SA01210657B1 - Continuous vapor phase process for the polymerization of olefins - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vapor-phase and continuous polymerization method of an olefin free of clogging of vapor phase polymerization apparatus, having high polymerization activity and capable of producing a polyolefin excellent in stereoregularity when continuously polymerizing the olefin in a vapor phase. SOLUTION: This method for continuously polymerizing an olefin in a vapor phase is characterized by polymerizing or copolymerizing an olefin in the presence of (i) a catalyst for olefin polymerization formed of [A] a solid titanium catalyst containing magnesium, titanium and a halogen as essential components, [B] an organoalluminum compound catalyst component and [C] SiR1R2(OR3)2 (wherein R1 and R2 are each cyclopentyl group, cyclopentenyl group, cyclopentadienyl group or the like; R3 is methyl group or ethyl group) and (ii) a surfactant in an amount of 0.1-20 pts.wt. based on 100 pts.wt. olefin polymerization catalyst.

Description

Continuous Vapor Phase Process for Polymerization of Olefin Full Description BACKGROUND: The present invention relates to a continuous vapor phase process for polymerization of olefins without blockages/agglomerations in vapor phase polymerization equipment. Several proposals have been made in the production of a solid catalyst component consisting primarily of magnesium; titanium; halogen miles of electron” and is known to use this solid catalyst component to polymerize an alpha-olefin with ? at least two carbon atoms; A highly ordered stereoisomerized polymer can be produced with a production rate of dle and meanwhile; fa ge Olefins are preferably polymerized by the continuous vapor phase polymerization process; that is, continuous polymerization of olefins in a vapor phase; instead of the 0 polymerization in a liquid phase and the polymerization in a suspension phase; Where in the continuous vapor phase polymerization process, a polymer is obtained directly in the form of a powder that is easy to use. However, a problem arises when a polymer in powder form flows through tubes equipped with a polymerization reactor; Tubing connecting polymerization reactors to each stage Multistage vapor phase polymerization equipment using a fluidized bed reactor and various other equipment through which 0 polymer flows. This means that the flowability of the polymer sometimes deteriorates; Thus, the JS of the polymer accumulates in the so-called dead space; which forms parts of various equipment where flowability is poor; The polymers are arranged in sheets. As a result; The pipes are clogged in the worst condition. and in the event that the polymerization of the olefin is carried out by a continuous vapor phase polymerization process; and at Y. clogging of continuous vapor phase polymerization equipment; It is necessary to stop the polymerization reaction and check the equipment; Consequently, the polyolefin production efficiency decreases significantly; Which causes a problem. a

: Ugg for that; in the continuous vapor phase olefin polymerization process; There is a strong need to prevent clogging of the polymerization equipment. Such blockages/clumps of polymerization equipment are believed to occur for example because a portion of the polymerization equipment is in a vapor phase; Heat spots and the like are generated and 0 polymers are formed in the form of sheets; The said polymers then fall to block the bottom of the polymerization equipment; and/or fine particles from the top of the polymerization equipment in a vapor phase to clog the pipelines or pumps of the equipment. On the other hand; Tchd as a catalyst used in the process of preparing olefins, specifically propylene polymers; These catalysts produce a space-ordered polyolefin of Alle© grade as well as high polymerization efficiency. The present inventors made extensive efforts to discover a continuous vapor phase polymerization process for olefins by means of which a highly ordered vacuum polyolefin can be produced with high polymerization efficiency without blockages in any parts of the continuous vapor phase polymerization equipment. As a result of cll they found that by using «lis consisting of © ( ) a solid titanium catalyst component containing magnesium. titanium and halogen as basic components; (b) an organoaluminum compound catalyst component; and (c):(l51882)08 (where SR!83 each represents a cyclojib group; a cyclopenthenyl group; a cyclopentadienyl group; a cyclopentyl group substituting from one to four alkyl groups having from 1 to carbon atoms a cyclopentenyl group substituting from one to four alkyl groups with 1 to 1 carbon atoms a cyclojialing group bearing a substituted from one to four alkyl groups with 1 to 1 carbon atoms OR a group indenyl "indanyl group" a tetrahydroindenyl group or a fluorenyl group can bear a substituent of one to four alkyl groups with 1 to 1 carbon atoms; RC is a methyl group or ethyl group); The aforementioned SA problems can be completely eliminated and thus the present invention is applied. Take 10

The present invention is intended to solve the aforementioned problems associated with previous techniques and to provide a continuous vapor phase olefin polymerization process; as no blockages occur during the continuous vapor phase olefin polymerization; Capable of producing highly ordered vacuum polyolefins with high polymerization efficiency.

0+ General description of the invention

a for the invention; The continuous vapor-phase olefin polymerization process is characterized by the polymerization or copolymerization of olefins in the presence of an olefin polymerization catalyst composed of (a) a solid magnesium-containing titanium catalyst component; titanium and halogen as basic components; (b) an organoaluminum compound catalyst component; And

