CN106749789A - The continuous producing method of isotactic polybutylene-1 1 - Google Patents
The continuous producing method of isotactic polybutylene-1 1 Download PDFInfo
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- CN106749789A CN106749789A CN201611029540.8A CN201611029540A CN106749789A CN 106749789 A CN106749789 A CN 106749789A CN 201611029540 A CN201611029540 A CN 201611029540A CN 106749789 A CN106749789 A CN 106749789A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
A kind of continuous producing method of isotactic polybutylene-1 1 is the embodiment of the invention provides, belongs to high molecular polymer field, realize the continuous and stable production of isotactic polybutylene-1 1, it is ensured that product quality is continual and steady, while reducing the consumption of catalyst.Methods described includes：S1, charging, temperature be 10~85 DEG C, pressure be polymerisation that 1 butene monomers are carried out under conditions of 0.2~2.6MPa, reaction time are 1~4 hour, wherein, stability mixed gas are used for regulating system pressure, and the partial pressure of one of which gas is 0.2~1.4MPa in the stability mixed gas；S2, with identical ratio in S1 start charging, partial pressure is that the gas of 0.2~1.4MPa keeps its partial pressure constant in S1, proceed polymerisation, simultaneously reaction mass is released from the polymer reactor, the reaction mass that will be released removes the butene monomers of unreacted 1 by flashing, and obtains isotactic polybutylene-1 1.The present invention can be used for the industrialized production of isotactic polybutylene-1 1.
Description
Technical field
The present invention relates to high molecular polymer field, more particularly to a kind of continuous producing method of isotactic polybutylene-1-1.
Background technology
The industrialized production of PB Polybutene-1 typically uses liquid phase method.Liquid phase method can be divided into substance law and slurry process.Wherein, become silted up
Slurry processes are to carry out the method that slurry polymerization prepares isotactic PB Polybutene-1 as diluent using atent solvent such as alkane, are had
Reaction speed is fast, and the operating condition of influence reaction is easy to the advantages such as Monitoring and Controlling.But it is substantial amounts of due to being added in the method
Atent solvent so that reaction also needs to carry out later separation to atent solvent and unreacted monomer after terminating, and this not only has largely
Energy consumption, can also propose more complicated requirement to polymerization technique and polymer reactor.
The complicated technology and high cost caused in order to avoid atent solvent and monomer separation now to use direct with 1- butylene more
PB Polybutene-1 is prepared as the substance law of reaction monomers and solvent.Compared with slurry process, faster, be polymerized substance law reaction speed work
Skill is simple, and production efficiency is high.But because PB Polybutene-1 after polymerisation can be swelling in monomer, system can be made tacky, so as to make
Into mass transfer, heat transfer difficult.
So far, it is domestic generally to use batch process production technology.And Batch Process is used, product quality between each batch
Fluctuation is larger, it is impossible to meet downstream user demand.Additionally, the consumption for being also generally faced with catalyst is larger, production cost compared with
Problem high.
The content of the invention
The invention provides a kind of continuous producing method of isotactic polybutylene-1-1, the week long of isotactic polybutylene-1-1 is realized
Phase continuously produces, it can be ensured that product quality is continual and steady, downstream user demand is met, while also improving the work of catalyst
Property, reduce the consumption of catalyst.
To reach above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of continuous producing method of isotactic polybutylene-1-1, methods described includes：
S1,1- butene monomers and catalyst, co-catalyst and external electron donor sequentially add polymer reactor, with
Hydrogen as molecular weight regulator, stability mixed gas as the pressure modifiers in polymer reactor, temperature be 10~
In the range of 85 DEG C, pressure be 0.2~2.6MPa, reaction time be 1~4 hour under conditions of carry out polymerisation, its
Described in stability mixed gas the partial pressure of one of which gas be 0.2~1.4MPa；
S2,1- butene monomers, catalyst, co-catalyst, external electron donor and hydrogen are opened according to identical ratio in S1
Begin charging, partial pressure is that the gas of 0.2~1.4MPa keeps its partial pressure constant in the stability mixed gas, proceeds polymerization
Reaction, while releasing reaction mass from the polymer reactor, the reaction mass that will be released removes unreacted 1- by flashing
Butene monomers, obtain isotactic polybutylene-1-1.
