CN110894249A - Homogeneous polymerization method and device for butene-1 - Google Patents
Homogeneous polymerization method and device for butene-1 Download PDFInfo
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Abstract
The invention belongs to the field of polyolefin materials, and discloses a homogeneous polymerization method and a homogeneous polymerization device for butene-1, wherein the homogeneous polymerization method comprises the following steps: 1) carrying out homogeneous continuous polymerization or batch polymerization in a liquid butene-1 system in the presence of a Ziegler-Natta type catalyst system; 2) the homogeneous polymer solution is continuously or intermittently discharged out of the reaction vessel; 3) adding a polymer heat stabilizer to the homogeneous polymer solution, and then heating the polymer solution to not less than 150 ℃; 4) and (3) feeding the heated homogeneous polymer solution into flash separation equipment to remove unreacted monomers to obtain the butene-1 polymer. The homogeneous polymerization method adopts a temperature control method to realize catalyst deactivation, does not need to add any deactivator, can play a role in catalyst deactivation, and can provide heat for a flash evaporation process.
Description
Technical Field
The invention belongs to the field of polyolefin materials, and particularly relates to a homogeneous polymerization method and a homogeneous polymerization device for butene-1.
Background
Butene-1 (co) polymers are well known polymorphic polymers in the art and are well suited for use in the fields of pipe, film, and blend modification.
At present, the butene-1 (co) polymerization process is mainly obtained in the presence of a catalyst, and is generally obtained by a homogeneous polymerization process, a slurry polymerization process, a solution polymerization process or a gas phase polymerization process. The catalyst used is mainly a Ziegler-Natta catalyst, but may also be a metallocene catalyst.
In the homogeneous polymerization process, the polymerization process is carried out in liquid butene-1, butene-1 (co) polymer generated in the reaction process is completely dissolved in butene-1 with or without inert hydrocarbon solvent to form homogeneous solution, and the polymer solution discharged from the polymerization reactor enters a polymer-unreacted monomer (butene-1) separation system after inactivation treatment. Patent document CN03800736.3 discloses no details about the process of deactivating or deactivating the active component after the reaction process and the process of separating the polymer-unreacted monomer (butene-1) in detail, wherein the homogeneous bulk polymerization is carried out at 70 to 75 ℃ using a Ziegler-Natta catalyst, and the reaction process is carried out in two stages (the hydrogen addition amount in the two stages may be the same or different), the catalyst activity is as high as 50kgPB-1/(gCat 2hr), and the isotactic index of the polymer is as high as 99%. Patent document CN03814198.1 discloses a liquid phase method for homo-or copolymerization of butene-1, in the presence of a catalyst system based on transition metal compounds, liquid butene-1 continuously reacts in one or more reactors connected in series, the polymerization temperature is 65 to 85 ℃, and the polymer generated by the reaction is completely dissolved in butene-1; the polymer solution flowing out of the reactor enters a stirred tank, and organic deactivator (such as propylene glycol, dipropylene glycol, glycerol and the like) is added into the stirred tank, and the deactivator and the butene-1 are easily separated by rectification when being combined; the deactivated polymer solution is passed into one or more volatilization chambers operating at reduced pressure to separate the polymer from the unreacted monomers (butene-1). Patent document CN201210422461.9 discloses a method for preparing high isotactic polybutene-1 by homogeneous polymerization, wherein the reaction temperature is 40-100 ℃, the activity of the catalyst can reach 20-30 kgPB-1/(gCat · hr), the isotacticity of the obtained polymer can reach 97-99%, after the reaction is finished, the polymer solution is discharged to a closed container filled with hot water, and steam is introduced from the bottom of the container to vaporize the unreacted monomer (butene-1) to realize the separation of the polymer and butene-1, and simultaneously the active catalyst component is inactivated by water, the separation method of the polymer-unreacted monomer is only suitable for small test procedures, and for medium test and even industrial scale devices, large blocks are likely to be formed when the polymer solution enters a water tank filled with hot water, and the subsequent material conveying process is very difficult.
