CN114989334A - In-situ nucleation isotactic polybutene-1 and its prepn - Google Patents

In-situ nucleation isotactic polybutene-1 and its prepn Download PDF

Info

Publication number
CN114989334A
CN114989334A CN202210606541.3A CN202210606541A CN114989334A CN 114989334 A CN114989334 A CN 114989334A CN 202210606541 A CN202210606541 A CN 202210606541A CN 114989334 A CN114989334 A CN 114989334A
Authority
CN
China
Prior art keywords
cocatalyst
nucleating agent
electron donor
main catalyst
external electron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210606541.3A
Other languages
Chinese (zh)
Inventor
郑伟平
丁其维
孔玉普
李海艳
贾福祥
袁文博
赵永臣
王耀伟
栾波
马韵升
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chambroad Chemical Industry Research Institute Co Ltd
Shandong Chambroad Petrochemicals Co Ltd
Original Assignee
Chambroad Chemical Industry Research Institute Co Ltd
Shandong Chambroad Petrochemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chambroad Chemical Industry Research Institute Co Ltd, Shandong Chambroad Petrochemicals Co Ltd filed Critical Chambroad Chemical Industry Research Institute Co Ltd
Priority to CN202210606541.3A priority Critical patent/CN114989334A/en
Publication of CN114989334A publication Critical patent/CN114989334A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids
    • 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

Abstract

The application provides an in-situ nucleation isotactic polybutene-1 and a preparation method thereof. The preparation method provided by the invention comprises the following steps: a) mixing a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent for reaction, and then removing the solvent to obtain a material A; b) mixing the material A with a cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer and introducing hydrogen, and performing butene-1 body prepolymerization under a low-temperature condition; the low temperature condition is less than or equal to 10 ℃; c) heating to carry out bulk polymerization to obtain in-situ nucleation isotactic polybutene-1; wherein: the main catalyst is a Ziegler-Natta catalyst; the cocatalyst is an alkyl aluminum compound; the polymer nucleating agent monomer is a vinyl compound; the external electron donor is a silane compound. The preparation method provided by the invention realizes that the isotactic polybutene-1 with excellent crystallization performance can be obtained under the condition of lower concentration of the nucleating agent.