0 (c) SiR'Ry(OR’), where L8 and 82 represent a cyclopentyl group; toroidal pentintel group; A cyclopentadienyl group, a cyclopentyl group bearing Son from one to four alkyl groups having from 1 to ; atoms (mS) a cyclopentenyl group Sa converts from one to four alkyl groups with 1 to 2 carbon atoms; a cyclopentadienyl group substituting from one to four alkyl groups with 1 to 1 carbon atoms; or indenyl group; jill group (tetrahydroindenyl group or fluorenyl group) Shan can carry from one to four alkyl groups having from 1 to ; carbon atoms; representing 83 de sana methyl

or an ethyl group). and in invention; Olefins can be polymerized in the presence of a specified amount of surfactant x with the catalyst of components (a); (b) and (c) aforementioned. In the continuous vapor-phase olefin polymerization process Gay of the present invention the catalyst consists of a solid titanium catalyst component (a); Organoaluminum compound catalyst (b) and special organosilicon catalyst component (c) A surfactant may be used. Thus there are no blockages in the vapor phase polymerization equipment when vo-olefins are continuously polymerized in the vapor phase and a highly ordered stereoisomerized polyolefin can also be produced; It's 101

Low amount of hydrocarbon soluble components and narrow composition distribution with high production rate. Brief Explanation of Drawings: Figure [1] shows a schematic view of the Ey-0 continuous vapor phase olefin polymerization equipment of the present invention. Detailed description The continuous vapor phase process of olefin polymerization and the olefin polymerization catalyst used in the dy process of the invention are described more precisely below. In the present invention the term “polymerization” is sometimes used not only in the sense of ©-homopolymer but Lad in the sense of a copolymer; and the term “polymer” is sometimes used not only in the sense of a homopolymer but in the sense of a copolymer as well. Continuous vapor phase Gy of the present invention; polymerizes or copolymerizes the olefin in the presence of an olefin polymerization catalyst which will be mentioned below. The olefin polymerization catalyst of the present invention consists of a solid titanium catalytic component (a); and a catalytic component of a special organosilicon compound (c).Fig. [1] shows a schematic view of the continuous vapor-phase polymerization equipment used in the present invention.In the polymerization of olefins (or copolymerization) using fluidized x-bed reaction equipment in A vapor phase; a solid catalyst is fed eg to a fluidized bed reactor (3) in powdered solid state and/or Als suspended in solvent through a catalyst feed line (1) and a gaseous olefin is fed eg continuously from a line gas feed (3) and forced into the reactor from the bottom of the fluidized bed reactor (?) through a gas dispersing plate (4) Jie perforated plate using a rotary Sle blower; jie pump; (not shown in the figure) through a circulating gas ve line (7) and accordingly a fluidized bed (reaction system) (0) remains in Alla fluidized and displays yesqy

Those olefins pushed into the fluidized bed (0) in which a solid catalyst is maintained in a fluidized state for a polymerization reaction and thus a polymer in the form of a powder (polyolefin powder). The resulting polyolefin powder is continuously extracted from the fluidized bed reactor (7) through a line Unreacted gaseous olefins passing through

0 The fluidized bed (0) at a hysteresis zone (IF) is provided at the top of the fluidized bed reactor (7) and is extracted from the fluidized bed reactor (7) through an oY gas discharge line) and the heat of polymerization is removed using heat exchanger (not shown in the figure); It is administered into the fluidized bed (©) through the circulating gas line (7). A molecular weight modifier such as hydrogen may be fed from an optional portion of the fluidized bed reaction equipment in a vapor phase;

. Sabil JB Gas Feed Line (3)

Vapor phase polymerization equipment such as upright stirred tank type and horizontal stirred tank type can also be used instead of fluidized bed tank type.

The solid titanium catalyst component (1) used in the present invention is a highly effective catalyst component containing primarily magnesium, titanium and halogens.

ve The solid titanium catalyst component (a) can be prepared by contacting a magnesium compound and a compound

titanium as described below.

The titanium compound used in the preparation of the solid titanium catalyst component (a) of the present invention may be a tetravalent titanium compound represented by the formula Xe (THOR) where R is a hydrocarbon group; X represents halogen; and 0 < 9 < 4.

TiCl die Specific examples of the titanium compound include titanium tetrahalide Y. (Ti(OC,H5)Cly «Ti(OCH;)Cly titanium alkoxy trihalide µTily, TiBry and (tolat- 0-180; <Ti(OC,Hs)Cly «Ti(OCH3),Cly, Jia titanium and Ti(O-n-C4Ho)sCl ¢Ti(OC,Hs);Cl (0011):0 trihalide trihalide Titanium like

Among these are titanium compounds containing halogens are preferred; Especially titanium tetrahalide compounds.” More specifically, titanium tetrachloride compounds. These titanium compounds can be used alone or in combination with two or more compounds. They can be used as dilute -0 solutions in hydrocarbon compounds or halogenated hydrocarbon compounds. The magnesium compounds used in the preparation of the solid titanium catalyst component A can be a reducible magnesium compound and a non-reducible magnesium compound. That the magnesium compound that has reducibility, for example, be a magnesium compound with a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples include © of the reducible magnesium compound dimethylmagnesium; Diethyl Magnesium; Dipropyl Magnesium; dibutyl magnesium; magnesium diamyl; Magnesium Dihexyl; Didecyl Magnesium; magnesium ethyl chloride; magnesium propyl chloride; magnesium butyl chloride; magnesium hexyl chloride; magnesium amyl chloride; butyl ethoxy magnesium; ethyl butyl magnesium and butyl magnesium halide. These magnesium compounds may be used alone or as a complex combined with an organo-aluminium complex described below. These magnesium compounds are either liquid or solid. Particular examples of an irreducible magnesium compound include magnesium chloride halide compounds; magnesium bromide; magnesium iodide and magnesium fluoride; magnesium jie; Ethoxy Chloride Jie Magnesium Alkoxy Halide Compounds © Magnesium » Isopropoxy Magnesium Chloride; magnesium butoxy chloride and ethoxy magnesium chloride; Magnesium aryloxy halide compounds such as phenoxy-magnesium chloride; ethoxy-magnesium; Jie and methylphenoxy-magnesium chloride; Magnesium alkoxy compounds

