copolymer product obtained therefrom, and the structure and distribution of the various components in the copolymer are difficult to control, which may affect the properties of the copolymer product to some extent.
In the technical scheme of the invention, the gas-phase bulk polymerization adopts a horizontal reactor. Compared with a gas-phase fluidized bed reactor, the horizontal reactor has the advantages of high equipment efficiency, high catalyst utilization efficiency, uniform comonomer content of the product, strong adaptability even if the comonomer content in the product is higher or the molecular weight of the polymer is very low, which may cause powder to be sticky. Because the catalyst introduced into the horizontal reactor is polypropylene powder which is fully polymerized in the liquid phase body in the loop reactor, hot spots generated by catalyst aggregation can not occur in the horizontal reactor, so that the horizontal reactor can carry out gas-phase polymerization under wider and higher reaction pressure (2.1-3.0 Mpa) and wider reaction temperature (60-130 ℃) without generating hot spots, does not generate plasticized blocks, and has good reaction controllability.
In one embodiment of the invention, a plurality of polymerization loop units are connected in parallel, each polymerization loop unit being capable of carrying out the same or a different polymerization reaction; and simultaneously feeding the polymerized product into a horizontal reaction kettle for gas-phase copolymerization. When the same polymerization reaction is carried out in each polymerization loop unit, the technical scheme of the invention can improve the yield of polypropylene and overcome the defect of small yield of a loop reactor by connecting a plurality of polymerization loop units in parallel and then connecting the polymerization loop units with a horizontal reactor in series. When different polymerization reactions are carried out in each polymerization loop unit, the technical scheme of the invention can design the structure and the performance of the copolymer by connecting a plurality of polymerization loop units in parallel and then connecting the polymerization loop units with a horizontal reactor in series, and simultaneously can combine the advantages of the loop reactor and the horizontal reactor, the dispersion of materials such as a catalyst is good, hot spots are not easy to generate, the production efficiency is high, and the polypropylene with excellent comprehensive performance can be obtained.
Preferably, the second olefin monomer is at least two of ethylene, propylene or butylene.
The olefin monomer can be at least one of C2-C12 olefin monomers. It should be noted that, with respect to the present preparation method, the olefin monomer is not particularly limited, and may be selected according to actual needs after the target product is determined. The gas-phase bulk polymerized olefin monomer can be gas-phase copolymerization of propylene and propylene, or propylene and ethylene, butylene and alpha-olefin above butylene to produce propylene homopolymer, or random copolymer, or impact copolymer.
Preferably, the mole percentage of the ethylene in the second olefin monomer is less than or equal to 60 percent.
In the preparation of impact polypropylene, ethylene units may be incorporated into the polypropylene to improve its properties. The traditional modification mode of physical blending is gradually replaced by the modification mode of chemical copolymerization due to poor modification effect. The technical scheme of the invention obtains a product with good low-temperature impact resistance and high glossiness by adjusting and optimizing olefin monomers, such as copolymerization of ethylene, propylene and butylene.
The process flow of the invention is as follows: propylene and additives such as a catalyst and the like sequentially enter a prepolymerization loop to be prepolymerized, liquid-phase bulk polymerization is carried out in a polymerization reaction loop, and then the propylene and the additives enter a horizontal reactor to be gas-phase bulk polymerization for homopolymerization or copolymerization. In producing impact copolymers, a prepolymerization loop, a polymerization loop produce a propylene homopolymer of lower molecular weight, and a horizontal reactor produces a propylene and ethylene or alpha olefin copolymer of higher molecular weight.
The reaction in the horizontal reactor mainly comprises gas-phase bulk polymerization of propylene and ethylene, C4 and alpha-olefin above C4; in the production of impact copolymers, polymers of higher molecular weight are produced in a horizontal reactor. The technical scheme of the invention adopts a step polymerization process combining liquid phase bulk polymerization in a loop reactor and gas phase bulk polymerization in a horizontal reactor to carry out propylene homopolymerization and copolymerization of propylene and ethylene, C4 and alpha-olefin above C4, and can produce the method for preparing the polypropylene homopolymer and copolymer with adjustable molecular weight distribution in a wide range.
Preferably, the reaction temperature of the second polymerization is 60 to 80 ℃, and the reaction pressure is 2.0 to 3.0MPa. More preferably, the second polymerization temperature is 65-75 ℃, the reaction pressure is 2.4-2.5 Mpa.