Description

In-situ nucleation isotactic polybutene-1 and its prepn
Technical Field
The invention relates to the field of high polymer materials, in particular to in-situ nucleation isotactic polybutene-1 and a preparation method thereof.
Background
The isotactic polybutene-1 is a linear polyolefin material synthesized by taking butene-1 as a monomer, has the characteristics of outstanding heat resistance, creep resistance, good toughness, wear resistance, excellent machinability and the like, can be used for manufacturing floor heating pipelines, easily-peeled films, plates and the like, has wide application prospect, and is also called plastic gold.
However, isotactic polybutene-1 has various crystal structures, and is obtained through melt extrusion, cooling and crystallization under normal conditions to form a II-type crystal, wherein the crystal form II is in an unstable state thermodynamically and can spontaneously convert to a more stable crystal form I at room temperature, the crystal form conversion period is as long as 7 days, the storage period of the product after molding is prolonged, and the production cost is increased; and the isotactic polybutene-1 material produced by the traditional preparation technology does not contain a nucleating agent component, so that the obtained polybutene-1 has low crystallinity and crystallization defects, influences the physical and mechanical properties of the material, particularly has poor product size stability, and seriously influences the application of the polybutene-1.
At present, the crystal transformation process of isotactic polybutene-1 is accelerated mainly by adding a nucleating agent in the polybutene-1 processing process in industrial production, and the crystal defects are improved. The concentration of the added nucleating agent is higher, usually 500-2000 ppm, and the addition amount of the nucleating agent with high concentration not only affects the physical and mechanical properties of the isotactic polybutene-1, but also generates relatively unpleasant odor in the processing process to cause environmental pollution, and the nucleating agent cannot be uniformly dispersed in the matrix of the isotactic polybutene-1 to affect the quality stability of products. In addition, the addition of a high concentration of nucleating agent substantially increases the processing cost of isotactic polybutene-1.
The polyolefin in-situ nucleation technology is a technology for directly forming a polymer nucleating agent in the polyolefin synthesis process, can replace the traditional nucleation technology for adding the nucleating agent in the subsequent processing process of the polyolefin, has better dispersion effect because the nucleating agent in the in-situ nucleation technology exists in a polymerization system before the polymer is formed, can achieve the same effect as an expensive high-performance nucleating agent with lower cost, and simultaneously improves the processing performance and the mechanical property compared with the traditional nucleation technology, especially improves the basic performance of the product size stability.
However, theoretically, the in-situ polyolefin nucleation technology has certain advantages over the nucleation technology of adding a nucleating agent in the subsequent processing process of polyolefin, but in actual production, how to really achieve better effect still faces certain challenges.
Disclosure of Invention
In view of the above, the present invention aims to provide an in-situ nucleated isotactic polybutene-1 and a preparation method thereof. The preparation method provided by the invention can be used for smoothly preparing the in-situ nucleated isotactic polybutene-1 under the condition of the low-concentration polymer nucleating agent, and the obtained isotactic polybutene-1 has high crystallinity, high crystallization temperature and shorter crystal form transition period, so that the isotactic polybutene-1 with excellent crystallization performance can be obtained under the condition of lower nucleating agent concentration.
The invention provides a preparation method of in-situ nucleation isotactic polybutene-1, which comprises the following steps:
a) mixing a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent for reaction, and then removing the solvent to obtain a material A;
b) mixing the material A with a cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer and introducing hydrogen, and performing butene-1 body prepolymerization under a low-temperature condition;
the low temperature condition is less than or equal to 10 ℃;
c) heating to carry out bulk polymerization to obtain in-situ nucleation isotactic polybutene-1;
wherein:
the main catalyst is a Ziegler-Natta catalyst;
the cocatalyst is an alkyl aluminum compound;
the polymer nucleating agent monomer is a vinyl compound;
the external electron donor is a silane compound.
Preferably, the polymeric nucleating agent monomer is selected from at least one of vinylcyclohexane, vinylcyclopentane, vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene and styrene.
Preferably, in the step a), the cocatalyst is selected from at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, dihexyl aluminum monochloride and dioctyl aluminum monochloride;
in the step b), the cocatalyst is selected from at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, dihexyl aluminum monochloride, and dioctyl aluminum monochloride.
Preferably, the external electron donor is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, di-tert-hexyldimethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, di-tert-hexyldiethoxysilane, diphenyldiethoxysilane, dicyclohexyldiethoxysilane, di-tert-butyldiethoxysilane, di-tert-hexyldiethoxysilane, di-cyclohexyldiethoxysilane, di-tert-butyldiethoxysilane, di-butyldimethoxysilane, di-n, At least one of dicyclopentyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, thexyltrimethoxysilane, t-butyltrimethoxysilane, and thexyltrimethoxysilane.
Preferably, the Ziegler-Natta catalyst is a magnesium chloride supported titanium tetrachloride spherical catalyst;
the solvent is an alkane solvent.
Preferably, in step a):
the molar ratio of the cocatalyst to the titanium in the main catalyst is (1-100) to 1;
the mass ratio of the polymer nucleating agent monomer to the main catalyst is (0.2-5) to 1;
the dosage ratio of the main catalyst to the solvent is (1-100) mg to 1 mL;
the reaction temperature is 0-50 ℃, and the reaction time is 5-20 h.
Preferably, in step b):
the molar ratio of the cocatalyst to the titanium in the main catalyst in the step a) is (50-500) to 1;
the molar ratio of the external electron donor to the titanium in the main catalyst in the step a) is (5-30) to 1.
Preferably, the molar ratio of the titanium to the liquid-phase butene-1 monomer in the main catalyst is (1 × 10) -7 ～1×10 -5 )∶1；
In the step b), the partial pressure of hydrogen is 0.5-5 bar;
in the step b), the temperature of the prepolymerization is-30 ℃ to 10 ℃, and the time is 0.5 to 3 hours.
Preferably, in the step c), the temperature of the bulk polymerization is 10-60 ℃, and the time is 2-20 h;