Wherein, the unreacted 1- butene monomers for removing will be flashed to be fed in the polymer reactor.
Specifically, the stability mixed gas include nitrogen, inert gas or C1-C4Any two kinds or two in alkane
More than kind.
Preferably, the temperature of polymerisation is 50~85 DEG C.
Preferably, the pressure of polymerisation is 1~2.6MPa.
Preferably, the reaction time of polymerisation is 1.5~3.5 hours.
Specifically, the catalyst is Titanium series catalyst.
The co-catalyst is AlR3、AlR2Cl、AlRCl2, wherein R is 2 to 8 straight chains of carbon atom, side chain or cycloalkanes
Hydrocarbon.
The external electron donor is one or more in silane compound, ethers, lipid.
Preferably, in S1 and/or S2, carry out under agitation.
The invention provides a kind of continuous producing method of isotactic polybutylene-1-1, in the method, with suitable initial strip
Part starts polymerisation, polymerization reaction system is reached the equilibrium state of stabilization so that the material in polymer reactor has good
Can transporting；Then start charging in the same scale, proceed polymerisation, while releasing one from polymer reactor
Quantitative reaction mass, makes the carrying out of system continuous-stable under equilibrium state, so as to by under the equilibrium state, constantly charging is same
When discharging repeat polymerisation, obtain PB Polybutene-1 product, realize the continuous and stable production of PB Polybutene-1, it is ensured that product
Continuous quality stabilization, effectively eliminates the mass deviation between product when batch is produced, and meets the original of downstream product processing enterprise
Material demand.
Also, the method makes that polymerisation is steady in a long-term in the state of the equilibrium to be carried out continuously, by stability mixed gas
In the partial pressure of any one gas be maintained at 0.2~1.4MPa, can so play a part of similar co-catalyst, urged with helping
Agent is cooperated, and improves the activity of catalyst, and then reduces the consumption of catalyst, reduces production cost.
Brief description of the drawings
The schematic flow sheet of the continuous producing method of isotactic polybutylene-1-1 that Fig. 1 is provided for one embodiment of the invention；
It is poly- that the continuous producing method of isotactic polybutylene-1-1 that Fig. 2 diagrammatically illustrates one embodiment of the invention offer is used
Close reactor.
Specific embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described in conjunction with the embodiments specifically below, shown
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made all belongs to
In the scope of protection of the invention.
As shown in figure 1, the embodiment of the invention provides a kind of continuous producing method of isotactic polybutylene-1-1, methods described bag
Include：
S1,1- butene monomers and catalyst, co-catalyst and external electron donor sequentially add polymer reactor, with
Hydrogen as molecular weight regulator, stability mixed gas as the pressure modifiers in polymer reactor, temperature be 10~
85 DEG C, pressure be 0.2~2.6MPa, reaction time be 1~4 hour under conditions of carry out polymerisation, the stability
The partial pressure of one of which gas is 0.2~1.4MPa in mixed gas；
S2, by 1- butene monomers, catalyst, co-catalyst, external electron donor and hydrogen according to identical ratio in S1
Start charging, partial pressure is that the gas of 0.2~1.4MPa keeps its partial pressure constant in the stability mixed gas, proceeds to gather
Reaction is closed, while releasing reaction mass from the polymer reactor, the reaction mass that will be released removes unreacted by flashing
1- butene monomers, obtain isotactic polybutylene-1-1.
A kind of continuous producing method of isotactic polybutylene-1-1 is the embodiment of the invention provides, is opened under suitable primary condition
Dynamic polymerisation, makes polymerization reaction system reach the equilibrium state of stabilization so that the material in polymer reactor have it is good can
Transporting；Then start charging with primary condition identical ratio, proceed polymerisation, while from polymer reactor
A certain amount of reaction mass is released, makes the carrying out of system continuous-stable under equilibrium state, so as to by continuous under the equilibrium state
Charging discharging simultaneously repeats polymerisation, obtains PB Polybutene-1 product, realizes the continuous and stable production of PB Polybutene-1, really
Protect product quality continually and steadily, effectively eliminate the mass deviation between product when batch is produced, meet downstream product processing and look forward to
The raw materials requirement of industry.
Meanwhile, the method makes that the polymerisation of 1- butene monomers is steady in a long-term in the state of the equilibrium to be carried out continuously, will be steady
The partial pressure of any one gas in qualitative mixed gas is maintained at 0.2~1.4MPa, can so play similar co-catalyst
Effect, cooperated with co-catalyst, it is possible to increase the activity of catalyst, and then reduce the consumption of catalyst, reduce
Production cost.
In the method, applicable catalyst can be Titanium series catalyst, i.e. titanium-containing catalyst, such as supported titanium catalyst,
It is preferred that can be titanium system Natta (Natta) catalyst.
Further, the consumption of catalyst can be the mass ratio (g of supported titanium catalyst and 1- butene monomers：Kg) it is
1:10~200, such as 1:10~20,1:20~50,1:100~180.
Reactivity is improved in order to cocatalyst, co-catalyst is added during the course of the reaction.Applicable helping is urged
Agent can be alkyl aluminum, specially AlR3、AlR2Cl、AlRCl2, wherein, alkyl R is 2 to 8 direct-connected, the side chains of carbon atom
Or cycloalkyl, for example can be respectively C2-C8Straight chained alkyl or C3-C8Branched alkyl or C3-C8Cycloalkyl, its
In, C2-C8Straight chained alkyl can be ethyl, C3-C8Branched alkyl can be isobutyl group, C3-C8Cycloalkyl can be ring
Propyl group.
In the alkyl aluminum as co-catalyst, the mol ratio of the Titanium in contained aluminium and the supported titanium catalyst
Can be 150~550, such as 250,300,350,400 etc..
In order to further adjust the isotacticity of the PB Polybutene-1 for preparing during the course of the reaction, during the course of the reaction
It is also added into external electron donor.Applicable external electron donor can be for one or more in silanization thing, ethers, lipid.
Wherein, silane compound for example can be diphenyldimethyl silane, VTES, vinyl front three
TMOS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, diisobutyl dimethoxy
Silane, diisopropyl dimethoxy silane, dicyclopentyl dimethoxyl silane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl
Trimethoxy silane, di-t-butyl dimethoxysilane, tertiary hexyl trimethoxy silane, tert-butyl trimethoxy silane, uncle oneself
Base trimethoxy silane；Ethers for example can be：Dimethyl ether, Anaesthetie Ether, dipropyl ether, isopropyl sec-butyl ether, Zhong Ding
Base ether isoamyl ether, isopropyl amyl ether, sec-butyl isoamyl ether etc..
Further, the mol ratio of the Titanium in the external electron donor and the supported titanium catalyst can for 10~
30.In order that the isotacticity of the PB Polybutene-1 for preparing is higher, the mol ratio of external electron donor/titanium can be located at 10~30
In the range of, such as 15,20,25 etc..
In the method, used as pressure modifiers, regulating system pressure makes polymerisation exist to stability in use mixed gas
Carried out under the pressure condition of 0.2~2.6MPa.Wherein, stability gas refers to safety, polymerisation will not occur in the present invention
Gas, such as nitrogen；Conventional inert gas, such as helium, neon or argon gas；And for example C1-C4Alkane, such as methane, ethane,
Propane, normal butane, iso-butane etc..Therefore, stability mixed gas refer to by any in aforementioned stable gas in the present invention
Two or more admixture of gas for constituting, i.e. stability mixed gas include any two kinds in aforementioned stable gas
Or it is two or more, i.e., including nitrogen,
Inert gas and C1-C4In alkane it is any two or more, preferably include nitrogen, helium, neon, methane,
In ethane, propane, normal butane, iso-butane it is any two or more.
In order to better illustrate this point, table 1 specifically lists the possible composition of stability mixed gas.
Table 1
During the entire process of polymerisation is carried out, ensure that the pressure of system is maintained by being passed through stability mixed gas
In 0.2~2.6MPa, wherein, partial pressure is that the gas of 0.2~1.4MPa is protected in polymerization process in stability mixed gas
Hold its partial pressure constant, that is to say, that the stagnation pressure of system is maintained by the partial pressure for adjusting other gases in stability mixed gas
In 0.2~2.6MPa.