JY Isopropoxy Magnesium; Magnesium Butoxy” p--Ectoxy Magnesium and Hexoxy Magnesium; Magnesium aryloxy compounds such as magnesium phenoxy and dimethyl ro 101 spray

A

phenoxy-magnesium; and magnesium salts of carboxylic acids such as magnesium laurate and magnesium stearate. The irreducible magnesium compound can be a compound derived from the reducible magnesium compound separately or at the time of preparation of the catalyst component. This can be done on For example, by contacting a reducible magnesium compound with 0 polysiloxanes; a halogen-containing silan compound; Jie such a compound an aluminum halogen-containing compound; An ester or an alcohol. In addition to the reducible and non-reducible magnesium compounds, the magnesium compound used in the invention can also be the aforementioned reducible dled, a superimposed compound, a binary compound with another metal, or a mixture with a metal compound another and may be a mixture of two or more of the above-mentioned compounds. Lal In accordance with the present invention; Among these compounds; Magnesium compounds that have no reducibility are preferred; Magnesium compounds containing halogens are preferred. Magnesium chloride compounds are often preferred; Magnesium alkoxy chloride and magnesium aryloxy chloride. In the preparation of the solid titanium catalyst component (a) of the invention; It is preferable to use a vo-electronic material; For example, electronegative substances containing oxygen such as alcohols; phenols; ketones aldehydes; carboxylic acids; organic or inorganic acid esters; ethers; acid amides and acid anhydrides; and electron-containing nitrogen-containing substances such as ammoniaamines; Nitriles and iso-cyanates. The following (1) An organic silicon compound represented by the formula can also be used: (0) R,Si(OR)n as a donor material cf Zn 2+, where each of 0 and 8 represents a group Hydrocarbon;

Esters are the desired electron evaporators to be incorporated into the titanium catalyst component. Those esters with a structure represented by the following formulas R'-C-COOR' 8 GOR < etc. R OOR® ' R'-C-OCOR' } R'-C-COOR! mm J mm where 8 represents a hydrocarbon group with or without substituents; Each RE SR GR? represents a hydrogen atom or a hydrocarbon group with or without substituents; Both 83 and RY 0 represent a hydrogen atom or a substituent or unsubstituted hydrocarbon group. Preferably, at least one of them, Jia, has a substituent or unsubstituted hydrocarbon group. RY and RY can bond with each other. Examples of hydrocarbon groups bearing substituents for R' to RY include hydrocarbon groups with moieties containing heterotoms such as “SON” for example “OH” COOH “COOR” C-0-C Taroi -C-N-C- and NH,Ve Diesters are particularly preferred for dicarboxylic acids as they represent at least one moiety of the !8 and 82 alkyl groups with at least two carbon atoms. Among these multi-functional group esters; Compounds having the structural structures exemplified by the above general formulas are preferred. The best are esters formed between lll maleic acid or malonic acid bearing substituents and alcohols with two carbons on (JY) and specifically vo-esters formed between phtalic acid and alcohols with two carbons are preferred. The esters of the monocarboxylic acid represented by the formula RCOOR' are another group of electron-dissolving materials that can be incorporated into the titanium catalyst component, where each of the R' SR represents a hydrocarbyl group that can carry Son, and at least one of them represents a branched group of 101 ‏

: 0 (includes an annular aliphatic moiety) or a linear group containing a ring. Specifically. R can represent 3 for “(CH;),CH- mutated” “(CHs)CHy- “(CH;);C- “(CH;),CHCH,- cml ‘ —cid Nc ' CH; } 0 ars b" 0 where etc. If one notch of R and !8 represents any of the groups described above, the other notch may represent the group described above or some other group such as a linear or cyclic group. It includes Ald especially of those carboxylic esters formed between the carboxylic acids “Je Dimethyl acetic acid. Trimethyl acetic acid.” Alpha-methylbutyric acid “Beta-methylbutyric acid” Methacrylic acid and Benzoyl acetic acid; and Je alcohols Isopropatol; Isobutyl alcohol and te-butyl alcohol. Esters of carbonic acid can also be used as electron reagents. Particular examples include diethyl carbonate; “old” diisopropyl carbonate Jed ethyl carbonate and diphenyl carbonate. For the electron, they should not be used directly as eal gl materials, but (Say) also use compounds that can be converted to electron-exciting materials during the preparation of titanium catalyst components as raw materials. M and another electron-electronic material can be present in the titanium catalyst component; but its amount must be limited to a small amount where a large amount would have adverse effects.In the present invention; The solid titanium catalyst component (a) can be produced by contacting the aforementioned magnesium compound (or metallic magnesium) and the titanium compound, preferably the electron-electronic material, by a known method used to prepare a highly effective titanium catalyst component from the Lach1 compound