the cocatalyst is added in the form of a cocatalyst solution; the concentration of the cocatalyst solution is 0.5-8 mol/L;
the external electron donor is added in the form of an external electron donor solution; the concentration of the external electron donor solution is 0.1-5 mol/L.
The invention also provides the in-situ nucleation isotactic polybutene-1 prepared by the preparation method in the technical scheme.
The preparation method provided by the invention comprises the steps of mixing and reacting a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent to form the polymer nucleating agent in a system, introducing the cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer, and introducing hydrogen to directly perform low-temperature bulk prepolymerization and normal-temperature polymerization of butene-1 to finally prepare the in-situ nucleated polybutene-1 containing the low-concentration polymer nucleating agent, improve the crystallization temperature and the crystallinity of the in-situ nucleated polybutene-1, shorten the crystal form transition period, and realize low-cost preparation of the isotactic polybutene-1 with excellent crystallization performance at lower nucleating agent concentration.
Experimental results show that the content of the polymer nucleating agent in the in-situ nucleated polybutene-1 prepared by the invention reaches below 500ppm, the lower concentration of the nucleating agent is kept, and meanwhile, the obtained isotactic polybutene-1 has higher crystallinity, higher crystallization temperature and shorter crystal form transformation period, specifically, the product crystallization temperature reaches above 83 ℃, the crystallinity reaches above 48.5%, and the crystal form transformation period is shortened to below 145 hours. Further, under the preferable conditions, the concentration of the nucleating agent can be further reduced to below 250ppm (75-250 ppm), the crystallinity and the crystallization temperature of the isotactic polybutene-1 product are further improved, the crystal transformation period of the product is shortened, the crystallization temperature of the product is increased to above 87 ℃, the crystallinity is increased to above 52%, and the crystal transformation period is shortened to below 70 h.
Detailed Description
The invention provides a preparation method of in-situ nucleation isotactic polybutene-1, which comprises the following steps:
a) mixing a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent for reaction, and then removing the solvent to obtain a material A;
b) mixing the material A with a cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer and introducing hydrogen, and performing butene-1 body prepolymerization under a low-temperature condition;
the low temperature condition is less than or equal to 10 ℃;
c) heating to carry out bulk polymerization to obtain in-situ nucleation isotactic polybutene-1;
wherein:
the main catalyst is a Ziegler-Natta catalyst;
the cocatalyst is an alkyl aluminum compound;
the polymer nucleating agent monomer is a vinyl compound;
the external electron donor is a silane compound.
The preparation method provided by the invention comprises the steps of mixing and reacting a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent to form the polymer nucleating agent in a system, introducing the cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer, and introducing hydrogen to directly perform low-temperature bulk prepolymerization and normal-temperature polymerization of butene-1 to finally prepare the in-situ nucleated polybutene-1 containing the low-concentration polymer nucleating agent, and improving the crystallization temperature and the crystallinity of the in-situ nucleated polybutene-1 and shortening the crystal form transformation period, so that the isotactic polybutene-1 shows excellent crystallization performance at a lower nucleating agent concentration, and the preparation method has important significance in industry and commerce.
[ with respect to step a ]:
a) mixing a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent for reaction, and then removing the solvent to obtain a material A.
In the present invention, the steps a) to c) are preferably performed under a protective atmosphere, and specifically, before the charging, the gas replacement is performed with the reaction apparatus in advance to form a protective atmosphere in the reaction apparatus, and then the charging and the reaction of the steps a) to c) are performed. The kind of the gas for forming the protective gas atmosphere is not particularly limited in the present invention, and may be any inert gas conventionally used in the art, such as nitrogen, helium, argon, or the like.
In the invention, the main catalyst is a Ziegler-Natta catalyst, in particular to a magnesium chloride loaded titanium tetrachloride spherical catalyst. The source of the main catalyst is not particularly limited, and may be commercial products, for example, in some embodiments of the present invention, a CS series catalyst of Liaoning Yangke chemical group catalyst is used, and the titanium content is 2.3 wt%.
In the invention, the cocatalyst is an alkyl aluminum compound; preferably at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl-aluminum monochloride, diisobutyl-aluminum monochloride, dihexyl-aluminum monochloride and dioctyl-aluminum monochloride; more preferably one or two of the above alkyl aluminum compounds.
In the present invention, the cocatalyst is preferably added in the form of a cocatalyst solution, that is, the cocatalyst is dissolved in a solvent to prepare a cocatalyst solution, and then the cocatalyst solution is added into the reaction system. Wherein, the solvent used for preparing the solution is preferably at least one of n-hexane, n-heptane and n-octane. The concentration of the cocatalyst solution is preferably 0.5-8 mol/L, and more preferably 1 mol/L.
In the invention, the polymer nucleating agent monomer is a monomer for forming the polymer nucleating agent and is a vinyl compound; preferably at least one of vinylcyclohexane, vinylcyclopentane, vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene and styrene.
In the present invention, the solvent is preferably an alkane solvent, and more preferably at least one of n-pentane, isopentane, n-hexane, n-heptane, and n-octane.
In the present invention, in step a), the relationship between the amounts of the materials is preferably as follows:
the mol ratio of the cocatalyst to the titanium in the main catalyst is preferably (1-100) to 1, and specifically can be 1: 1, 10: 1, 20: 1, 30: 1, 40: 1, 50: 1, 60: 1, 70: 1, 80: 1, 90: 1 and 100: 1.