For example, if stability mixed gas include nitrogen and methane, can select for the partial pressure of methane to remain 0.2
~1.4MPa, then the partial pressure of methane always remains as 0.2~1.4MPa in whole polymerization process, by adjusting nitrogen
The stagnation pressure of system is maintained 0.2~2.6MPa by partial pressure.It is of course also possible to select for the partial pressure of nitrogen to remain 0.2~
1.4MPa。
And for example, if stability mixed gas include nitrogen, methane, ethane, can select for the partial pressure of ethane to remain 0.2
~1.4MPa, the partial pressure of ethane always remains as 0.2~1.4MPa in whole polymerization process, by adjust nitrogen and/
Or the stagnation pressure of system is maintained 0.2~2.6MPa by the partial pressure of methane.
0.2~1.4MPa is maintained at by by the partial pressure of one of which gas in stability mixed gas, preferably 0.5~
1.4MPa, more preferably 0.8~1.2MPa, can so play a part of similar co-catalyst, be cooperated with co-catalyst, carry
The activity of high catalyst, and then shorten the reaction time while reducing the consumption of catalyst, reduce production cost.
It should be noted that adding stability mixed gas to maintain system pressure during the entire process of polymerisation is carried out
When, the molecular weight needed for can also being together passed through appropriate hydrogen regulation.
In an alternate embodiment of the present invention, the pressure of polymerisation can be 1~2.6MPa, such as 1MPa, 1.2MPa,
1.8MPa, 2.0MPa, 2.3MPa, 2.6MPa etc..
In another alternative embodiment of the invention, the temperature of polymerisation can be 50~85 DEG C, for example, 50 DEG C, 53 DEG C,
60 DEG C, 62 DEG C, 70 DEG C, 74 DEG C, 80 DEG C, 83 DEG C etc..
In another alternative embodiment of the invention, reaction time can be 1.5~3.5 hours, for example, can be 1.5
Hour, 1.8 hours, 2.0 hours, 2.3 hours, 2.5 hours, 2.8 hours, 3 hours, 3.5 hours etc..
In an embodiment of the present invention, above-mentioned steps S1 and/or step S2 can under agitation be carried out.Preferably, stirring
Mixing down carries out above-mentioned steps S1 and step S2, so that reaction mass is sufficiently mixed.
For example, PB Polybutene-1 continuous producing method provided in an embodiment of the present invention can be as shown in Figure 2 with stirring
Carried out in the polymer reactor of device.Reaction mass is sent to by flash distillation by outlet valve after reaching the equalization point of polymerization reaction system
Tank, while sequentially adding 1- butene monomers, catalyst, co-catalyst, external electron donor and hydrogen by each charging aperture.
In an embodiment of the present invention, the material of releasing removes unreacted 1- butene monomers by flashing, and obtains Gao Quantong
PB Polybutene-1.Specifically, after reaction mass is flashed in flash tank, gaseous phase materials-unreacted monomer is removed, liquid phase thing
Material-isotactic polybutylene-1-1 is sent directly to granulation or next stage vacuumizes out powder, obtains graininess or powdered poly- fourth
Alkene -1.
Further, the gaseous phase materials of flash distillation removal can return to head tank after condensation, is fed in polymer reactor and uses
In reactor feed.
In order to preferably illustrate the continuous producing method of isotactic polybutylene-1-1 provided in an embodiment of the present invention, below will
It is described in detail in conjunction with specific embodiments.
Comparative example
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 50 DEG C by sequence, and system pressure is controlled in 2.3MPa；Open stirring and then add supported titanium to urge according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.5 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 2.3MPa.After reaction mass is flashed in flash tank, gaseous phase materials
Head tank is returned again to after condensation for reactor feed, liquid phase material is routed directly to granulation or next stage vacuumizes out powder,
Realize being carried out continuously for production.
Embodiment one
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 50 DEG C by sequence, is controlled in 1.0MPa system pressure by stability mixed gas, wherein, stability mixed gas
Including nitrogen, methane, the partial pressure of methane is 0.5MPa；Open stirring and then add supported titanium catalyst according to a certain percentage, help
Catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.5 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio starts charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that anti-
Material in device is answered to reach poised state, system pressure is maintained 1.0MPa, and the partial pressure of methane remains 0.5MPa.Reaction mass exists
After being flashed in flash tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to
Granulation or next stage vacuumize out powder, realize being carried out continuously for production.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 65-80%.
Embodiment two
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 10 DEG C by sequence, is controlled in 1.0MPa, wherein stability mixed gas system pressure by stability mixed gas
Including nitrogen, helium, the partial pressure of nitrogen is 0.2MPa；Open stirring and then add supported titanium catalyst according to a certain percentage, help
Catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 4 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 1.0MPa, and the partial pressure of nitrogen remains 0.2MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 50-75%.
Embodiment three
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 55 DEG C by sequence, is controlled in 2.3MPa system pressure by stability mixed gas, and stability mixed gas include
Nitrogen, helium, methane, wherein, the partial pressure of nitrogen is 1.4MPa；Open stirring and then add supported titanium catalysis according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 1.5 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 2.3MPa, and the partial pressure of nitrogen remains 1.4MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 75-95%.
Example IV
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 55 DEG C by sequence, is controlled in 2.3MPa system pressure by stability mixed gas, and stability mixed gas include
Nitrogen, helium, argon gas, wherein, the partial pressure of nitrogen is 1.2MPa；Open stirring and then add supported titanium catalysis according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 1.5 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 2.3MPa, and the partial pressure of nitrogen remains 1.2MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 75-87%.
Embodiment five
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 63 DEG C by sequence, is controlled in 1.9MPa, wherein stability mixed gas system pressure by stability mixed gas
Including methane, ethane, the partial pressure of methane is 0.5MPa；Open stirring and then add supported titanium catalyst according to a certain percentage, help
Catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.0 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 1.9MPa, and the partial pressure of methane remains 0.5MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 67-87%.
Embodiment six
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 63 DEG C by sequence, is controlled in 1.9MPa, wherein stability mixed gas system pressure by stability mixed gas
Including nitrogen, helium, ethane, the partial pressure of ethane is 0.5MPa；Open stirring and then add supported titanium catalysis according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.0 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 1.9MPa, and the partial pressure of ethane remains 0.5MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 60-70%.
Embodiment seven
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 63 DEG C by sequence, is controlled in 1.9MPa, wherein stability mixed gas system pressure by stability mixed gas
Including nitrogen, methane, ethane, the partial pressure of methane is 0.8MPa；Open stirring and then add supported titanium catalysis according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.0 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 1.9MPa, and the partial pressure of methane remains 0.8MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 80-97%.
Embodiment eight
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 85 DEG C by sequence, is controlled in 2.6MPa, wherein stability mixed gas system pressure by stability mixed gas
Including nitrogen, helium, methane, ethane, the partial pressure of nitrogen is 1.0MPa；Open stirring and then add supported titanium according to a certain percentage
Catalyst, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 1 hour.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 2.6MPa, and the partial pressure of nitrogen remains 1.0MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 80-92%.
Embodiment nine
1) certain liquid level stopping charging being reached in 1- butene monomers being added into polymer reactor shown in Fig. 2, intensification journey is controlled
Temperature is heated to 63 DEG C by sequence, is controlled in 1.9MPa, wherein stability mixed gas system pressure by stability mixed gas
Including methane, ethane, propane, the partial pressure of ethane is 0.8MPa；Open stirring and then add supported titanium catalysis according to a certain percentage
Agent, co-catalyst and external electron donor, while adding hydrogen as molecular weight regulator.Timing was by 2.0 hours.
2) by controlling feed rate, by 1- butene monomers, catalyst, co-catalyst, external electron donor according to step
1) identical ratio charging in, while reaction mass is sent to flash tank by the outlet valve for opening reactor bottom, it is ensured that reactor
Interior material reaches poised state, and system pressure is maintained 1.9MPa, and the partial pressure of ethane remains 0.8MPa.Reaction mass is in flash distillation
After being flashed in tank, head tank is returned again to after gaseous phase materials condensation for reactor feed, liquid phase material is routed directly to granulation
Or next stage vacuumizes out powder, being carried out continuously for production is realized.
As a result：Compared with comparative example, one ton of PB Polybutene-1 is often produced, the consumption of catalyst about reduces 60-70%.