magnesium; A titanium compound and an electron donor. The above components can come into contact in the presence of a DAT reacting agent such as silicone; phosphorus or aluminium. Several examples of the method for producing a solid titanium catalyst component (a) are briefly described and performed. (1) A magnesium compound or a composite of magnesium compound reacts with the electron-friendly material with a titanium compound in the liquid phase. This Jeli can be done in the presence of a crushing agent. Solid compounds can be crushed during the reaction. (7) It is not reducible and titanium compounds, both in the liquid state, in the presence of an electron solvator to precipitate a solid titanium composite. 1 (7) Lad reaction product obtained from step (7) reacts with titanium compound. (;) The reaction obtained from step (1) or (1) with an electrophilic substance and a titanium compound. (©) The magnesium compound or a superimposed compound of the magnesium complex and the electronexciter in the presence of the titanium compound is crushed; the solid product is treated with a halogen.” A halogen compound or an aromatic hydrocarbon In this method, the magnesium compound or the superposition of the magnesium complex with the electron donor can be crushed in the presence of a pulverizer, etc. Alternatively, the magnesium compound or the superimposed complex of the magnesium complex and the electron donor is crushed in the presence of the compound titanium; It is pre-treated with a reaction aid and thereafter; treated with halogens”; etc. The catalyst may be an organoaluminium compound or a halogen-containing silicon compound. (7) The product obtained from step (1) to (£) is treated with a halogen compound halogen or with a hydrocarbon. (V) A reaction product obtained by contacting magnesium dihydrocarbyl oxide and a halogen-containing alcohol with the donor material for electron and titanium compound. Yedy vy alkoxy (same) a magnesium compound such as a magnesium salt of (A) magnesium acid or aryloxymagnesium reacts with an electron donor; a titanium compound and/or a halogen-containing hydrocarbon. aforementioned Above to prepare the titanium catalyst component (A) to (1) Among the methods of using liquid titanium halide Cus it is preferable to use titanium compound in the method of annealing 0 a halogenated hydrocarbon is used after or during Cus and in the Glial method) at the same time as preparing the catalyst preparation. The amounts of ingredients used in the preparation of the solid titanium catalyst component (A) may vary depending on the method of preparation. and for example; used from about 0.01 to 000 mol; Preferably from 05 to ? mall; of electron donor material and of about #0 mol; of titanium compound per mole of compound 006 to 0.09 moles; Preferably from 0 magnesium. The catalyst component of titanium solid (1) obtained in this way includes magnesium; halogen and electron stimulant as basic ingredients. 0 titanium and in the catalyst component titanium solid (a); the ratio varies The atomic number of halogen/titanium is vo and the molecular ratio ranges from 6) 0 emo of about ;-5060; Preferably from about mY and preferably from about 1,001 Electron material / titanium from about, and the atomic ratio of magnesium / titanium ranges from about 1-000; Preferably of about RH the solid titanium catalyst component includes (1) magnesium halide with a crystal size smaller than Tr m/g; 00 commercial magnesium halides and typically has a specific surface area of at least Tr m/g. Since Ave to 100 m'/g; better than about 001 to 1 preferably from about the above components are found to form a compact structure of solid titanium catalyst component (a); the composition does not change Solid titanium catalyst component (a) substantially when washed with hexane.‎ 1o04V

0 and the titanium steel (A) catalyst component can be used alone. And according to desire. It can be used after diluting with an inorganic compound or as an organic silicone compound; Aluminum or polyolefin compound. When a diluent of this (Jal) is used, the catalytic component (a) shows high catalytic activity even when it has a smaller specific surface area than those mentioned above. Methods for preparing the high-activity titanium catalyst component are described in Japanese patent publications. /yaYe is broken as a solution to a solution. Ee AEVAVA There are a number of compounds that have at least one aluminum-carbon bond in the molecule and compounds with at least one carbon-aluminum bond in the molecule can be used as the catalytic component of organoaluminium compound (B). Examples of compounds include (1) organic aluminum compounds represented by the general formula R'wALOR? ),H,X, where each of L8 and RP represent a hydrocarbon group with from 1 to 15 carbon atoms” and preferably from 1 to ; carbon atoms and they may be the same or different; and X represents a halogen atom; em 5p en represents numbers that satisfy the conditions for represented in 1 gm < kF>n2 1 b KF <p2 02f < ? 5 = qtptntm : and (1) © alkylated compounds superimposed between a metal of group (1) and aluminum represented by the general formula for solution 1 M' Cus representing NaLi or ©O as defined above. Examples include On organic aluminum compounds with the general formula (1) Alias compounds with the general formula ,,:(th0)uh.l8 where l and WSR? are customary lel and it is preferable for © to represent “a number that fulfills the conditions represented in 0 # h < « < ; l

0 Compounds represented by the general formula Cun RIGA, !8 as defined X del represents a halogen; It is preferable to represent “a number that fulfills the conditions represented in F>m> 0 compounds represented by the general formula RAH, where L is as defined above; Preferably, Jia Tae “ satisfies the conditions represented by 1 < “ < 1 and

Compounds represented by the general form k,(1)012e'8 dua l 8 and 82 as defined above; Xs represents halogen; and ©” m and f represents Tala ef fulfills the conditions represented by Fm > 0 0 and < at > gm << to har N=qtptntm

Among these compounds; Trialkyl aluminum compounds and alkyl aluminum compounds resulting from the bonding of two or more of the aforementioned aluminum compounds are preferred.

1 The catalyst component of organosilicon compound (c) is an organosilicon compound containing in from a cyclopentyl group; Bla pentenyl group cyclopentadienyl group; Or a derivative of any of these groups can be used. The preferred organosilicon compound is represented by the following general formula; SiR'R*(OR?),

where 8 and RP represent a cyclopentyl group; Cyclopentinyl group; cyclopentadienyl group; A cyclopentyl group is a substituent of one to four alkyl groups having from 1 to ; carbon atoms A Sha-bearing cyclopentenyl group has one to four alkyl groups having from 1 to ; carbon atoms Shay-bearing cyclopentadienyl group has one to four alkyl groups having from 1 to ; carbon atoms or an indenyl group; ila group).