The mass ratio of the polymer nucleating agent monomer to the main catalyst is preferably (0.2-5) to 1, and specifically can be 0.2: 1, 0.5: 1, 1.0: 1, 1.5: 1, 2.0: 1, 2.5: 1, 3.0: 1, 3.5: 1, 4.0: 1, 4.5: 1 and 5.0: 1; the content of the polymer nucleating agent in the isotactic polybutene-1 can reach below 500ppm by controlling the proportion range, the lower concentration of the nucleating agent is kept, and meanwhile, the obtained isotactic polybutene-1 has higher crystallinity, higher crystallization temperature and shorter crystal form transformation period, specifically, the crystallization temperature of a product reaches above 83 ℃, the crystallinity reaches above 48.5 percent, and the crystal form transformation period is shortened to below 145 hours. In the invention, the mass ratio is more preferably (0.5-5) to 1, and under the preferable ratio, the crystallinity and the crystallization temperature of the isotactic polybutene-1 product can be further improved, the crystal form conversion period can be further shortened, specifically, the crystallization temperature of the product is increased to be higher than 87 ℃, the crystallinity is increased to be higher than 52%, and the crystal form conversion period is shortened to be lower than 70 h. In the invention, the mass ratio is most preferably (0.5-1.5): 1, and under the preferred ratio, the concentration of the nucleating agent can be further reduced to be below 250ppm (75-250 ppm), and the obtained isotactic polybutene-1 has higher crystallinity, higher crystallization temperature and shorter crystal form transformation period.
The optimal dosage ratio of the main catalyst to the solvent is (1-100) mg to 1 mL.
In the invention, 4 materials of a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent are mixed and then react. The reaction is a polymerization reaction, in the reaction process, the cocatalyst reduces titanium tetrachloride loaded on the surface of the spherical main catalyst into low-valent titanium such as titanium trichloride or titanium dichloride, and the low-valent titanium is used as an active center to initiate a polymer nucleating agent monomer to perform polymerization reaction on the spherical surface of the main catalyst to generate the polymer nucleating agent, and the polymer nucleating agent is uniformly distributed on the surface of the spherical main catalyst. In the present invention, the reaction temperature is preferably 0 to 50 ℃, and specifically may be 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃. The reaction time is preferably 5-20 h, and specifically can be 5h, 10h, 15h and 20 h. After the above reaction, a reaction solution is obtained.
In the present invention, after the above reaction, the solvent is removed from the obtained reaction solution. In the present invention, the solvent removal method is preferably: and vacuumizing the reaction system by using a diaphragm vacuum pump to remove and separate the solvent. The temperature condition for the above operation is preferably 30 to 60 ℃. After removal of the solvent, material a was obtained.
[ regarding step b ]:
b) and mixing the material A with a cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer and introducing hydrogen, and performing butene-1 bulk prepolymerization under a low-temperature condition.
In the invention, the cocatalyst is an alkyl aluminum compound; preferably at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl-aluminum monochloride, diisobutyl-aluminum monochloride, dihexyl-aluminum monochloride and dioctyl-aluminum monochloride; more preferably one or two of the above alkyl aluminum compounds. The cocatalyst can be the same or different, preferably the same, as the cocatalyst employed in step a).
In the present invention, the cocatalyst is preferably added in the form of a cocatalyst solution, that is, the cocatalyst is dissolved in a solvent to prepare a cocatalyst solution, and then the cocatalyst solution is added into the reaction system. Wherein, the solvent used for preparing the solution is preferably at least one of n-hexane, n-heptane and n-octane. The concentration of the cocatalyst solution is preferably 0.5-8 mol/L, and more preferably 1 mol/L.
In the invention, the molar ratio of the cocatalyst to the titanium in the main catalyst in the step a) is preferably (50-500) to 1, and specifically can be 50: 1, 100: 1, 150: 1, 200: 1, 250: 1, 300: 1, 350: 1, 400: 1, 450: 1 and 500: 1.
In the present invention, the external electron donor is a silane compound, preferably vinyltriethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-t-hexyldimethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldiethoxysilane, di-t-hexyldiethoxysilane, diphenyldiethoxysilane, di-t-butyldiethoxysilane, di-t-hexyldiethoxysilane, di-t-butyldiethoxysilane, di-hexyldiethoxysilane, di-hexyldimethoxysilane, di-butyloxysilane, di-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n, di-t-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n, di-s, di-butyldimethoxysilane, di-n-butyldimethoxysilane, di-n-butyldimethoxysilane, di-n-butyldimethoxysilane, di-n, At least one of dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, thexyltrimethoxysilane, t-butyltrimethoxysilane, and thexyltrimethoxysilane; more preferably one or two of the above silane compounds.
In the present invention, the external electron donor is preferably added in the form of an external electron donor solution, i.e., the external electron donor is dissolved in a solvent in advance to prepare an external electron donor solution, and then the external electron donor solution is added into a reaction system. Wherein, the solvent used for preparing the solution is preferably at least one of n-pentane, isopentane, n-hexane and n-higher alkane. The concentration of the external electron donor solution is preferably 0.1-5 mol/L, and more preferably 0.2 mol/L.
In the invention, the molar ratio of the external electron donor to the titanium in the main catalyst in the step a) is preferably (5-30) to 1, and specifically can be 5: 1, 10: 1, 15: 1, 20: 1, 25: 1 and 30: 1.
In the present invention, a liquid phase butene-1 monomer is added to the system in addition to the above materials. In the present invention, theThe molar ratio of titanium to liquid-phase butene-1 monomer in the procatalyst in step a) is preferably (1X 10) -7 ～1×10 -5 ) 1, specifically 1 × 10 -7 ∶1、1×10 -6 ∶1、1×10 -5 ∶1。
In the invention, hydrogen is also introduced into the system. In the invention, the partial pressure of the hydrogen is preferably 0.5-5 bar, and specifically may be 0.5bar, 1bar, 1.5bar, 2bar, 2.5bar, 3bar, 3.5bar, 4bar, 4.5bar, 5 bar.
In the invention, the mixing of the materials is preferably carried out under a low temperature condition, namely, the system is cooled to the low temperature condition in advance, and then the materials are added. The low temperature condition is that the temperature is less than or equal to 10 ℃, more preferably-30 ℃ to 10 ℃, and specifically can be-30 ℃, 25 ℃, 20 ℃, 15 ℃, 10 ℃, 5 ℃, 0 ℃, 5 ℃ and 10 ℃.
In the invention, after all the materials are added, the butene-1 is subjected to bulk prepolymerization under low temperature. In the present invention, the low temperature condition is a temperature of 10 ℃ or less, more preferably-30 ℃ to 10 ℃, and specifically-30 ℃, 25 ℃, 20 ℃, 15 ℃, 10 ℃, 5 ℃, 0 ℃, 5 ℃, 10 ℃. The time for performing the prepolymerization under the low temperature condition is preferably controlled to be 0.5-3 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h and 3 h. And (3) pre-polymerizing the above bulk to obtain a prepolymer.