As shown in embodiment one to nine, the continuous producing method of isotactic polybutylene-1-1 provided in an embodiment of the present invention is realized
The continuous production of PB Polybutene-1, so as to obtaining the isotactic polybutylene-1-1 of steady quality.Additionally, passing through embodiment one to nine
Contrast with comparative example can show that method provided in an embodiment of the present invention in reaction system by adding stability gaseous mixture
Body regulating system pressure, remains 0.2~1.4MPa, by adjusting it by a kind of partial pressure of the gas in stability mixed gas
The partial pressure of its gas maintains system pressure, improves the activity (averagely can about improve 20 times) of catalyst, is shortening reaction
The consumption of polymerisation catalysts is greatly reduced while time so that under product ton production cost is accordingly obtained significantly
Drop.Although the synthesis material of isotactic polybutylene-1-1 is alreadyd exceed 30 years, fail to realize large-scale industrial production always
With application.This is higher mainly due to the price and production cost of PB Polybutene-1.By Gao Quantong provided in an embodiment of the present invention
PB Polybutene-1 continuous producing method, reduces the production cost of PB Polybutene-1, promotes the industrialized production of PB Polybutene-1 and answers
With.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Change the protection domain still in the invention.
Claims (10)
1. a kind of continuous producing method of isotactic polybutylene-1-1, it is characterised in that methods described includes：
S1,1- butene monomers and catalyst, co-catalyst and external electron donor sequentially add polymer reactor, with hydrogen
As molecular weight regulator, stability mixed gas as the pressure modifiers in polymer reactor, temperature be 10~85 DEG C,
Pressure is 0.2~2.6MPa, reaction time is to carry out polymerisation under conditions of 1~4 hour, wherein, the stability
The partial pressure of one of which gas is 0.2~1.4MPa in mixed gas；
S2, by 1- butene monomers, catalyst, co-catalyst and external electron donor according to identical ratio in S1 start charging,
Partial pressure is that the gas of 0.2~1.4MPa keeps its partial pressure constant in the stability mixed gas, proceeds polymerisation, together
When release reaction mass from the polymer reactor, will release reaction mass by flash remove unreacted 1- butylene lists
Body, obtains isotactic polybutylene-1-1.
2. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that will be removed by flashing
Unreacted 1- butene monomers be fed in the polymer reactor.
3. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the stability mixing
Gas includes nitrogen, inert gas or C1-C4In alkane it is any two or more.
4. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the temperature is 50~
85℃。
5. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the pressure is 1~
2.6MPa。
6. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that when the reaction is stopped
Between be 1.5~3.5 hours.
7. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the catalyst is titanium
Series catalysts.
8. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the co-catalyst is
AlR3、AlR2Cl or AlRCl2, wherein R is 2 to 8 straight chains of carbon atom, side chain or cycloalkyl.
9. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that the external electron donor
It is one or more in silane compound, ethers, lipid.
10. the continuous producing method of isotactic polybutylene-1-1 according to claim 1, it is characterised in that in S1 and/or S2
In, carry out under agitation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759684A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method and device of polybutene-1 |
| CN114478875A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for producing polyethylene by adopting intermittent liquid phase method and polyethylene |
| CN116253818A (en) * | 2021-12-09 | 2023-06-13 | 中国石油化工股份有限公司 | Process for preparing poly-1-butene |
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| US4503203A (en) * | 1983-12-20 | 1985-03-05 | Union Carbide Corporation | Preparation of granular stereoregular butene-1 polymers in a fluidized bed |
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| US4503203A (en) * | 1983-12-20 | 1985-03-05 | Union Carbide Corporation | Preparation of granular stereoregular butene-1 polymers in a fluidized bed |
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| 杜强国 等: "《塑料工业手册 苯乙烯系树脂》", 31 October 2004, 化学工业出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112759684A (en) * | 2019-11-01 | 2021-05-07 | 中国石油化工股份有限公司 | Preparation method and device of polybutene-1 |
| CN112759684B (en) * | 2019-11-01 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation method and device of polybutene-1 |
| CN114478875A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Method for producing polyethylene by adopting intermittent liquid phase method and polyethylene |
| CN116253818A (en) * | 2021-12-09 | 2023-06-13 | 中国石油化工股份有限公司 | Process for preparing poly-1-butene |
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