© - Tetrahydroindenyl group or Fluorenyl group Son can carry from one to four alkyl groups having from 1 to ; carbon atoms 83 represents an instance group or an ethyl group. The preferred compound represented by the formula: (5:882)013 includes those compounds dus R' is a cyclopentyl group; Cyclopentinyl group»; β-pentadienyl group is a Sha-bearing cyclopentyl group from one to four alkyl groups having from 1 to ; carbon atoms Which alkyl group? to ; Carbon atoms bearing a de sane substituent of cyclopentyl can carry Yyodyv vo to ; carbon atoms pentenyl group 1 substitutes from one to four alkyl groups with from to ; 1 carbon atoms from one to four alkyl groups of Sn bearing ils to; 1 cyclopentadienyl group bearing a substituent of one to four alkyl groups of tetrahydrininyl or Ae sane (Jia Carbon atoms; or indenyl group; group to 1 of one to four alkyl groups of Show a fluorenyl group can carry 0 to 1 of Son a cyclopentyl group or a cyclopentyl group bearing 83 ar; carbon atoms; methyl or ethyl group. The most preferred compound in particular is dipentylcyclodeethoxysilane or dipentylcyclodeethoxysilane or dipentylcyclodeethoxysilane. In the present invention, it may effectively protect the catalyst for the above-mentioned olefin polymerization 01 parts part by weight; preferably from 0.59 to 01 to 1.1 which also has about a part by weight of said catalyst in vapor phase polymerization equipment of 001 by weight; on the basis of blockages. Vapor phase polymerization equipment with a feed efficiency of about 1000 m; Yeo reducer to 1 to 5060 gfa m (ppm); It is preferred from 1 surface tension depending on the polymer powder continuously or intermittently for such portions when the polymer powder flows into vapor phase polymerization equipment where it is polymerized using the aforementioned olefin polymerization catalyst. Examples of a reducer are included. surfactants ionic surfactants such as high molecular weight alcohol sulfate; Ethylene oxide sulfate (Aled) is a sulfate to a higher molecular weight alcohol; phosphate high molecular weight alcohol; phosphate from the addition of ethylene oxide to a higher molecular weight alcohol; Cationic surfactants of the type of quaternary ammonium salt and amphoteric surfactants of the betathine type and surfactants other than “Jia” compounds containing 11L (11:011:0©)- or 1L (011:01)011 ethers (0)-(provided that Jie is ionic ©

Yoav vs Glycerine Monostearic Acid Ester; a glycerine dimethyl ester; Ester (Ye to “triglycerine fatty acid; fatty acid ester of diglycerine”; ester of fatty acid from the addition of ethylene oxide to a high molecular weight alcohol; poly(ald) ester of poly-7 (SENN) 7-hydroxyethyl) aliphatic amide” SEEN fatty acid of a polyalcohol; (7-hydroxyisopropyl) aliphatic amide. SENN hydroxyethyl) aliphatic amide 0 In the continuous vapor phase polymerization process according to the invention; Polymerization (principal polymerization) in the presence of the above-mentioned catalyst and preferably, the primary polymerization to be described below takes place prior to the primary polymerization. Lad at least part of an organoaluminium compound (B). This © can be made from or all of the catalyst component of the organosilicon compound (C). The concentration of catalyst used in the initial polymerization can be much higher than the concentration Typically the concentration of the solid titanium (a) catalyst component in the polymerization is in the range of 100 mmol; the best is from about 0.05 to Yoo to 1.01 starting from about

Ga in terms of titanium atoms per liter of inert hydrocarbon medium will be described as No oJ se

SiS and as intended; The amount of the catalyst component of organoaluminum compound (B) is 1 g; On the basis of 01 to 1.7 preferably from aa 5000 to 11 mol polymer preparation; Preferably from 100 to 11 titanium catalyst component steel (A) and usually from about 100 to 1000 moles per mole of titanium atom contained in titanium catalyst component is about 1.89 © steel (A). Better, the primary polymerization is carried out by adding an olefin and the catalyst components mentioned above to an inert hydrocarbon medium and reacting the olefin under mild conditions. oli, propane, butane, and jie are aliphatic hydrocarbons

0 &kerosene; cycloaliphatic hydrocarbons such as cyclopentane; cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene; toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and mixtures thereof. Among these hydrocarbons, aliphatic hydrocarbons are preferred. In the present invention; A liquid olefin may be used in place of part or all of the inert hydrocarbon intermediate. The olefin used in the initial polymerization of Slee may be or be different from; Olefin should be used in the main polymerization. And when the olefin is used in the polymerization (AHN), a polymer with a high degree of crystallinity can be prepared from alpha-olefin with ? to 01 carbon atoms”; preferably who? to 01 carbon atoms. The reaction temperature of the prepolymerization is such that the resulting prepolymer essentially formed does not dissolve in the inert hydrocarbon medium. in a desirable way; sale ranges from about minus 01 to 01 (degrees Celsius); Preferably from about 01 to Av cau, and the best is from Safar Mathwi to 50 dm. vo and hydrogen molecular weight adjusting agent Jie can be used in the initial polymerization. vocally; The molecular weight adjusting factor is used in such an amount as to ensure that the prepolymerized polymer has an autoviscosity [on] measured in decalin at 126 dM; about SY dL/g; The best is from about 159 to 100 dL/g. The initial polymerization proceeds as desired so as to form about 0.1 to 00001 g; © and preferably from about 1.7 to 5060© can of polymer per gram of titanium catalyst component (1) and if the amount of polymer produced by the initial polymerization method is large fan, the effectiveness of the olefin polymer production in the main polymerization can be reduced in some cases Sometimes, when the resulting olefin polymer is molded into a film and the like, fish eyes may form. The initial polymerization can be done in batches or continuously.