[ with respect to step c ]:
c) heating to carry out bulk polymerization to obtain the in-situ nucleation isotactic polybutene-1.
In the present invention, after the prepolymerization in step b), the temperature is further raised to carry out bulk polymerization. In the present invention, the temperature of the bulk polymerization is preferably 10 to 60 ℃, and specifically 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃. In the present invention, step c) is carried out by further raising the temperature for bulk polymerization, i.e. the temperature for bulk polymerization > the temperature for bulk prepolymerization in step b), implying that the temperature for bulk polymerization in step c) is not 10 ℃ as compared to the temperature for bulk prepolymerization in step b). In the invention, the time of the bulk polymerization is preferably 2-20 h, and specifically can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h and 20 h. After the bulk polymerization, the in-situ nucleation isotactic polybutene-1 is generated in the system.
In the present invention, after the above bulk polymerization, the obtained reaction solution is preferably subjected to the following post-treatment: introducing the unreacted butene-1 monomer into a butene-1 recovery tank through an exhaust valve, and refining and recovering for recycling. After the post-treatment, the in-situ nucleation isotactic polybutene-1 is obtained.
The invention also provides the in-situ nucleation isotactic polybutene-1 prepared by the preparation method in the technical scheme. The in-situ nucleation isotactic polybutene-1 prepared by the preparation method has the advantages that the concentration of the nucleating agent is lower and is below 500ppm, particularly 75-250 ppm; the crystallization temperature is above 87 ℃, the crystallinity is above 52%, and the crystal form transformation period (the transformation period from the crystal form II to the crystal form I) is below 70 h.
The preparation method provided by the invention comprises the steps of mixing and reacting a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent to form a polymer nucleating agent in a system, introducing the cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer, and introducing hydrogen to directly perform low-temperature bulk prepolymerization and normal-temperature polymerization of butene-1 to finally prepare the in-situ nucleated polybutene-1 containing the low-concentration polymer nucleating agent, improve the crystallization temperature and the crystallinity of the in-situ nucleated polybutene-1, shorten the crystal form conversion period, and realize low-cost preparation of isotactic polybutene-1 with excellent crystallization performance under a lower nucleating agent concentration.
Experimental results show that the content of the polymer nucleating agent in the in-situ nucleated polybutene-1 prepared by the invention reaches below 500ppm, the lower concentration of the nucleating agent is kept, and meanwhile, the obtained isotactic polybutene-1 has higher crystallinity, higher crystallization temperature and shorter crystal form transformation period, specifically, the product crystallization temperature reaches above 83 ℃, the crystallinity reaches above 48.5%, and the crystal form transformation period is shortened to below 145 hours. Further, under the preferable condition, the concentration of the nucleating agent can be further reduced to be below 250ppm (75-250 ppm), the crystallinity and the crystallization temperature of the isotactic polybutene-1 product are further improved, the crystal form transformation period is shortened, the crystallization temperature of the product is increased to be above 87 ℃, the crystallinity is increased to be above 52%, and the crystal form transformation period is shortened to be below 70 h.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples and comparative examples, the main catalyst used was a commercially available magnesium chloride-supported titanium tetrachloride type, CS series from Liaoning Yangke group catalyst, and the titanium content was 2.3 wt%. The reaction device is a 3L high-pressure polymerization kettle, and the distance between a stirring paddle of the reaction device and the bottom of the polymerization kettle is 1-3 mm. The solvent used in step S1 is a solvent from which moisture and impurities are removed by the refining treatment.
Comparative example 1
After a 3-liter autoclave is fully replaced by high-purity nitrogen, 100mg of a main catalyst, 20mL of a cocatalyst solution (the cocatalyst is triethylaluminum, a solvent is n-hexane, the solution concentration is 1mol/L) and 5mL of an external electron donor solution (the external electron donor is diisobutyldimethoxysilane, the solvent is n-heptane, the solution concentration is 0.2mol/L) are sequentially added, then 800g of liquid-phase butene-1 and 1bar of hydrogen are added, and bulk prepolymerization is carried out for 1h at the temperature of 0 ℃; and finally, raising the temperature of the reaction kettle to 35 ℃, and continuing to polymerize for 4 hours to obtain the polybutene-1.
Example 1
S1, after fully replacing a 3L autoclave with high-purity nitrogen, sequentially adding 100mg of main catalyst, 0.5mL of cocatalyst solution (the cocatalyst is triethylaluminum, the solvent is n-hexane, the solution concentration is 1mol/L), 20mg of vinylcyclohexane (VCH, the density is 0.805g/mL, the purity is more than or equal to 98 percent, the water content is less than or equal to 100ppm) and 100mL of n-hexane, and polymerizing for 10 hours at 30 ℃. After the polymerization is finished, the reaction kettle is vacuumized by a diaphragm vacuum pump at the temperature of 30 ℃ to extract and separate the solvent, and a material A is obtained.
S2, cooling the temperature of the kettle to 0 ℃, adding 20mL of a cocatalyst solution (the cocatalyst is triethylaluminum, the solvent is n-hexane, the solution concentration is 1mol/L) and 5mL of an external electron donor solution (the external electron donor is diisobutyldimethoxysilane, the solvent is n-heptane, the solution concentration is 0.2mol/L), then introducing 800g of liquid-phase butene-1 and 1bar of hydrogen, and carrying out bulk prepolymerization for 1h at 0 ℃.
S3, heating the reaction kettle to 35 ℃, and continuing to polymerize for 4h to obtain the in-situ nucleated polybutene-1.
Example 2
The procedure is as in example 1, except that the amount of VCH is adjusted to 50 mg.
Example 3
The procedure is as in example 1, except that the amount of VCH is adjusted to 100 mg.
Example 4
The procedure is as in example 1, except that the amount of VCH is adjusted to 150 mg.
Example 5
The procedure is as in example 1, except that VCH is adjusted to 150mg and dicyclohexyldimethoxysilane is used as external electron donor.
Example 6
The procedure is as in example 1, except that VCH is adjusted to 150mg and dicyclopentyldimethoxysilane is used as external electron donor.
Example 7