Compared with a homogeneous polymerization process, the slurry polymerization process can obtain polymer particles in the polymerization process, and the subsequent separation process of polymer and unreacted monomer is greatly simplified, but the defects are that the activity of the catalyst is low (less than 10kgPB-1/gCat), so that the ash content of the polymer is high, the isotacticity of the polymer is low, and the results are all harmful to the performance of the polymer.
Patent document CN200610170962.7 discloses a method for preparing polybutene-1 by liquid phase bulk polymerization, in which a catalyst is prepolymerized at a low temperature and then added into a reactor, the reaction temperature is 30-70 ℃, ethanol is added after the reaction is finished to deactivate active components, the polymer obtained by the method is in a particle state, and the isotacticity is 94-99%, but the patent document does not disclose activity data of the catalyst and a subsequent separation method of polymer-unreacted monomer (butene-1). Patent documents CN2007100113587.X and CN201010198121.3 disclose a preparation method of high isotactic polybutene-1, which adopts a bulk precipitation synthesis process, the reaction temperature is 0-70 ℃, the obtained polymer is powdery particles, the isotacticity of the polymer is 80-98%, but the catalyst activity is less than 5kgPB-1/(gCat 3 hr). Patent document CN201210417622.5 discloses a method for preparing high isotactic polybutene-1, wherein a catalyst is subjected to low-temperature slurry prepolymerization and then added into a reactor, the reaction temperature is 30-60 ℃, and the obtained polymer has good particle morphology, the isotacticity is 96-98%, but the catalyst activity is less than 3.5kgPB-1/(gCat hr).
The gas phase butene-1 polymerization process has the advantages of obtaining granular polymer without the problems of dissolution or swelling in gaseous butene-1, but the polymerization activity of the catalyst is very low due to the low concentration of the monomer in the reaction process. Monte corporation, in patent document CN99800235.6, discloses a method for gas phase polymerization of butene-1 using a Z-N catalyst system, in which polymerization is carried out in a first gas phase reactor (60 ℃ C.) for 11hr to give a yield of about 1.4kgPB-1/gCat, and then in a second gas phase reactor at 70 ℃ C. for 9hr to give a yield of about 5.0 kgPB-1/gCat.
In order to reduce the catalyst residue (ash) in butene-1 polymerization products and simultaneously to improve the isotacticity of the polymer, homogeneous phase is the most suitable polymerization method. For the homogeneous polymerization process, after the polymerization process is completed, the resulting polybutene-1 and the unreacted monomers must be separated, usually by flash separation. The residual active substance in the polymer solution must be deactivated before entering the flash separation, otherwise the reaction will continue during the separation and the polymer of different composition formed at this stage will affect the properties of the final product. It is known in the art to add a deactivating compound after the polymerization process has ended. Water, oxygen, carbon dioxide, carbon monoxide, alcohols are well known as highly effective activators of Ziegler-Natta catalysts. The addition of such a deactivator, while effective in terminating the continuation of the polymerization reaction, also poses a problem in that the deactivator must be separated from the unreacted monomer at the stage of recovering the unreacted monomer, which obviously increases the complexity of the process flow and the operating cost of the process for recovering the unreacted monomer.
In addition, the polymer solution is deactivated and then enters a flash separation stage, in which heat is supplied to the polymer solution to vaporize the unreacted monomers and separate them from the polymer. In the flash separation process, the higher the temperature of the polymer solution, the more favorable the separation of the unreacted monomers, and the lower the viscosity of the polymer solution, which is favorable for the transportation process. However, the present inventors have found that it is obviously necessary to avoid the result that polybutene-1 obtained by the polymerization process is degraded rapidly by heating at a relatively high temperature (e.g., higher than 250 ℃).
Disclosure of Invention
In view of the above circumstances, an object of the present invention is to provide a method and an apparatus for homogeneously polymerizing butene-1. The homogeneous polymerization method adopts a post-treatment method for efficiently inactivating residual active catalyst components, does not need to add any new equipment, does not introduce any activator, and can avoid introducing new impurities into the butene-1 recovered in the flash evaporation process, thereby effectively reducing the operation cost.