"

After the initial polymerization as mentioned above or without the Ad procedure has been pre-polymerized; The primary olefin polymerization takes place in the presence of the olefin polymerization catalyst described above composed of a solid titanium catalyst component ϕ) an organoaluminium catalyst component (b) and an organosilicon catalyst component (c).

Examples include olefins that can be used in the lead polymerization; ethylene propylmen; 1-butene; These olefins can be used alone or in combination. In a preferred embodiment of the invention; Polypropylene or 1-butene homopolymerizes; or co-polymerized a mixed olefin containing propylene or 1-butene as the main constituent. And when the mixed olefin is used; sell

© Proportion of propylene or 1-butene as the main constituent (0 mol % on JV) preferably at least %V mol.

and in the continuous vapor phase polymerization process, Gd of the present invention; More specifically, the polymerization of an alpha-olefin with * and more carbon atoms can prepare a polymer that has a high steric ordering coefficient with a high catalytic activity.

in the homopolymerization or copolymerization of olefins; A compound with multiple unsaturated bonds such as an unconjugated Oe diene can be used as a starting material for the polymerization. and in the continuous vapor phase polymerization process Gy of the present invention; The catalytic component of the organoaluminium complex (b) is used in such an amount that the metal atoms in the catalytic component of the organoaluminum complex are used in an amount usually ranging from about 1 to © 00001 se (preferably from about © to 90860 edge per mole of Titanium atoms in titanium catalyst component A in the polymerization system Furthermore, the amount of catalyst component of organosilicon compound C ranges from about 12,000 to 10 mol; preferably from about 1.00 to ?mol Particularly better is about 1.06 to 1 mole in terms of Si atoms in the catalytic component of organosilicon (c) per mole of metal atoms in organosilicon (b) ve. ‏

a in the continuous vapor phase polymerization process; A catalyst component of an organoaluminium compound (b) and a catalytic component of an organosilicon titanium compound (c) can come into contact at the same time as the main polymerization or before the main polymerization. And in this contact before the main polymerization; It can select any two desired components and touch them together. alternatively; Parts of only two or three components can come into contact with each other.‎ 0 of the invention; Both catalyst components can come into contact before polymerization in Ga and in the process are inert; or in an olefin medium. Sle medium and when the catalyst component of the organo-aluminum compound (b) and the catalyst component of the organosilicon compound (c) are partially used in the primary polymerization; The catalyst that has undergone primary polymerization is used with the remaining components of the catalyst. The prepolymerization catalyst may contain the prepolymerization product. The use of hydrogen at the same time as the primary polymerization enables the control of the weight and in this case the molecular le of the resulting polymer; The resulting polymer has a magma flow rate which decreases both the spatial arrangement coefficient of the resulting polymer and the catalyst efficiency. dm; and specify 001 Yon dm; preferably from about 0 kg/cm. In the invention; it can be 00 kg/cm; preferably at about ? to 001 is the polymerization takes place Also in two or more phases under different reaction conditions. The olefin polymer obtained in this way can be a homogeneous polymer, a random copolymer or a bulk copolymer. The amount of solid catalyst component is high; the residual amount of catalyst in the polymer can be relatively low; a process can be omitted to remove the catalyst from the polymer (ll) and in particular its halogen content. According to mold corrosion can be effectively prevented when forming olefin polymer output to materials

Furthermore; The olefin polymer produced using the Gay catalyst of the invention contains a small amount Tan of an amorphous polymer component and therefore a small amount of a soluble hydrocarbon component. accordingly; A film formed from this polymer has a low surface viscosity. and when an olefin polymerization catalyst according to the invention is used for copolymerization of an olefin; 0 The resulting copolymer has a narrow composition distribution. According to the present invention; The continuous vapor-phase process of polymerization of the olefin is carried out using a special polymerization catalyst composed of a solid titanium catalyst component ϕ) an organoaluminium composite catalyst component (b) and a special organosilicon catalyst component (c); and then; It not only prevents clogging of vapor-phase polymerization equipment but also produces a polymer with a high steric ordering rate of Je production rate (SUI) when the polyolefin produced by the continuous vapor-phase polymerization process according to the invention has excellent particle size distribution properties; particle diameter and bulk density and also has a small amount of soluble hydrocarbon component and has a small composition distribution. The following examples are the present invention more specifically without any intent to limit the invention to these examples. 17 liters of 7-ethylhexyl alcohol at 16 d.m. for © hours to form a homogeneous solution. 1 kg L was added