The procedure is as in example 1, except that the amount of VCH is adjusted to 150mg and the reaction conditions in step S1 are such that the polymerization is carried out at 20 ℃ for 15 h.
Example 8
The procedure is as in example 1, except that the amount of VCH is adjusted to 150mg and the reaction conditions in step S1 are such that the polymerization is carried out at 40 ℃ for 8 h.
Example 9
The procedure was as in example 1, except that the amount of VCH was adjusted to 150mg and the amount of the external electron donor solution was 2.5 mL.
Example 10
The procedure was as in example 1, except that the temperature of the reaction vessel was raised to 40 ℃ in step S3.
Example 11: testing
1. Testing of the content of Polyvinylcyclohexane (PVCH) in the polymers: calculated by testing the conversion of Vinylcyclohexane (VCH). Further, the amount of VCH remaining in the reaction solution after completion of the polymerization and before the solvent separation in step S1 was analyzed by gas chromatography; toluene was used as internal standard. The residual VCH amounts in the above examples and comparative examples were 0.
2. Measurement of melt Mass Flow Rate (MFR): the load is 2.16kg and the test temperature is 190 ℃ according to the measurement of GB/T3682.1-2018.
3. Measurement of isotacticity (DE-ins): the determination of the method is carried out by adopting an ether extraction method, 2g of dried polymer sample is put into a Soxhlet extractor to be extracted by boiling ether for 24h, and the ratio of the polymer mass (g) to 2(g) obtained by drying the residue to constant weight is the isotacticity.
4. DSC test: in a nitrogen atmosphere, firstly heating a 5-10 mg sample from room temperature to 200 ℃ at a speed of 10 ℃/min, and keeping the temperature at 200 ℃ for 5min to eliminate the thermal history; then, the sample was cooled to room temperature at a rate of-10 ℃/min; finally, the sample was reheated to 200 ℃ at a rate of 10 ℃/min. The crystallization temperature (T) of the sample was calculated using the second temperature rise curve according to the following relation c ) And degree of crystallinity (X) c ) Melting Point (T) m ) Also measured according to the secondary heating curve: xc (%). DELTA.H m /ΔH * f 100%, wherein Δ H m Is the melting enthalpy, Δ H, of the secondary temperature rise curve * f Is the standard melting enthalpy (62J/g) for polybutene-1 form II.
5. Testing of catalytic activity: calculating CA as Q/W according to the following formula cat ·t×10 -3 With the unit of kgPB (gcat h) -1 Wherein CA is the catalytic activity of the catalyst, Q is the mass (g) of the product in the polymerization reaction, W cat The amount of the main catalyst is (g), and t is the polymerization time (h) of the butene-1.
6. Crystal transition period (t) 90 ) The test of (2): the crystal form detection adopts wide-angle X-ray diffraction (WAXD), the test adopts a Cu target as an anode metal material, a produced Kalpha line with the wavelength of 0.154nm, the test voltage is 40kV, the current is 40mA, the scanning speed is 5 degrees/min, and the scanning range is 5 degrees to 40 degrees. The test samples were rapidly cooled from 200 ℃ to 25 ℃ at a rate of-50 ℃/min and samples at different annealing times were characterized at 25 ℃. WAXS test results show diffraction observed at 11.9 °, 16.9 ° and 18.5 °The injection peaks can be respectively assigned to crystal faces (200), (220) and (213) of the crystal form II in the polybutene-1; the diffraction peaks observed at 10.0 °, 17.5 ° and 20.4 ° can be assigned to the (110), (300) and (220/+211) crystal planes of polybutene-1 form I, respectively, I (110) I And I (200) II The integrated intensities of the diffraction peaks representing the crystal planes of the crystal form I (110) and the crystal plane of the crystal form II (200), respectively, were measured using a spectrometer I /[I(110) I +0.67I(200) II ]Represents the percent of complete transformation of form I (X) I )，t 90 Namely, the crystal form I finishes 90 percent conversion (X) after the polybutene-1 is melted and cooled I 90) of the time.
The test results are shown in table 1:
table 1: butene-1 polymerization and Polymer characterization results
Figure BDA0003671580250000121
Note: VCH/Cat is the mass ratio of vinyl cyclohexane to main catalyst; t is the polymerization temperature of VCH; t is the VCH polymerization time; ED is an external electron donor, D1 is diisobutyldimethoxysilane, D2 is dicyclohexyldimethoxysilane, and D3 is dicyclopentyldimethoxysilane; example 9, ED/Ti 10, other comparative examples ED/Ti 20; example 10 butene-1 bulk polymerization temperature was 40 ℃ and other examples comparative example was 35 ℃.
It can be seen that examples 1-10 and comparative example 1 all showed good catalytic activity, and the products all had high isotacticity.
Crystallization temperature is a good indicator of the efficiency of the nucleating agent, with higher crystallization temperatures meaning more efficient nucleation in the final product. As shown by the test results in Table 1, compared with comparative example 1, examples 1 to 10 all show better nucleation effect, the crystallization temperature of polybutene-1 is increased from 72.3 ℃ to more than 83.2 ℃, the crystallinity is increased from 43.9% to more than 48%, and the crystal form transformation period is shortened to less than 145 h.
In examples 1 to 10, in examples 2 to 10, under the preferred conditions (i.e., the mass ratio of the polymer nucleating agent monomer to the main catalyst is 0.5 to 1.5: 1), the content of the nucleating agent is increased, so that the crystallization temperature, the crystallinity and the crystal transformation period of the obtained isotactic polybutene-1 are further improved significantly, specifically, the crystallization temperature of the product is increased to over 87 ℃, the crystallinity is increased to over 52%, and the crystal transformation period is shortened to under 70 h. In addition, compared with the crystal form transformation periods of examples 2 to 10, the crystal form transformation period of comparative example 1 and example 1 is shortened to 144h from 162h only by the nucleating agent concentration of 29ppm, and when the nucleating agent concentration exceeds 75ppm (but still is kept at the lower nucleating agent concentration of 250ppm), the crystal form transformation period is greatly shortened to only 41 to 68h, which proves that the preferable parameter conditions lead to the unexpected improvement of the crystal form transformation period. Moreover, the concentration of the nucleating agent in the embodiments 2-10 is below 250ppm, compared with the prior art, the concentration of the nucleating agent is greatly reduced, and the isotactic polybutene-1 with excellent crystallization performance is obtained under the condition of low concentration of the nucleating agent.
The foregoing examples are provided to facilitate an understanding of the principles of the invention and their core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that approximate the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims (10)