The first aspect of the present invention provides a homogeneous polymerization process of butene-1, comprising the steps of:
1) carrying out homogeneous continuous polymerization or batch polymerization on the liquid butene-1 system in the presence of a Ziegler-Natta catalyst system;
2) continuously or intermittently discharging the homogeneous polymer solution obtained in the step 1) out of the reaction vessel;
3) adding a polymer heat stabilizer into the homogeneous polymer solution discharged in the step 2), uniformly mixing the polymer heat stabilizer and the homogeneous polymer solution, and heating the obtained mixed solution to be not less than 150 ℃;
4) and 3) feeding the heated mixed solution in the step 3) into flash separation equipment, and removing unreacted monomers to obtain the butene-1 polymer.
The second aspect of the present invention provides a homogeneous polymerization apparatus for butene-1, comprising, in terms of the direction of flow of the materials: optional pre-complexing reactor, one or more reactors connected in series, material mixing equipment and one or more flash separation equipment, wherein a booster pump and a heater are arranged in front of each flash separation equipment.
The homogeneous polymerization method of the invention realizes the deactivation of the catalyst by adopting a temperature control method, and the method does not need to add any deactivator at the end stage of the polymerization process, thereby not only playing the role of catalyst deactivation, but also providing heat for the flash evaporation process. In addition, the addition of the polymer heat stabilizer effectively avoids the degradation of the polybutene-1 at higher temperature, and has no adverse effect on the performance of the polymer.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 shows a process flow diagram of a preferred embodiment of the homogeneous polymerization process of the present invention.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, there is provided a homogeneous polymerization process of butene-1 comprising the steps of:
1) carrying out homogeneous continuous polymerization or batch polymerization on the liquid butene-1 system in the presence of a Ziegler-Natta catalyst system;
2) continuously or intermittently discharging the homogeneous polymer solution obtained in the step 1) out of the reaction vessel;
3) adding a polymer heat stabilizer into the homogeneous polymer solution discharged in the step 2), uniformly mixing the polymer heat stabilizer and the homogeneous polymer solution, and heating the obtained mixed solution to be not less than 150 ℃;
4) and 3) feeding the heated mixed solution in the step 3) into flash separation equipment, and removing unreacted monomers to obtain the butene-1 polymer.
Preferably, in step 1), the liquid butene-1 system is subjected to a homogeneous continuous polymerization.
According to the invention, in step 1), the butene-1 polymer formed during the polymerization is completely dissolved in butene-1 to form a homogeneous polymer solution.
In the present invention, the Ziegler-Natta type catalyst system comprises the following components conventionally used in the art: a Ziegler-Natta catalyst, an organoaluminum compound, and optionally an external electron donor.
The components of the above-mentioned Ziegler-Natta type catalyst system may be selected according to the invention using conventional choices in the art.
Preferably, the Ziegler-Natta catalyst is TiCl supported on magnesium chloride4. Generally, the Ziegler-Natta catalyst also contains a certain amount of internal electron donor to improve the stereoregularity of its product. The internal electron donor is esters, ethers, amines and the like known in the art, and for example, the internal electron donor may be at least one selected from 1, 3-diketones, 1, 3-diethers, alkoxyketones, succinates, 1, 3-diol esters, 1, 4-diol esters, 1, 5-diol esters, hydroxy acid esters and higher phthalic acid esters.
In the present invention, the organoaluminum compound may be selected from an alkylaluminum compound, preferably trialkylaluminum, and more preferably at least one of triethylaluminum, triisobutylaluminum and tri-n-butylaluminum.
According to the invention, the external electron donor can be an ether compound, an ester compound or a silane compound, preferably a silane compound, more preferably of the general formula R1 mR2 nSi(OR3)4-m-nWherein m and n are integers between 0 and 3, and m + n is less than or equal to 4, R1、R2And R3Each independently selected from halogen, hydrogen atom or C1-C18Alkyl or haloalkyl, C3-C18Cycloalkyl radical, C6-C18And (4) an aryl group.