In the production of impact copolymers, the temperature of the gas-phase bulk polymerization is controlled above the dew point and below the softening point of the polymer, generally between 60 and 80 ℃ and preferably between 65 and 75 ℃.
Since the catalyst for polymerization is added to the reaction system in the liquid bulk polymerization in the loop reactor, which is initially polymerized in the prepolymerization loop and continues to grow in the subsequent liquid bulk polymerization, the polymer slurry fed into the horizontal reactor contains polypropylene powder after polymerization growth, and thus, even at an operating pressure of up to 3.0Mpa and an operating temperature above the dew point, the copolymerization in the horizontal reactor does not generate hot spots due to the aggregation of the catalyst to generate plasticized masses.
Preferably, the catalyst used in the second polymerization is used in an amount of 0.02 to 0.10% by mass of the second olefin.
The amount of the catalyst can be determined according to the actual production needs and the structure and properties of the target polymer.
Preferably, the catalyst is used in an amount of 0.02 to 0.03%, 0.03 to 0.04%, 0.04 to 0.05%, 0.05 to 0.06%, 0.06 to 0.07%, 0.07 to 0.08%, 0.08 to 0.09%, and 0.09 to 0.10% by mass of the second olefin.
Preferably, the second polymerization in step 3) further comprises the step of adding a first auxiliary agent; the second auxiliary agent comprises a molecular weight regulator.
In gas-phase bulk polymerization, polymerization is likewise carried out using hydrogen as molecular weight regulator, the concentration of hydrogen being adjustable within wide limits according to the molecular weight of the polymer to be produced. Generally, the hydrogen concentration in the second polymerization is slightly less than that in the first polymerization, and the specific value is determined according to the molecular structure and properties of the product to be produced. The molecular weight and structure of the polymer obtained in the loop reactor as well as in the horizontal reactor can be controlled by adjusting and varying the hydrogen concentration.
In the gas-phase bulk polymerization, the type of catalyst used is similar to that used in the first polymerization, and the amount of the catalyst used may be adjusted within a wide range depending on the molecular weight of the polymer to be produced.
Preferably, the horizontal reactor is provided with a transverse stirring shaft, and the stirring shaft is provided with a plurality of stirring paddles.
Preferably, the shape of the stirring paddle is selected from the group consisting of T-shape, rectangular shape, wedge shape and open shape.
In the horizontal reactor propylene polymerization process, agglomeration is one of the hidden troubles seriously affecting the long-term stable operation of the device and the product quality. Analysis of a large number of study data shows: when the stirring paddle adopts the blade paddle for stirring, the back mixing degree of materials in the reactor is maximum and is closest to the fully mixed flow, which is not beneficial to the consistency control of the retention time of the materials in the reactor, increases the difficulty of the quality control of the polymer, and the obtained copolymer has uneven structure and unstable performance; the T-shaped, rectangular, wedge-shaped and open-type paddles have better effect; preferably, the horizontal kettle with T-shaped paddle is used for stirring, and the back mixing degree of the materials in the reactor is minimum and is closest to the plug flow.
The technical scheme of the invention adopts a horizontal reactor and a T-shaped stirring paddle, and the unique reactor ensures that the distribution range of the residence time of various material particles in the reactor is narrow, and can produce copolymer products with very good rigidity and impact resistance. Further, such near plug flow reactors may avoid short circuiting of the catalyst within the reactor. When ethylene is present in the second olefin, rather than forming a fine powder within the homopolymer particles that could reduce the low temperature impact strength of the copolymer, large particles of the copolymer can be formed and form unwanted colloids. Thus, the narrow reaction residence time distribution of the process can meet the requirements for high impact copolymers that can only be produced using multiple fully mixed reactor homopolymerizers. In addition, due to the unique reactor design, the product transition time of the process is very short, theoretically the product transition time is 2/3 shorter than that of a continuous stirred reactor or a fluidized bed reactor, so that the product switching is easy and the transition products are very few.
Preferably, the horizontal reactor sequentially comprises a gasification separation zone and a gas-phase polymerization reaction zone from the feeding direction to the discharging direction; a clapboard is arranged between the gasification separation zone and the gas phase polymerization reaction zone; a gap is arranged between one end of the clapboard and the side wall of the horizontal reactor.
In the technical scheme of the invention, the polymer slurry obtained from the loop reactor can be directly introduced into the horizontal reactor without treatment such as flash evaporation and degassing.
The horizontal reactor can be divided into a plurality of polymerization subareas with different polymerization temperatures and gas-phase components by partition plates, and each of the polymerization subareas is provided with an independent external circulation cooling system. The recycle gas and the condensate can be returned to the bottom of the horizontal reactor together. The entering catalyst can be slurry liquid which is subjected to prepolymerization and slurry polymerization with propylene.
The horizontal reactor adopts a propylene flash mode to remove heat. Liquid propylene is injected into the reactor from various feed points in a manner to keep the reactor bed dry, and after vaporization of the liquid propylene, the partial pressure of the monomer is less than its dew point pressure and sufficient to remove the heat of reaction. The feed rate of liquid propylene and its vaporization in the reactor must be tightly controlled in operation to ensure a balance between the degree of dryness of the reactor and the reaction temperature range.
The material inlet end of the horizontal reactor is provided with a gasification separation zone, the polymer slurry produced by the loop reactor firstly enters the gasification separation zone of the horizontal reactor, the liquid phase in the slurry is gasified in the zone due to the action of polymerization heat, and most of hydrogen and part of propylene are separated and leave the horizontal reactor. The polypropylene powder after the separation and removal of most of hydrogen and part of propylene enters a gas-phase polymerization reaction zone through a gap between the partition plate and the side wall of the horizontal reactor. The polymerization in the gas phase polymerization zone can be carried out at a set hydrogen concentration and a set ratio of propylene to comonomer to produce a homopolymer or copolymer having a higher molecular weight than that of the liquid phase bulk polymerization.
The said gas-phase polymerization zone may be an integral zone or it may be divided into several sub-zones of the gas-phase polymerization zone by providing partitions inside it. The horizontal reactor with the gas-phase polymerization zone subareas has the reaction effect equivalent to that of a plurality of gas-phase polymerization kettles connected in series, the reaction conditions of each zone can be independently controlled, and the product design and the product production can be realized flexibly through one device.
Furthermore, the horizontal reactors can be connected in series. When a plurality of horizontal reactors are connected in series, the vaporization separation zone may be provided only in the 1 st horizontal reactor connected to the loop reactor.
When a plurality of horizontal reactors are connected in series, the molecular weight of the gas-phase polymerized polymer gradually increases from the 1 st horizontal reactor connected to the loop reactor; however, if necessary, the molecular weight of the copolymer to be produced may be controlled so that the same polymer as that polymerized in the horizontal reactor 1 may be produced.
The horizontal reactor and the matching device matched with the horizontal reactor to run are collectively called as a gas phase reaction zone. Specifically, in the gasification separation zone, the horizontal reactor of the invention is provided with a polymer slurry inlet for receiving polymer slurry introduced into the loop reactor or the extractor; the device is also provided with an exhaust port for exhausting the separated gasified propylene gas and hydrogen; if necessary, a quenching liquid inlet for propylene may be provided to lower the reactor temperature, through which quenching liquid for propylene may be sprayed as needed, and the reactor temperature may be adjusted by removing heat through vaporization of cold liquid-phase propylene. In the gas-phase polymerization zone, the horizontal reactor is also provided with the following external matching devices, including an external circulation condenser, a condensate tank, a condensate reflux pump, a circulating fan of non-condensable gas and the like. In the case of gas-phase homopolymerization, the condensed liquid and the non-condensable gas may be returned to the gas-phase polymerization zone; however, in the production of the copolymerization product, the condensed liquid and the non-condensable gas are not allowed to return to the vaporization separation zone so as not to affect the reaction conditions in the gas-phase polymerization zone.
The method can prepare products with various structures and properties according to product design, for example, the range of the ethylene content in gas-phase copolymerization can be randomly adjusted within less than or equal to 50 percent. The structure and the performance of the polymer obtained by the technical scheme of the invention can be designed, and different designs can be carried out according to actual needs in actual operation to obtain products meeting various requirements.
The invention also provides the high-impact high-gloss polypropylene prepared by the methodAlkene, detected according to ASTM D256 standard, has a normal temperature impact strength of not less than 60KJ/m 2 (ii) a The low-temperature impact strength is more than or equal to 50KJ/m 2 (ii) a The glossiness of the paint is more than or equal to 85 percent according to the GB/T8807 standard detection.
In the detection method, the low temperature is-20 ℃.
The preparation method adopts a process method of liquid phase bulk polymerization in a loop reactor combined with gas phase bulk polymerization in a horizontal reactor, and simultaneously can carry out polymer structure design according to actual requirements in the presence of a proper catalyst, and the generated polypropylene particles are large, uniform and spherical, the molecular weight distribution can be adjusted, and the product has the advantages of wide and narrow range, high crystallinity and good optical performance; and the copolymerized ethylene content and the distribution in the ethylene copolymer are fine and uniform, and the low-temperature impact resistance is good.
The invention also provides application of the high-impact high-gloss polypropylene prepared by the method.
The following is further illustrated by the specific examples:
example 1
The feed system that this embodiment adopted includes: the batching tank 1 is internally provided with a stirrer; metering tank 2 (comprising a first metering tank 21 and a second metering tank 22 which are connected in parallel with each other), the inlet of which is connected with the outlet of the dosing tank 1; a diaphragm metering pump 3, the inlet of which is connected with the outlet of the metering tank 2; the inlet of the buffer tank 5 is connected with the outlet of the diaphragm metering pump 3, and the outlet is connected with the polymerization reactor 6; a stirrer, a temperature controller and a pressure regulator are arranged in the buffer tank 5; and a stirrer 4 with a pipeline structure is arranged in a conveying pipeline connecting the diaphragm metering pump 3 and the buffer tank 5 and is used for continuously keeping the components of the catalyst premixed liquid uniform in the conveying process. Two sets of buffer tanks 5 of the feeding system are arranged, and one set of buffer tank is connected with the prepolymerization loop pipe and used for enabling the components of the prepolymerization loop pipe to be uniform and adjusting the temperature of the prepolymerization loop pipe and the temperature of the prepolymerization loop pipe; the other set is connected with the horizontal reactor for making the components thereof uniform and adjusting the temperature thereof and the temperature of the horizontal reactor.
The preparation method of the high impact high gloss polypropylene comprises the following steps: a prepolymerization loop, a polymerization reaction loop and a horizontal reactor which are connected in series are adopted; the prepolymerization ring pipe is a single-ring pipe; the polymerization reaction loop comprises two polymerization reaction units connected in parallel; each of said polymerization units comprises two annular tubes connected in series; the horizontal reactor is internally provided with a gas-phase separation zone and a gas-phase copolymerization reaction zone; the polymerization reaction units are connected with the inlet end (gas phase separation area) of the horizontal reactor, and the preparation steps are as follows:
firstly, introducing propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 10-12 ℃ and the reaction pressure to be 4.0-4.1 Mpa, and reacting for 5min; wherein, in the catalyst, the mole ratio of the magnesium compound carrier, the ferrous chloride, the octanol and the cyclic phosphate ester is 1:10:2:2; the cocatalyst is triethyl aluminum; the dosage of ferrous chloride and triethyl aluminum is 1:100; the mass concentration of the catalyst is 50%.
Introducing ethylene and propylene into a polymerization reaction ring pipe to serve as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.05 percent of the mass of the liquid phase propylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 3.2-3.3 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 90 percent, and the volume percentage of the ethylene is 10 percent; the reaction temperature is 73-75 ℃; the reaction pressure is 2.3-2.4 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.05 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is tested according to ASTM D256 standard, and the normal temperature impact strength is 68.8KJ/m 2 Low temperature impact strength of 54KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and was found to be94.2％。
The infrared spectrogram shows that the high-gloss impact-resistant co-polypropylene resin is different from common propylene-ethylene random co-polypropylene and conventional impact-resistant co-polypropylene.
Example 2
The reactor was the same as in example 1, and the specific preparation steps were as follows:
firstly, introducing propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 38-40 ℃ and the reaction pressure to be 2.8-2.9 Mpa, and reacting for 5min; wherein in the catalyst, the mole ratio of the magnesium compound carrier, titanium tetrachloride, 1-pentadecanol and cyclohexyl methyl dimethoxy silane is 1:40:10:10; the cocatalyst comprises tri-n-propyl aluminum; the molar ratio of titanium tetrachloride to tri-n-propylaluminum is 1:10; the mass concentration of the catalyst is 50%.
Introducing ethylene and propylene into a polymerization reaction ring pipe to serve as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.10 percent of the mass of the liquid phase propylene; the reaction temperature is 60-62 ℃, and the reaction pressure is 3.9-4.0 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 80 percent, and the volume percentage of the ethylene is 20 percent; the reaction temperature is 65-67 ℃; the reaction pressure is 2.4-2.5 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin liquid; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase. The catalyst is a catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin; the performance of the product obtained in this example was examined. The impact strength is measured according to the ASTM D256 standard, and the normal temperature impact strength is 66.7KJ/m 2 Low temperature impact strength of 60.2KJ/m 2 (ii) a The glossiness of the paint is measured according to the GB/T8807 standard and is 94.0 percent。
Example 3
The reactor was the same as in example 1, and the specific preparation steps were as follows:
firstly, feeding propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 20-22 ℃ and the reaction pressure to be 3.5-3.6 Mpa, and reacting for 3min; wherein, in the catalyst, the molar ratio of the magnesium compound carrier, the copper chloride, the n-hexanol and the dicyclopentyldimethoxysilane is 1; the cocatalyst is triethyl aluminum; the amount of cupric chloride to triethylaluminum is, in terms of mole ratios, 1:500; the mass concentration of the catalyst is 60%.
Introducing ethylene and propylene into a polymerization reaction ring pipe to serve as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.08 percent of the mass of the liquid phase propylene; the reaction temperature is 78-80 ℃, and the reaction pressure is 2.7-2.8 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 70 percent, and the volume percentage of the ethylene is 30 percent; the reaction temperature is 60-62 ℃; the reaction pressure is 2.9-3.0 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.10 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is measured according to ASTM D256 standard, and the normal temperature impact strength is 69.0KJ/m 2 Low temperature impact strength of 68.8KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 93.2%.
Example 4
The reactor was the same as in example 1, and the preparation procedure was as follows:
firstly, feeding propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 20-22 ℃ and the reaction pressure to be 3.5-3.6 Mpa, and reacting for 5min; wherein, in the catalyst, the molar ratio of the magnesium compound carrier, the cobalt chloride, the n-hexanol and the dicyclopentyldimethoxysilane is 1; the cocatalyst is triethyl aluminum; the molar ratio of copper chloride to triethyl aluminum was 1:100; the mass concentration of the catalyst is 50%.
Introducing ethylene and propylene into a polymerization reaction ring pipe to serve as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.05 percent of the mass of the liquid phase propylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 3.2-3.3 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 60 percent, and the volume percentage of the ethylene is 40 percent; the reaction temperature is 72-74 ℃; the reaction pressure is 2.4-2.5 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is tested according to ASTM D256 standard, and the normal temperature impact strength is 67.5KJ/m 2 Low temperature impact strength of 71.3KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 91.0%.
Example 5
The reactor was the same as in example 1, and the preparation procedure was as follows:
firstly, introducing propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 20-22 ℃ and the reaction pressure to be 3.5-3.6 Mpa, and reacting for 5min; wherein in the catalyst, the molar ratio of the magnesium compound carrier to the titanium tetrachloride to the n-hexanol to the dicyclopentyldimethoxysilane is 1; the cocatalyst is triethyl aluminum; the amount of cupric chloride to triethylaluminum is, in terms of mole ratios, 1:500, a step of; the mass concentration of the catalyst is 50%.
Introducing ethylene and propylene into a polymerization reaction ring pipe to serve as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.05 percent of the mass of the liquid phase propylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 3.2-3.3 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled at 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 50 percent, and the volume percentage of the ethylene is 50 percent; the reaction temperature is 72-74 ℃; the reaction pressure is 2.4-2.5 Mpa; the catalyst is a catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is measured according to ASTM D256 standard, and the normal temperature impact strength is 65.8KJ/m 2 Low temperature impact strength of 73.2KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 89.0%.
Example 6
The reactor was the same as in example 1, and the preparation procedure was as follows:
firstly, introducing propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 20-22 ℃ and the reaction pressure to be 3.5-3.6 Mpa, and reacting for 5min; wherein, in the catalyst, the molar ratio of the magnesium compound carrier, titanium tetrachloride, n-hexanol and dicyclopentyldimethoxysilane is 1; the cocatalyst is triethyl aluminum; the molar ratio of copper chloride to triethyl aluminum was 1:100, respectively; the mass concentration of the catalyst is 50%.
Introducing ethylene and propylene into a polymerization reaction ring pipe as raw materials; wherein, the mol percent of the propylene is 96 percent, and the mol percent of the ethylene is 4 percent; the dosage of the catalyst is 0.05 percent of the mass of the liquid phase propylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 3.2-3.3 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 40 percent, and the volume percentage of the ethylene is 60 percent; the reaction temperature is 72-74 ℃; the reaction pressure is 2.4-2.5 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is measured according to ASTM D256 standard, and the normal temperature impact strength is 65.4KJ/m 2 Low temperature impact strength of 74.8KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 86.5%.
Example 7
The reactor was the same as in example 1, and the preparation procedure was as follows:
firstly, introducing propylene and a catalyst into a prepolymerization ring pipe, controlling the reaction temperature to be 20-22 ℃ and the reaction pressure to be 3.5-3.6 Mpa, and reacting for 5min; wherein, in the catalyst, the molar ratio of the magnesium compound carrier, titanium tetrachloride, n-hexanol and dicyclopentyldimethoxysilane is 1; the cocatalyst is triethyl aluminum; the amount of cupric chloride to triethylaluminum is, in terms of mole ratios, 1:100, respectively; the mass concentration of the catalyst is 50%.
Introducing propylene into a polymerization reaction ring pipe as a raw material; the dosage of the catalyst is 0.05 percent of the mass of the liquid phase propylene; the reaction temperature is 70-72 ℃, and the reaction pressure is 3.2-3.3 Mpa; introducing hydrogen with volume concentration of 1000ppm to control the reaction; the reaction time in each loop was controlled to 15min.
Introducing the obtained ethylene-propylene random copolymer into a horizontal reactor, continuously introducing ethylene and propylene into the horizontal reactor, and carrying out copolymerization reaction in the presence of a catalyst; wherein, the volume percentage of the propylene is 50 percent, and the volume percentage of the ethylene is 50 percent; the reaction temperature is 72-74 ℃; the reaction pressure is 2.4-2.5 Mpa; the catalyst is the same as the catalyst for liquid-phase bulk polymerization, and the dosage of the catalyst is 0.08 percent of the mass of the second olefin; introducing hydrogen with the volume concentration of 800ppm to control the reaction, and obtaining the propylene polymer of the ethylene-propylene rubber phase.
The performance of the product obtained in this example was examined. The impact strength is measured according to ASTM D256 standard, and the normal temperature impact strength is 66.2KJ/m 2 Low temperature impact strength of 76.0KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 86.8%.
As can be seen from the test data of the above examples, as the content of ethylene in the copolymer increases, the normal temperature impact resistance of the copolymer tends to increase first and then decrease; although the increase of the content of the rubber phase was high, the impact strength at ordinary temperature floated only in a small range of 65 to 69MPa, indicating that the impact resistance at ordinary temperature was not significantly affected by the content of the rubber phase in this range. The low-temperature impact resistance of the product is obviously improved along with the increase of the content of the rubber phase, and can reach 76.0KJ/m 2 The low-temperature impact resistance is better; at the same time, the gloss of the product is not significantly affected as the rubber phase content increases.
Comparative example 1
The formulation and process parameters were the same as in example 2. The only point of change is that instead of using the feed system proposed by the present invention, a suspension of propylene polymerization catalyst and liquid phase propylene is passed directly into the polymerization reactor. The performance of the product obtained in the comparative example was examined. The impact strength is tested according to the ASTM D256 standard, and the normal temperature impact strength is 62KJ/m 2 Low temperature impact strength of 58KJ/m 2 (ii) a The gloss was measured according to GB/T8807 and found to be 91%.
The propylene polymer is polymerized in a ring pipe at the front polymerization stage by homopolymerization of propylene and then gas-phase impact copolymerization of the propylene and ethylene or twice copolymerization of the propylene and the ethylene to respectively generate random copolymerization polypropylene and impact copolymerization polypropylene, and a polymerization process is controlled to obtain a homopolymer or a random copolymer, so that the crystallization of a continuous phase part is reduced, and the glossiness of a product is improved; meanwhile, the random copolymer is used as a continuous phase, so that the compatibility of the continuous phase and a dispersed phase rubber phase can be further improved, and a product with more uniform and refined dispersed phase distribution can be obtained.
In the propylene polymer, the content of ethylene can be designed according to actual requirements, and the content of ethylene in the product can be adjusted in a larger range. The propylene polymer can be controlled by a loop reactor process to obtain a homopolymer or a random copolymer with narrow molecular weight distribution; then the mixture is passed through a horizontal reactor for copolymerization. The retention time of reaction materials in a horizontal reactor is basically consistent, the reaction time of various materials can be controlled to be uniformly maintained, the materials in the horizontal reactor move in a plug flow manner, the materials are fully back-mixed in the radial direction of the reactor, no back-mixing is caused in the axial direction, so that the reaction conditions at each position in the reactor are basically consistent, the molecular weight distribution of the obtained copolymer is narrow, the size of a rubber disperse phase is far smaller than that of a conventional impact-resistant copolymerized polypropylene disperse phase, the size of a rubber phase of a product is small, the dispersibility is good, the distribution is uniform, the product can achieve higher glossiness and rigidity, and the good impact resistance of the product is ensured.
According to the feeding method and the feeding system of the propylene catalyst, the components of the catalyst suspension are controlled to be uniform, the temperature of the catalyst premix liquid before the catalyst suspension liquid is introduced into the polymerization reactor and the pressure of the buffer are controlled to enable the catalyst premix liquid to enter the polymerization reactor after the catalyst premix liquid and the buffer have the same conditions as the polymerization reaction, the influence of the catalyst feeding process on the polymerization reaction is reduced to the minimum degree, the process conditions of the polymerization reaction are controlled, and the preparation of high-performance polypropylene with a designable molecular structure is further guaranteed; as can be seen from the test data of the product properties of comparative example 1 and example 2, this feeding method has a great effect on the improvement of the product properties. Furthermore, the feeding method and the feeding system can carry out stirring control on all links through which the catalyst premixed liquid flows, so that the catalyst premixed liquid is continuously in a state of uniform components, the catalyst can not be settled in the conveying process, and the blockage of a feeding pipeline is avoided, thereby reducing the occurrence probability of production faults and improving the production efficiency.
The present invention is capable of other embodiments, and various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the invention.
Claims (24)
1. A process for feeding a propylene polymerization catalyst, characterized in that it comprises the following steps:
1) Uniformly mixing a propylene polymerization catalyst with liquid-phase propylene to obtain a catalyst premix;
2) And the catalyst premixed liquid is sequentially metered, conveyed and buffered, and then is introduced into a propylene polymerization reactor to participate in propylene polymerization reaction, wherein the components of the catalyst premixed liquid in the metering, conveying and buffering processes are controlled to be uniform, and the temperature of the catalyst premixed liquid in the buffering process is controlled to be the same as the temperature of the catalyst premixed liquid during the propylene polymerization reaction.
2. The feeding method according to claim 1, wherein the metering process comprises stirring and circulating the catalyst premix solution in a metering tank and precisely metering by a diaphragm metering pump.
3. The feeding method according to claim 1, wherein the conveying process employs a pipeline provided with an agitator.
4. The feeding method according to claim 1, wherein the buffering process comprises stirring and circulating the catalyst premix in the buffer tank, and then adjusting the temperature of the catalyst premix and the pressure in the buffer tank.
5. A feeding system of a propylene polymerization catalyst is characterized by comprising a batching tank, a metering tank, a diaphragm metering pump, a conveying pipeline and a buffer tank which are connected in sequence, wherein the buffer tank is connected with a propylene polymerization reaction device; preferably, the stirrer arranged in the conveying pipeline is an inclined paddle type stirrer, the inclined paddle type stirrer is composed of two straight blades, and the two blades are reversely turned by 45-60 degrees.
6. The feeding system according to claim 5, wherein said metering tanks comprise at least two, preferably said metering tanks are connected in parallel.
7. The feeding system of claim 5, wherein a protection valve is disposed between the metering tank and the diaphragm metering pump; preferably, the diaphragm metering pump is a stroke-adjustable diaphragm metering pump.
8. A system according to claim 5, wherein a plurality of agitators are provided within the conveying conduit, preferably with a spacing between adjacent agitators of less than 2m.
9. A preparation method of high impact high gloss polypropylene is characterized by comprising the following steps:
1) Introducing the catalyst premix into a loop reactor by using the feeding method of claims 1-4 to perform a first polymerization with a first olefin monomer;
2) Introducing the catalyst premixed solution into a horizontal reactor by adopting the feeding method of claims 1-4 to perform second polymerization with the product obtained in the step 1) and a second olefin monomer.
10. The production method according to claim 9, wherein the first polymerization comprises a prepolymerization reaction and a liquid-phase bulk polymerization reaction which occur in this order; the reaction temperature of the prepolymerization reaction is 10-40 ℃, the reaction pressure is 2.8-4.1 Mpa, and the reaction time is 3-5 min; the reaction temperature of the liquid-phase bulk polymerization is 55-95 ℃, the polymerization pressure is 2.2-6.5 Mpa, preferably, the reaction temperature is 60-80 ℃, and the reaction pressure is 2.7-4.0 Mpa.
11. The production method according to claim 9, wherein during the prepolymerization, the first olefin monomer is propylene; and in the first polymerization process, the mass concentration of the propylene polymerization catalyst in the catalyst premix is more than or equal to 50%.
12. The production method according to claim 11, wherein the propylene polymerization catalyst comprises a main catalyst and a cocatalyst; wherein, the first and the second end of the pipe are connected with each other,
the main catalyst comprises a magnesium compound carrier, transition metal halide, alcohol with 2-15 carbon atoms and an electron donor, and the molar ratio of the four is 1: (1-40): (0.01-10): (0.01 to 10);
the cocatalyst comprises an organoaluminum compound; the organic aluminum compound comprises alkyl aluminum and/or alkyl aluminoxane serving as a hydrolysis product of the alkyl aluminum;
the ratio of the transition metal halide to the organoaluminum compound is, in terms of mole ratios, 1: (10 to 500).
13. The method as claimed in claim 12, wherein the electron donor is at least one selected from organic phosphorus compounds, organosilanes, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, and electron donors represented by formula I:
in the formula I, R 1 、R 6 Each independently selected from C 1 -C 12 Straight chain alkyl group of (1), C 3 -C 12 Branched alkyl of (2), C 3 -C 15 Cycloalkyl of (C) 3 -C 15 Aryl of (2); r is 2 、R 3 、R 4 、R 5 Each independently selected from H atom, halogen, C 1 -C 12 Straight chain alkyl group of (1), C 3 -C 12 Branched alkyl of C 3 -C 8 Cycloalkyl of, C 6 -C 15 Aryl of (C) 6 -C 15 Aralkyl group of (1); wherein R is 2 And R 3 、R 3 And R 4 、R 4 And R 5 Are independently connected into a ring or not.
14. The preparation method according to claim 10, wherein the first olefin monomer is propylene or an olefin mixture consisting of propylene with a molar percentage of 96% or more and other olefins with a molar percentage of 4% or less, and the other olefins are ethylene and/or butene during the liquid-phase bulk polymerization.
15. The production method according to claim 10, wherein the catalyst is used in an amount of 0.02 to 0.10% by mass based on the mass of the liquid-phase propylene in the first olefin monomer during the liquid-phase bulk polymerization.
16. The method of claim 10, wherein the liquid-phase bulk polymerization reaction employs a polymerization loop comprising a plurality of polymerization loop units connected in parallel, the polymerization loop units comprising a plurality of loop reaction tubes connected in series.
17. A process according to claim 16, wherein said polymerization loop is connected in series with said horizontal reactor.
18. The method of claim 9, wherein the second olefin monomer is at least two of ethylene, propylene and butene; preferably, the mole percentage of the ethylene in the second olefin monomer is less than or equal to 60 percent.
19. The method of claim 9, wherein the second polymerization is carried out at a reaction temperature of 60 to 80 ℃ and a reaction pressure of 2.0 to 3.0Mpa, and preferably at a reaction temperature of 65 to 75 ℃ and a reaction pressure of 2.4 to 2.5Mpa.
20. The production method according to claim 12, wherein the amount of the catalyst in the catalyst pre-mixture in the second polymerization process is 0.02 to 0.10% by mass based on the mass of the second olefin monomer.
21. The method of claim 9, wherein the first polymerization further comprises the step of adding a first auxiliary agent, the first auxiliary agent comprising a molecular weight regulator; the second polymerization further comprises the step of adding a second coagent, the second coagent comprising a molecular weight regulator.
22. The preparation method according to claim 9, wherein a transverse stirring shaft is arranged in the horizontal reactor, and a plurality of stirring paddles are arranged on the transverse stirring shaft.
23. The production method according to claim 9, wherein the horizontal reactor is internally divided into a gasification separation zone and a gas phase polymerization reaction zone along a feeding direction; a baffle plate is arranged between the gasification separation zone and the gas-phase polymerization reaction zone; a gap is arranged between one end of the clapboard and the side wall of the horizontal reactor.
24. A high impact high gloss polypropylene prepared by the process of any one of claims 9 to 23 having an impact strength at room temperature of 60KJ/m or more as measured in accordance with ASTM D256 2 (ii) a The low-temperature impact strength is more than or equal to 50KJ/m 2 (ii) a The glossiness of the paint is more than or equal to 85 percent according to the GB/T8807 standard detection.
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| CN109776702A (en) * | 2017-11-10 | 2019-05-21 | 北京华福工程有限公司 | The preparation method of polypropylene or propylene ethylene copolymers |
| CN111116785A (en) * | 2019-12-27 | 2020-05-08 | 浙江卫星能源有限公司 | Propylene polymerization method and apparatus |
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| EP1799725A1 (en) * | 2004-10-14 | 2007-06-27 | Basell Poliolefine Italia S.r.l. | Process for the gas-phase polymerization of olefins |
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