1. The preparation method of the in-situ nucleation isotactic polybutene-1 is characterized by comprising the following steps:
a) mixing a main catalyst, a cocatalyst, a polymer nucleating agent monomer and a solvent for reaction, and then removing the solvent to obtain a material A;
b) mixing the material A with a cocatalyst and an external electron donor, adding a liquid-phase butene-1 monomer and introducing hydrogen, and performing butene-1 body prepolymerization under a low-temperature condition;
the low temperature condition is less than or equal to 10 ℃;
c) heating to carry out bulk polymerization to obtain in-situ nucleation isotactic polybutene-1;
wherein:
the main catalyst is a Ziegler-Natta catalyst;
the cocatalyst is an alkyl aluminum compound;
the polymer nucleating agent monomer is a vinyl compound;
the external electron donor is a silane compound.
2. The method of claim 1, wherein the polymeric nucleating agent monomer is selected from at least one of vinylcyclohexane, vinylcyclopentane, vinyl-2-methylcyclohexane, 3-methyl-1-butene, 3-ethyl-1-hexene, 3-methyl-1-pentene, and styrene.
3. The preparation method according to claim 1, characterized in that in the step a), the cocatalyst is selected from at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, dihexylaluminum monochloride and dioctylaluminum monochloride;
in the step b), the cocatalyst is selected from at least one of triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, dihexyl aluminum monochloride, and dioctyl aluminum monochloride.
4. The method of claim 1, wherein the external electron donor is selected from the group consisting of vinyltriethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-t-hexyldimethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldiethoxysilane, di-t-hexyldiethoxysilane, di-t-butyldiethoxysilane, di-t-hexyldiethoxysilane, di-t-butyldimethoxysilane, di-butyldimethoxysilane, and a, At least one of diphenyldiethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentyltrimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyltrimethoxysilane, thexyltrimethoxysilane, t-butyltrimethoxysilane, and thexyltrimethoxysilane.
5. The method of claim 1, wherein the Ziegler-Natta catalyst is a magnesium chloride supported titanium tetrachloride spherical catalyst;
the solvent is an alkane solvent.
6. The method of claim 1, wherein in step a):
the molar ratio of the cocatalyst to the titanium in the main catalyst is (1-100) to 1;
the mass ratio of the polymer nucleating agent monomer to the main catalyst is (0.2-5) to 1;
the dosage ratio of the main catalyst to the solvent is (1-100) mg to 1 mL;
the reaction temperature is 0-50 ℃, and the reaction time is 5-20 h.
7. The method of claim 1, wherein in step b):
the molar ratio of the titanium in the main catalyst in the step a) to the titanium in the cocatalyst is (50-500) to 1;
the molar ratio of the external electron donor to the titanium in the main catalyst in the step a) is (5-30) to 1.
8. The method according to claim 1, wherein the molar ratio of the titanium to the liquid-phase butene-1 monomer in the main catalyst is (1 x 10) -7 ～1×10 -5 )∶1；
In the step b), the partial pressure of hydrogen is 0.5-5 bar;
in the step b), the temperature of the prepolymerization is-30 ℃ to 10 ℃, and the time is 0.5 to 3 hours.
9. The preparation method according to claim 1, wherein in the step c), the temperature of the bulk polymerization is 10-60 ℃ and the time is 2-20 h;
the cocatalyst is added in the form of a cocatalyst solution; the concentration of the cocatalyst solution is 0.5-8 mol/L;
the external electron donor is added in the form of an external electron donor solution; the concentration of the external electron donor solution is 0.1-5 mol/L.
10. An in-situ nucleated isotactic polybutene-1 prepared by the process of any one of claims 1 to 9.
CN202210606541.3A 2022-05-31 2022-05-31 In-situ nucleation isotactic polybutene-1 and its prepn Pending CN114989334A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210606541.3A CN114989334A (en) 2022-05-31 2022-05-31 In-situ nucleation isotactic polybutene-1 and its prepn