The external electron donor can be selected from one or more of the following compounds: tetramethoxysilane, tetraethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, methylisopropyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -methyldimethoxysilane.
Preferably, the homogeneous polymerization process comprises: the components of the Ziegler-Natta type catalyst system are pre-complexed at a temperature of-5 to 40 ℃, preferably 0-15 ℃.
In the present invention, the pre-complexing is carried out either on-line or off-line. The pre-complexed catalyst system is added continuously or intermittently to the polymerization vessel.
In the invention, the Ziegler-Natta catalyst system can achieve the polymerization yield of 10-30 kg PB-1/(gCat hr), and the residual catalyst amount in the obtained butene-1 polymer is less than 100ppm, so that the influence of the low catalyst residual amount on the polymer performance is negligible.
The homogeneous polymerization process of the present invention is suitable for the homopolymerization or copolymerization of butene-1, i.e., the liquid butene-1 system may or may not contain butene-1 comonomer. Preferably, the liquid butene-1 system contains 0 to 10 wt% of comonomer, based on the weight of butene-1. When a comonomer is present, it is preferred that the comonomer content is from 0.5 to 5 wt%.
In the present invention, the comonomer may be selected from comonomers conventionally used in the art, for example, the comonomer may be selected from ethylene, propylene, pentene-1, hexene-1 or octene-1.
According to the invention, step 1) is carried out in the presence or absence of inert hydrocarbonsUnder the condition of solvent, the inert hydrocarbon solvent can be C1-C4An alkane of (a); preferably, step 1) is carried out in the absence of an inert hydrocarbon solvent.
In the present invention, step 1) is carried out in one or more reaction vessels connected in series. Preferably, the reaction vessel is a stirred tank reactor or a loop reactor with an axial flow pump.
The comonomer concentration in each reaction vessel can be controlled to be the same or different according to the product requirements, thereby producing butene-1 polymers with different compositions. In addition, the polymerization process uses hydrogen as a molecular weight regulator, and the hydrogen concentration of each reaction vessel can be controlled to be the same or different according to the product requirements, thereby producing polymers with narrow or wide molecular weight distribution.
According to the invention, in step 1), the polymerization conditions comprise: the reaction temperature is 50-100 ℃, and the reaction pressure is 1.0-10.0 MPaG. Preferably, the reaction temperature is 60 to 80 ℃ and the reaction pressure is 2.0 to 4.0 MPaG.
According to the invention, the content of butene-1 polymer in the homogeneous polymer solution discharged in step 3) is from 1 to 50% by weight, preferably from 15 to 30% by weight.
In the present invention, the polymer heat stabilizer used may be a solid heat stabilizer or a liquid heat stabilizer, preferably a liquid heat stabilizer. Specifically, the polymer heat stabilizer can be selected from at least one of hindered phenol stabilizers, hindered amine stabilizers, phosphite stabilizers and sulfur-containing compound stabilizers; hindered phenol stabilizers and/or phosphite stabilizers are preferred.
The heat stabilizer added in the step 3) can prevent the polybutene-1 obtained in the polymerization process from being degraded by heating in the subsequent flash separation process. The device for mixing the homogeneous polymer solution with the polymeric heat stabilizer is one or more mixing devices connected in series, and the mixing devices can be tank type devices with stirring or static mixers.
In the present invention, after adding the polymer heat stabilizer to the homogeneous polymer solution, the mixed solution of the polymer and the heat stabilizer is fed to a heating system by a pump suitable for a high viscosity fluid, such as a gear pump or a screw pump, and heated to not less than 150 ℃ at this stage, one reason for heating the polymer solution is that heat is supplied by a downstream flash separation process, and another reason is that the inventors have found through experiments that the polymerization activity of the Ziegler-Natta catalyst is zero or close to zero at a temperature of not less than 150 ℃, so that the catalyst deactivation effect is achieved. In addition, on the basis of realizing the catalyst deactivation, in order to prevent the degradation of the polymer and ensure the quality of the polymer, the heating temperature of the mixed solution is preferably 150-250 ℃, and more preferably 150-200 ℃.
The method for killing the catalyst does not need to add any new equipment, does not introduce any activator, and does not introduce new impurities into the butene-1 recovered in the flash evaporation process. Obviously, the catalyst deactivation process of the present invention effectively reduces operating costs.
According to the invention, the deactivated polymer solution is fed to a flash separation system. The flash separation apparatus comprises one or more flash separation devices in series, which may be a flash evaporator or a screw devolatilizer.
In the invention, the operation temperature of the flash separation equipment is 100-250 ℃, and preferably 120-200 ℃.
Preferably, the flash separation apparatus comprises a plurality of flash separation devices connected in series, the first stage of the flash separation apparatus is operated at a pressure of from 0 to 4.0MPaG, preferably from 0.5 to 3.0MPaG, and the remaining stages of the flash separation apparatus are operated under vacuum, preferably at an operating pressure of not more than 20 KPaA.
The flash separation equipment adopts the process parameters to remove the residual unreacted monomers in the polymer as much as possible; a heating device is arranged on the feed line of each flash separation device to provide the heat required for the flash process, and a gear pump or screw pump suitable for high-viscosity fluid is arranged at the bottom of each flash separation device to send the polymer solution to the downstream device.
The butene-1 flash gas obtained in the flash separation process is sent to a monomer recovery unit, and because no new substance is introduced into the catalyst deactivation method adopted by the invention, the removal of the deactivator is not required to be considered in the monomer recovery process. The butene-1 polymer obtained by the present invention can be pelletized by using an extruder, and additives used in the art, such as an antioxidant and a light stabilizer, are usually added during the pelletization.
The remaining parameters of the present invention, which are not defined, are within the ordinary skill of the art.
For the purpose of enhancing the understanding of the homogeneous polymerization process of the present invention, a preferred embodiment (a process flow diagram of which is shown in FIG. 1) is provided for illustration, but the scope of the present invention is not limited by this embodiment.
A preferred embodiment of the invention is described according to fig. 1: a Ziegler-Natta catalyst 1, an alkyl aluminium 2 and an external electron donor 3 are added into a pre-complexation reactor R1, and the temperature and the residence time of the pre-complexation reactor are respectively 10 ℃ and 10 min. The product of the pre-complexation reactor was fed directly to the first reactor R2, while butene-14, hydrogen 5 and comonomer ethylene 6 were also fed to the first reactor, which was operated full of kettle at a temperature, pressure and residence time of 65 ℃, 2.0MPaG and 2hr, respectively. The product of the first reactor exits at the top and enters a second reactor R3, along with butene-18, hydrogen 9 and comonomer ethylene 10, which is also a full tank operation, at a temperature, pressure and residence time of 65 ℃, 2.0mpa g and 1.5hr, respectively. Wherein both reactors are equipped with stirrers.
The hydrogen concentration and comonomer concentration of the two reactors are adjusted as required, and may be the same or different, thus enabling the production of polybutene-1 homopolymers or random copolymers of different composition and different molecular weight distribution. Typically, the first reactor has a lower hydrogen concentration or comonomer concentration than the second reactor.
The polymer solution discharged from the top of the second reactor is a high-viscosity solution 11, and enters a static mixer X4, and a heat stabilizer 12 is added into the mixture X4, and the polymer solution and the heat stabilizer are uniformly mixed in X4. The polymer solution from X4 was pressurized by gear pump P5 and sent to first flash vessel front heater E6, heated to 150 ℃ and sent to first flash vessel D7. In the first flash vessel, most of the unreacted monomer is vaporized and flows out of the top of D7 and into the monomer recovery unit. The high-concentration polymer solution at the bottom of the D7 is pressurized by a gear pump P8 and then sent to a front heater E9 of a second flash evaporator, and the high-concentration polymer solution is heated to 200 ℃ and then enters a second flash evaporator D10. In D10, the residual unreacted monomers were removed as far as possible, and polybutene-1 was fed in the form of molten polybutene-1 in the bottom to the pelletizing system by means of a gear pump P11 at the bottom of D10.
According to a second aspect of the present invention, there is provided a homogeneous polymerization apparatus for butene-1, comprising, in terms of the direction of flow of the materials: optional pre-complexing reactor, one or more reactors connected in series, material mixing equipment and one or more flash separation equipment, wherein a booster pump and a heater are arranged in front of each flash separation equipment.
Preferably, the homogeneous polymerization apparatus comprises two reactors and two flash separation devices.
Preferably, the material mixing equipment is a static mixer, the flash evaporation separation equipment is a flash evaporator, and the booster pump is a gear pump or a screw pump.
Preferred embodiments of the present invention will be described in more detail below.
The present invention is described in detail below with reference to specific examples, which are intended to be illustrative only and not limiting.
The data relating to the polymers in the experimental, examples and comparative examples were obtained according to the following test methods:
① isotactic index the isotactic index of polybutene-1 is measured by placing a certain amount of sample in a vacuum oven at 70 deg.C, vacuum-drying to extract residual monomers and water in the sample, vacuum-drying to constant weight, accurately weighing 1-2 g of the sample in a filter paper cylinder, sealing the upper opening with a paper clip, placing in an extractor, extracting with boiling ether for 24h, taking out, drying in the vacuum oven to constant weight, and determining the content of non-extractables as the isotactic index of polybutene-1.
② melt Mass Flow Rate (MFR) the melt mass flow Rate tester (CEAST 7026) was used to test the melt Mass Flow Rate (MFR) according to ASTM D1238 at a temperature of 190 ℃ with a weight of 2.16 kg.
It was first verified by experimental examples that the deactivation temperature of the Ziegler-Natta catalyst in catalyzing the homogeneous polymerization of butene-1 is not lower than 150 ℃.
Experimental examples 1 to 4
A Ziegler-Natta catalyst was prepared as described in example 1 of patent document CN85100997, using triethylaluminium as cocatalyst and diisopropyldimethoxysilane as external donor.
0.06g/h of catalyst, 0.4g/h of triethylaluminum and 0.05g/h of diisopropyldimethoxysilane were continuously fed into the pre-complexation reactor. The pre-complexed product continuously flowed out of its bottom and into the first reactor (20L pressure-resistant stirred tank), while 11.2kg/h of liquid butene-1 and 0.25g/h of hydrogen were also fed into the first reactor. The product of the first reactor was continuously discharged and fed to a second reactor (20L pressure-resistant stirred tank), while 6.3kg/h of liquid butene-1 and 5.3g/h of hydrogen were added to the second reactor, the polymerization temperature and pressure were controlled at 65 ℃ and 3.0MPag, and the average residence time was 1 h. The operating conditions for each reactor in the experimental examples are shown in Table 1:
TABLE 1
Experimental examples 5 to 8
The Ziegler-Natta catalyst prepared by the method described in example 1 of patent document CN93102795 was used, and the alkylaluminum, the precomplexation and polymerization process conditions used in examples 5-8 were the same as those in examples 1-4, i.e., example 5 was the same as example 1, example 6 was the same as example 2, example 7 was the same as example 3, and example 8 was the same as example 4.
Experimental examples 9 to 12
Examples 9 to 12 used the Ziegler-Natta catalyst prepared by the method described in example 3 of patent document CN200810117894, and examples 9 to 12 used alkylaluminum, pre-complexing, polymerization process conditions, and the like, which correspond to examples 1 to 4, respectively, that is, example 9 was the same as example 1, example 10 was the same as example 2, example 11 was the same as example 3, and example 12 was the same as example 4.
The total activity of the catalysts of examples 1-12, the melt mass flow rate of the polymer obtained in each reactor and the isotactic index are shown in Table 2.
TABLE 2
As can be seen from the data in Table 2, the three catalysts all have higher catalytic activity at a polymerization temperature of 65 ℃ and the isotactic index of the obtained polymer is also very high. However, when the polymerization temperature is increased to 140 ℃, the activity of the catalyst is greatly reduced, only by a few hundred times (although its isotactic index is still high). When the polymerization temperature reached 150 ℃ or higher, the activity of the catalyst was close to 0 (no polymer was obtained in some of the experimental examples), indicating that the Ziegler-Natta catalyst was deactivated by increasing its temperature to not lower than 150 ℃.
The results of the above experimental examples are applied to the examples of the present invention, and examples 1 to 3 of the present invention are intended to illustrate the homogeneous polymerization process of butene-1 of the present invention.
Example 1
The catalyst, aluminum alkyl, pre-complexing and polymerization process conditions used in this example were the same as in experimental example 1. The polymer solution from the second reactor was continuously discharged and fed to a static mixer to which 3.0g/h of a thermal stabilizer (octyldiphenylamine, liquid) was added. And (3) boosting the pressure of the material discharged from the static mixer to 5.0MPag by a gear pump, then sending the material to a front heater of the first flash evaporator, and heating the material to 150 ℃ and then entering the first flash evaporator. The temperature of the first flash vessel was 150 ℃, the pressure was 0.4MPaG, the residence time was 30min, in the first flash vessel, about 85% of the unreacted monomer was vaporized and flowed out from its top into the monomer recovery unit, while the high concentration polymer solution at its bottom was pumped by a gear pump to the front heater of the second flash vessel, after warming to 200 ℃, into the second flash vessel. The temperature of the second flash evaporator is 200 ℃, the pressure is 20kPaA, the residence time is 15min, the second flash evaporator is operated in vacuum to remove residual unreacted monomers as far as possible, and polymer melt at the bottom of the second flash evaporator is pumped to a granulation system by a gear pump.
Example 2
The aluminum alkyl, pre-complexing and polymerization process conditions, and devolatilization process conditions used in this example were the same as in example 1. The difference from the embodiment 1 is that: a Ziegler-Natta catalyst prepared using the method described in patent document CN93102795, example 1.
Example 3
The aluminum alkyl, pre-complexing and polymerization process conditions, and devolatilization process conditions used in this example were the same as in example 1. The difference from the embodiment 1 is that: a Ziegler-Natta catalyst prepared using the method described in example 1 of patent document CN 200810117894.
Comparative example 1
The catalyst, aluminum alkyl, pre-complexing and polymerization process conditions, devolatilization process conditions, etc. used in this comparative example were the same as in example 1. The difference from the embodiment 1 is that: no heat stabilizer was added to the static mixer.
Comparative example 2
The catalyst, aluminum alkyl, pre-complexing and polymerization process conditions, devolatilization process conditions, etc. used in this comparative example were the same as in example 2. The difference from the embodiment 2 is that: no heat stabilizer was added to the static mixer.
Comparative example 3
The catalyst, aluminum alkyl, pre-complexing and polymerization process conditions, devolatilization process conditions, etc. used in this comparative example were the same as in example 3. The difference from the embodiment 3 is that: no heat stabilizer was added to the static mixer.
The polymers of the first reactor, the second reactor, the first flasher and the second flasher in the examples and comparative examples were sampled to measure the melt mass flow rate and isotacticity, and the results of the measurements are shown in Table 3.
TABLE 3
As can be seen from the data in Table 3, in examples 1-3, the polymer solution was added with a heat stabilizer before being added to the flash evaporator, so that the deactivation of the catalyst was achieved and the stability of the polymer was ensured; in comparative examples 1-3, no thermal stabilizer was added to the polymer solution prior to entering the flash evaporator, and the melt mass flow rate of the polymer increased significantly at the higher temperature of the second flash, indicating that the polymer had degraded.
The method of the invention does not need to add any activator at the end stage of the polymerization process, can play a role of activating and provide heat for the flash evaporation process, and in addition, unreacted monomer steam generated in the flash evaporation process is not mixed with any activator component, the recovery process is simpler, and the energy consumption is lower.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (13)
1. A homogeneous polymerization process of butene-1, characterized in that it comprises the following steps:
1) carrying out homogeneous continuous polymerization or batch polymerization on the liquid butene-1 system in the presence of a Ziegler-Natta catalyst system;
2) continuously or intermittently discharging the homogeneous polymer solution obtained in the step 1) out of the reaction vessel;
3) adding a polymer heat stabilizer into the homogeneous polymer solution discharged in the step 2), uniformly mixing the polymer heat stabilizer and the homogeneous polymer solution, and heating the obtained mixed solution to be not less than 150 ℃;
4) and 3) feeding the heated mixed solution in the step 3) into flash separation equipment, and removing unreacted monomers to obtain the butene-1 polymer.
2. A homogeneous polymerization process of butene-1 according to claim 1, comprising: the components of the Ziegler-Natta type catalyst system are pre-complexed at a temperature of-5 to 40 ℃, preferably 0-15 ℃.
3. A homogeneous polymerization process of butene-1 according to claim 1 wherein the liquid butene-1 system comprises 0 to 10 wt% of a comonomer selected from ethylene, propylene, pentene-1, hexene-1 or octene-1, based on the weight of butene-1.
4. Process for the homogeneous polymerization of butene-1 according to claim 1, wherein step 1) is carried out in the presence or absence of an inert hydrocarbon solvent C1-C4An alkane of (a); preferably, step 1) is carried out in the absence of an inert hydrocarbon solvent.
5. A homogeneous polymerization process of butene-1 according to claim 1 wherein step 1) is carried out in one or more reaction vessels connected in series; the reaction vessel is a stirred tank reactor or a loop reactor with an axial-flow pump.
6. Process for the homogeneous polymerization of butene-1 according to claim 1 or 5, wherein in step 1) the polymerization conditions comprise: the reaction temperature is 50-100 ℃, and the reaction pressure is 1.0-10.0 MPaG; preferably, the reaction temperature is 60 to 80 ℃ and the reaction pressure is 2.0 to 4.0 MPaG.
7. The homogeneous polymerization process of butene-1 according to claim 1, wherein the butene-1 polymer content in the homogeneous polymer solution discharged in step 3) is 15 to 30% by weight.
8. The homogeneous polymerization process of butene-1 according to claim 1, wherein the polymeric heat stabilizer is at least one selected from the group consisting of hindered phenolic stabilizers, hindered amine stabilizers, phosphite stabilizers and sulfur-containing compound stabilizers; hindered phenol stabilizers and/or phosphite stabilizers are preferred.
9. Process for the homogeneous polymerization of butene-1 according to claim 1 or 8 wherein said polymeric thermal stabilizer is added to the homogeneous polymer solution by means of one or more mixing devices in series; the mixing device is a stirred tank or a static mixer.
10. The homogeneous polymerization process of butene-1 according to claim 1, wherein in step 3) the obtained mixed solution is heated to 150-.
11. A homogeneous polymerization process of butene-1 according to claim 1 wherein said flash separation apparatus comprises one or more flash separation devices in series, said flash separation devices being flash evaporators or screw devolatilizers; the operating temperature of the flash separation device is 100-250 ℃, and preferably 120-200 ℃.
12. A homogeneous polymerization process of butene-1 according to claim 11 wherein said flash separation means comprise a plurality of flash separation units connected in series, the first stage of the flash separation means being operated at a pressure comprised between 0 and 4.0MPaG, preferably between 0.5 and 3.0MPaG, the remaining stages of the flash separation means being operated under vacuum, preferably at an operating pressure not higher than 20 kpa.
13. A homogeneous polymerization apparatus for butene-1, comprising, in terms of the direction of flow of the materials: optional pre-complexing reactor, one or more reactors connected in series, material mixing equipment and one or more flash separation equipment, wherein a booster pump and a heater are arranged in front of each flash separation equipment;
preferably, the homogeneous polymerization apparatus comprises two reactors and two flash separation devices; the material mixing equipment is a static mixer, the flash evaporation separation equipment is a flash evaporator, and the booster pump is a gear pump or a screw pump.
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