of phthalic anhydride to the solution; and mix with stirring at 111 dm for an additional 1 hour to dissolve the phtalic anhydride in the homogeneous solution. The resulting homogeneous solution was cooled in this way to room temperature and 41.4 liters of the solution was added dropwise to 1110 liters of titanium tetrachloride and the solution was maintained at Yo 0 blood below zero over a period of time of 5 hours. and after the addition point by point; The temperature of the resulting solution was raised to 10 dC in two hours; When the temperature of the solution reached 0 dC; 4 kg of di-heptyl phthalate was added. and then; The temperature of the solution was raised to 7 dC in 1.1 hours; At the mentioned temperature, the solution was stirred for one hour. and then; The solid part was collected by filtration on (All) and the solid part was re-suspended in “WY. liter of titanium tetrachloride” and the temperature of the suspension was raised to 110 dm. When the temperature of the suspension reached 110 dm; added 1.44 kg of diisobutyl phthalates and stirred for a period of minutes at this temperature. After lll the solid part was collected again by hot filtration. After repeating these process steps (suspending in titanium tetrachloride, raising the temperature; adding diisobutyl phthalate) more than twice washing the resulting solid part with hexane (ae) until no titanium was detected in the washing products. The composition of the catalyst component of the solid titanium obtained in this way consisted of 767.4 by weight of titanium » 7061 by weight of magnesium; 0% by weight of diheptyl phthalate and 9615 by weight of diisobutyl phthalate.9 The polymerization of propylene was carried out using fluidized bed continuous vapor phase polymerization equipment at a JS pressure of YY kg/cm’.c, a residence time of 707 hours and a polymerization temperature of 8 dm and a linear gas velocity of 50 cm/sec. 1.176 mmol/h of the catalyst prepared above on the basis of titanium atoms” was added continuously, 11 mmol/h of dipentylcyclodemethylsilane and 17 mm - mole/hour of triethylaluminum YY kg/hour of propylene Wo l/hour of RY hydrogen (05 liters/hour) of nitrogen into the reactor. And at that moment; The composition of gas 70 » 31 in the polymerization reactor consisted of propylene hydrogen with a gram molecular ratio of 9677 mol propylene.

MFR kg/h of a propylene polymer with properties such as 16.5 obtained (oll dag by (LL) minutes) residues of p-heptane extraction at a boiling point of 0 g/#01 volume 0 g/mL. 1.47 by weight and an apparent specific gravity of 64.5. The polymerization was well balanced and no blockage occurred during the polymerization period. Example (?) Preparing a solid titanium catalyst component The homogeneous solution of magnesium chloride/7-ethylhexyl alcohol/phthalic anhydride x was cooled to room temperature; 41.4 L of (1) was added to the product in the same way as in the example L of titanium tetrachloride and the solution was kept At 171, the solution was reduced drop by drop to hours, and after adding it drop by drop, 1 dm rose below zero during a period of time that reached TE within hours, and when the temperature of 011 pa reached the temperature of the resulting solution to kg of diisobutyl phthalates At this temperature 1.7 aaa 011 was added to the solution and the solution was stirred for 0,000 hours. and then; collection of the solid part by hot filtration; A liter of titanium tetrachloride was returned. Then the temperature was raised to 177. The suspension of the solid part was raised in: d.m.; The suspension was stirred for one hour. And after collecting the solid part again, 0111 suspended to, by hot filtration; Washing the solid part collected with hexane until no titanium is detected in it; Washing products. 707.4 The composition of the solid titanium catalyst component obtained in this way consisted of titanium by weight » 96148 by weight of magnesium and 9617 by weight of diisobutyl phthalate. 101 ang rr Polymerization of propylene was carried out Using continuous vapor-phase polymerization equipment with a layer of 2 hours, a polymerization temperature of eli, kg/cm, and a time of YY, fluidized JIS at a pressure of dm, and a gas linear velocity of 50 cm/sec. 9 mmol/h of the catalyst prepared above on the basis of 1.97 mmol/h of dipentylcyclodemethoxysilane and 7 mmol/h of titanium atoms was added continuously. 0 aluminum” and 71 kg/hr of propylene” BI mol/hr of trihydrogen and *,1 L/hr of nitrogen into the reactor. And at that moment; The composition of gas 01 » Ye in the polymerization reactor consisted of hydrogen/propylene with a gram molecular ratio of 7677 mol and propylene with a molar ratio of 7677 mol.

MFR Jie kg/h of a propylene polymer has properties of 16.1 and as a result, 1 by (LL) is obtained at the boiling point lao minutes; Residues of extraction 101/mg amount by weight and an apparent specific gravity of 0.48 g/mL. 17 The polymerization was well balanced and no blockage phenomenon occurred during the polymerization period. (3) Example Primary polymerization > L. Add 100 L of hexane to a nitrogen-cleaner reactor with a capacity of 100 mol of triethylaluminium, 7 mol of dipentylcyclodemethylsilane and 1 mol 0 based on titanium atoms; of titanium catalyst component The steel whose synthesis was carried out in the weight d.m., an initial polymerization was carried out and a rate of 01 was determined, and then, by feeding propylene to the solution at (VY) feeding propylene at a rate sufficient for polymerization ?g of polymer per gram of catalyst steel polymerization - Preliminary for a period of hours After the primary polymerization, the liquid part was removed by filtration, and the separated solid part was dried. Residency of two hours and a polymerization temperature of YY. JIS fluidized at a pressure of cm/sec. 500 bp and a linear gas velocity of 8 mmol/h of the catalyst prepared above on the basis of 0101 and added continuously ,

0 titanium atoms” YY mmol/h of dipentylcyclodemethoxysilane and 1110 mmol/h of triethyl casas and 77 kg/h of propylene” 01 l/h of hydrogen and*, 0 liters/hour of nitrogen into the reactor. And at that moment; The gas composition in the polymerization reactor consisted of hydrogen/propylene with a molecular ratio of © » 701 and propylene with a ratio of 7614.

0 and as a result” he obtained 16.7 kg/hr of a propylene polymer with MFR Jie properties of VE g/0 min; The residue of p-heptane extraction at boiling point (IL) was 9697 by weight and an apparent specific gravity of 1.44 g/mL.

The polymerization was well balanced and the phenomenon of blockage did not occur during the polymerization period. Yoav

Claims (1)

rs Claims A continuous steam-phase process for polymerization of olefin comprising the polymerization or copolymerization of 1-01 olefins in the presence of Y an olefin polymerization catalyst composed of (1) (a) a solid titanium catalyst component containing magnesium ; titanium and halogen as basic ingredients; (b) an organoaluminum complex catalyst; and SiR'Ry(ORY), (c) 3l where L8 and L82 represent a cyclopentyl group; Cyclopentinyl group; cyclopentadiethyl group; A cyclopentyl group bearing one to four substituents of alkyl groups A to ; carbon atoms 1 to 4 Cyclic pentinyl substituent bearing group has 3 to ; carbon atoms A cyclopentadienyl group bearing a substituent of 1 alkyl groups having from 10 to ; carbon atoms or an ethinyl group; 1 to four alkyl groups having from 1 Soa a tetrahydrindenyl group or a fluorenyl group can carry (ula) a VY group to ; carbon atoms 1 represents group 1 of one to four alkyl groups with 1 methyl or an ethyl group. in vapor phase to prevent equipment blockages; In Y the presence of an olefin polymerization catalyst formed from r(a) a solid magnesium-containing titanium catalyst component; titanium and halogen as basic ingredients; ¢ (b) an organoaluminum complex catalyst; f ° SIR'R*(ORY), (C) 5 cyclopentyl group cyclopentynyl group; RP group where !8 and v are cyclopentadienyls; A cyclopentyl group bearing one to four substituent alkyl groups A Yoav 4 by 1 to ; carbon atoms a cyclopentenyl group bearing one to four z-substituted 1 alkyl groups having from 1 to ; carbon atoms A cyclopentadienyl substituent group has from 1 to four alkyl groups having from 1 to ; carbon atoms or an indenyl group; VY indanyl group” a tetrahydroindenyl group or a fluorenyl group can carry a substituent” from one to four alkyl groups having 1 to 1 carbon atoms; RO represents a Ve methyl group or an 1 ethyl group. *- A continuous vapor-phase process for the polymerization of a Gay olefin of protection claim (1) or (7)” where Y the aforementioned titanium solid catalyst component also includes an electronegative in addition to 1 magnesium; titanium and a halogen. 1; - A continuous vapor-phase process for the polymerization of an olefin according to any of the claims of protection from (1) to Cus oY) the catalyst component of organic aluminum compound (b) is used in an amount of 1 to 001 v mol in terms of metal atoms contained in component (b) based on 1 mole of a titanium atom present in titanium catalyst component (a) in the polymerization system ADAM 0#- continuous vapor phase process for the polymerization of an olefin pursuant to any of the claims of 1) ( to o£) X where the catalytic component of organosilicon (c) is used in the amount of 0.000 to 0 Y mol in terms of 5 atoms present in component (c) for each metal atom present in the catalytic component of the compound organic aluminium (b). Cus A polymer of crystallinity Alle is prepared by an initial polymerization of an alpha-olefin with 1 to 0 carbon atoms using solid titanium catalyst component (a) in combination with at least part t of the catalytic component of an organoaluminium (B). 101 inca Ale-7#0 continuous vapor-phase polymerization of an olefin in accordance with any of the claims from (1) to 0” () Y, where said electron transfer material is dipentylcyclodemethoxysilane 1-Dicyclic Jy Dicyclotoxisilane. =A process aid is a vapor phase polymerization equipment from blockages and includes polymerization or polymerization in form Y Co-Olefins Continuously Using Continuous Vapor Phase Polymerization Equipment'; in v The presence of an olefin polymerization catalyst formed from (i) a solid titanium catalyst component containing magnesium, titanium and halogen as primary ingredients; (b) an organoaluminum compound catalyst component; And 1 )—( Warta 2)0 5105 v, where L8 and RP represent a cyclopentyl group”; Cyclopentinyl group; group A cyclopentadienyl; A cyclopentyl group substituently carries one to four alkyl groups 4 by 1 to ; carbon atoms Pentinyl ring holds alternate from one to four sets 0 alkyl groups with 1 to ; carbon atoms A cyclopentadienyl group bearing a substituent of 1 to four alkyl groups having 1 to ; carbon atoms or an indenyl group; Soa an indanyl group» a tetrahydroindenyl group or a fluorenyl group can carry VY 11 from one to four alkyl groups having 1 to ; carbon atoms RP represents a group Vi is an ethyl group or instance. Gadde -1 for protection claim (A) where Lad includes said titanium steel catalyst component l Electron plus magnesium; Titanium and halogen. -01 Gig process for protection claim (A) (4) where the catalyst component of organic aluminum ro compound (B) is used in an amount of 1 to 7006010 moles in terms of the metal atoms present in component (B) on ‎YodyVv Ya v basis 1 mole of titanium atom present in the titanium catalyst component (1) in the polymerization system. of Y is an organosilicon compound in the amount of 1.001 to 01 moles in terms of: 5 atoms present in the ¥ component (c) for every mole of metal atom present in the catalytic component of the organosilicon compound ¢ (=<). ~ -\Y \ a process in accordance with any of the claims from (A) to 11' where a catalyst for the polymerization of aptd is prepared for a polymer with a high degree of crystallinity by carrying out an initial polymerization of an alpha-olefin in it from * to 01 OST atoms using said solid titanium catalyst component (1) in combination with at least a portion of the catalytic component of organoaluminum compound (B). to (VY) where said electron solvator Y is dipentylcyclodethoxysilane and dipentylcyclodethoxysilane. Vidqy