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210606541.3A CN114989334A (en) 2022-05-31 2022-05-31 In-situ nucleation isotactic polybutene-1 and its prepn

Publications (1)

Publication Number Publication Date
CN114989334A true CN114989334A (en) 2022-09-02

Family

ID=83030204

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210606541.3A Pending CN114989334A (en) 2022-05-31 2022-05-31 In-situ nucleation isotactic polybutene-1 and its prepn

Country Status (1)

Country Link
CN (1) CN114989334A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505217A (en) * 2022-10-10 2022-12-23 山东京博石油化工有限公司 In-situ nucleation polybutene alloy and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819596A (en) * 2012-11-16 2014-05-28 中国石油天然气股份有限公司 Preparation method for isotactic poly (1-butene)
CN109196003A (en) * 2016-07-12 2019-01-11 博里利斯股份公司 It is used to prepare the solid catalyst of the polyolefin of nucleation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819596A (en) * 2012-11-16 2014-05-28 中国石油天然气股份有限公司 Preparation method for isotactic poly (1-butene)
CN109196003A (en) * 2016-07-12 2019-01-11 博里利斯股份公司 It is used to prepare the solid catalyst of the polyolefin of nucleation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115505217A (en) * 2022-10-10 2022-12-23 山东京博石油化工有限公司 In-situ nucleation polybutene alloy and preparation method thereof

Similar Documents

Publication Publication Date Title
JP3857723B2 (en) Preparation of catalyst suitable for olefin polymerization
US6291385B1 (en) Catalyst for polymerization or copolymerization of olefin
JP5718314B2 (en) Cyclic organosilicon compounds as electron donors for polyolefin catalysts
JP6209056B2 (en) Narrow molecular weight distribution polypropylene and preparation method thereof
JP5726169B2 (en) Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
JP2012508278A (en) Propylene homopolymerization and copolymerization catalysts and methods for their preparation and use
KR20020025901A (en) Solid catalyst component and catalyst for olefin polymerization
EP3670546A1 (en) Solid catalyst for propylene polymerization and method of producing block copolymer using the same
CN107949588B (en) Catalyst for polymerization of olefins
JP2004527636A (en) Olefin polymerization catalyst composition and method for producing the same
CN107428995B (en) Oxalic acid diamides as modifiers for polyolefin catalysts
CN114989334A (en) In-situ nucleation isotactic polybutene-1 and its prepn
US6703456B2 (en) Process for producing catalyst for α-olefin polymerization, and process for producing α-olefin polymer
CN108148153B (en) Solid catalyst and method for preparing propylene polymer or copolymer using the same
KR101795317B1 (en) A solid catalyst for propylene polymerization and a method for preparation of polypropylene
JP3354987B2 (en) Catalyst system for stereospecific polymerization of α-olefin, its polymerization method and obtained polymer
CN107840917B (en) Solid catalyst component for olefin polymerization, catalyst system and prepolymerization catalyst
JP2014513736A (en) Catalysts for olefin polymerization reactions containing silanes substituted with thienyl groups.
JP2003040918A (en) Solid catalyst component and catalyst for polymerizing olefins
JP3885336B2 (en) α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer
KR101699590B1 (en) A solid catalyst for propylene polymerization and a method for preparation of polypropylene using the catalyst
KR101123523B1 (en) A method for preparation of a solid catalyst for polymerization of propylene
CN114752009A (en) In-situ nucleated polypropylene and preparation method thereof
CN115505217A (en) In-situ nucleation polybutene alloy and preparation method thereof
JP2003261612A (en) Solid catalyst component for polymerizing olefins and catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination