TW379231B - Process for the (co) polymerization of olefins - Google Patents

Description

A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (f) 1 1 The present invention is a multi-step process for the polymerization of olefins 1 1 2 = CHR polymerization in two or more reactors. R is hydrogen or an alkyl group, IS group, or aryl group with 1 I and 1-1 sulfonium atoms. At least ___ 値 r-n 1 1 please in the reactor > — »or A variety of these olefins are polymerized in the presence of a catalyst. See 1 I 1 # 1 combination reaction. This catalyst contains an alkyl-aluminum compound and titanium supported on an active halogen substrate. And / or the reaction product 9 of a vanadium compound to obtain —- 1 species | olefin polymer 〇 in at least — 'other reactors will be the first anti-boxing 1 | _ XM-1 reactor operation Medium% deactivation in this species Hydrocarbon polymer and% 1 products containing at least --- 値 M-71 bond transition metal compound contacted with fte (when this page is present 1) Existing polymerization of ___ 'or more such olefins Cfi 2 = CHR I | Reaction 9 to obtain a new polymerization composition directly from the reactor Ο 1 | From the multi-step system for olefin polymerization known in the patent literature-1 1 method> it is two frn or more Polymerization in the reactor 9 and this-Order 1 is also a topic of particular interest in practical industrial applications. 0 In any reactor 1 1 * Independently change process parameters (such as temperature, pressure, act early species 1 1 The concentration and the concentration of hydrogen or other molecular weight regulators) are possible 1 | properties can be controlled in the composition and the properties of the final product 9 provide more bomb-M® 'linear 0-1 1 in multiple steps The method is usually used in different steps / reactors 1 | The catalyst used is the same: the product 1 obtained in a reactor is discharged 1 and sent directly to the next step m / reactor * without Change the nature of the catalyst. I 1 Multi-step process can be applied (for example) to the preparation of olefins (co) polymers with broad molecular weight distribution (MWD) 1 1 9 It is used in different reactors |- 3 1 1 1 1 This paper size applies the Chinese National Standard (CNS) A4 specification (2iOX297 mm) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 'B7 V. Description of the invention (>) Produce polymers with different molecular weights Ingredients. The molecular weight in each reactor, as well as the MWD range of the final product, is usually controlled by a molecular weight regulator of different concentration, and such regulator is preferably hydrogen. The multi-step method can also be used for the preparation of highly impact resistant propylene copolymers, which is obtained by continuously polymerizing a mixture of propylene and propylene with ethylene. In the first step, propylene is pseudo-polymerized or copolymerized with a small amount of ethylene and / or olefins having 4-10 sulfonic atoms to obtain a stereoregular polymer; in the second step, the ethylene A mixture of propylene is polymerized in the presence of the catalyst-containing polymer obtained in the first step to obtain a polypropylene composition with improved impact strength. This type of method is described in U.S. Patent No. 4,521,566. In this patent, a polypropylene composition with high impact strength is conventionally prepared in a multi-step process, which includes at least one homopolymerization step of propylene, and at least one polymerization step of ethylene / propylene mixture, in In both steps, the reaction is performed in the presence of a catalyst containing a titanium compound supported on the active magnesium halide. In the European patent application EP-A-433989, a method for preparing a polypropylene composition is described which contains 2G to 99% by weight of a crystalline (co) polymer, and the crystalline (co) ) The polymer contains at least 95% by weight of propylene units; and 1 to 80% by weight of S: amorphous ethylene / propylene copolymer, in which the amorphous copolymer contains 20 to 90% by weight of ethylene units. This production method is carried out in two steps: in the first step, the liquid propylene is injured, and crystalline propylene is produced (total) -4-------;-;-equipment-(please first Read the note on the back ir ^ write this page) The size of the paper for this guideline is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (y) 1 1 The amount of polymer produced in the first polymerization step (i) is preferably between 1 1 and 9 relative to the total amount of polymer produced in steps (A) and (C). 0% by weight, and more preferably between 2D and 80% by weight. 1 | Please I The catalyst used in the first polymerization step U) includes the following: First, the reaction product between 1 and 1 1 • Back surface 1 I () A solid component 9 which includes a transition metal selected from titanium or vanadium. Note I • The compound is supported on an active magnesium halide. Do not contain transition metal dimple Μ1 - π bond square This solid component may also contain X An electrical sub-fill of bonding thereof to the body (the inner portion to the body). Generally speaking, this internal precursor is used when 1 part of the solid writing page is used to prepare the steric 1 I specific polymerization medium for propylene, 1-butene and similar α-olefins, 1 | Because it must have high stereospecificity to obtain polymers with a high isotactic index of 1 1 to 90-(ii) an alkyl-aluminum compound, and--electron donor compounds (外 II 部 予Body 9 This kind of compound can be used selectively) 〇1 1 When a stereoregular polymer 1 is formed in the first polymerization step U) [(for example, a propylene polymer with a high isotactic index (is 〇ta cticity in dex) ) Time 9 This type of external prosthesis is used to provide the high three-dimensionality required by the catalyst-1. I to be heterosexual. 0 demon »When the European patent application EP-A-3 6 14 9 No. 3 _ 1 I 逑When the diethers are used as internal donors, the three-dimensional treatment of the catalyst itself is high enough, and the use of external donors is unnecessary. 1 1 From the patent literature > Active magnesium halide (preferably 1) is known as active magnesium halide, which can be used as the carrier of Zieger-Na-tta catalyst. US Patent No. 1 1 4 , 2 9 8, 7 1 8 and 4. 4 9 5, 3 38 first -8 ~ first proposed to use these compounds for 1 1 1 1 1 This paper size applies Chinese National Standard (CNS) A4 specifications (210X297) (%) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) Polymer; In the second step, it was performed in a hydrocarbon solvent to produce an amorphous ethylene / propylene copolymer. In both steps, the same catalyst is used, which is composed of a chiral metal dicyclopentadiene and an alumoxane. In European Patent Application EP-A-433990, a A two-step process for preparing a propylene-based polymer composition similar to that described in European Patent Application EP-A-433989. In the first step, crystals are formed by conducting a polymerization reaction in liquid propylene. Propylene (co) polymer; in the second In step, by a gas phase polymerization reaction, the raw ethylene / propylene copolymer become amorphous. Also, in this example, the catalyst used in the two reactors is the same, and it looks like it consists of a metal dicyclopentadiene and an aluminoxane. In German patent application DE 4 1 3 0 4 2 9 a multi-step process for producing block copolymers is described, which is carried out entirely in the gas phase. In the first step, a propylene homopolymer or copolymer matrix was produced, which contained 45 to 95¾ of the total product weight. In the second step, a previously prepared polypropylene matrix and The catalyst used was reacted in the presence of the catalyst, and an ethylene / cr-olefin copolymer was prepared, which contained 0.1 to 79.9% by weight of ethylene units, and its amount comprised between 5 and 55¾ of the total product weight. . In both steps, the same metal dicyclopentadiene catalyst is used to carry out the reaction in the gas phase. The current methods in this field have various limitations. One limitation is due to the use of the same catalyst in different method steps, so that the product characteristics obtained in each step are not always the best condition --- ---; --j-^ ------ 1T ------ ^ t-(Please read the precautions on the back of this page to write this page) A paper size applies to the Chinese National Standard (CNS ) A4 size (210 X 297 mm) A7 B7 Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4-) 1 1 〇 Example 9 If using a multi-step method 1 1 Diene titanium-based catalyst to prepare heterogeneous copolymers 9 The properties of the rubber copolymer made in the second step 1 1 are very poor. 0 This catalyst is known to be 1 | Please 1 Ethylene / propylene copolymers with fairly long identical monomer unit bond segments First, smell 1 1 Λ 1 9 The result makes the product elastic Poor quality. Back 1 I have now found a multi-step production method 9 which can prepare a variety of olefin polymerization. Note I Converged composition 9 and use different catalysts in different steps in each step.% Tong 1 1 〇 Special What is • The method of the present invention includes the first --- step and --- 値 %% write this page 1 1 two steps »where the-step is in the presence of titanium or vanadium instantaneous 9 to make an olefin polymer And in the second step > deactivate the sister media used in 1 | in the first stage and the third step is in the olefin polymer 1 1 and the transition metal M containing at least one 値 Μ-π bond ( Selected from the group consisting of titanium, strontium, vanadium- 1 or 1) compounds and / or their reaction products in the presence of 9 polymerization 1-order I or more olefins, such olefins can be polymerized with the olefin polymerized in the first step The hydrocarbons 1 1 are the same or different. 0 1 1 The characteristics of the method of the present invention include 1 I (A)-a first polymerization step »where one or more of these olefinic lines CH 2 = CHR in one or more reactions Polymerization in the reactor 9 It is like polymerization in the presence of a catalyst containing a reaction product of an alkyl alkyl-aluminum compound and a solid component. The solid component contains a transition that does not contain a 1 M ~ K bond. A compound of metal M1 (selected from titanium or vanadium) 9 and 1 | An active form of halogenated m is $ to produce an olefin homopolymer or 1] copolymer 9 1 1 (B) processing steps 9 of which in the -6th痼 In the polymerization step (Α) 1 1 1 1 1 This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) V. Description of the invention (r A7 B7 The product will be (regardless of the order): Deactivation of the catalyst present in step (A) The obtained (a) contacted with the compound (b) and a transition gold and an alkyl M are selected from the group consisting of (C) a second polymerization inverse to the product obtained in one or more reactors. The olefin produced by one of the slivers is expressed as) a hydrocarbon homopolymer or more than 5%, and preferably. In the first place, there are large pores because the porosity situation is damaged by the polymerization reaction. It has a pore size (contact with the compound described below and a selective aluminum compound contact, and this transition metal has at least one μM-π bond of titanium, vanadium, a junction and a feeding step, One or more of these olefins are polymerized, and the polymerization reaction is performed under the conditions of the processing step (B). In the porosity of the copolymer in the first polymerization step (A) (the percentage of voids is More than 10¾ is preferred, and more than 15¾ is the polymer produced in (A), preferably it has pores with a porosity of more than 40%, which is usually greater than 1 00 0 0 angstroms. The percentage is expressed) And the distribution of the hole radius to determine the mercury method. Please read and read the service _ I lift r 'I binding line when the step is printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. In the air, when the material gathers, the co-gelatinous rubber gap WJ 孑 1 will be formed. The product is synthesized. (C) The riu of the production question will be met in the future. {Without a sudden and good Ucheng The more sudden body is step Gu Ke Ying Ke \ reverse per gram he \ 00 Juke 30 100 is the 10th largest in a large and constant flux of agglomerates into the health of the place. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ) A7 B7 Consumption cooperation by employees of the Central Bureau of Standards of the Ministry of Economic Affairs. Printing 5. Description of invention (r) 1 IZ i eg 1 er-N a 11 a. Catalytic effect from these patents. The active magnesium halide of the medium carrier or co-costadium carrier is characterized by 1 I X-ray optical resonance, which appears in the inactive halide, and the strongest diffracting rays in the S 1 1 spectrum will Reduces the intensity, and is replaced by an aperture. Read 1 | Read 1 1 instead > Compared with the strongest ray 9, its maximum intensity will be shifted to the lower back 1 I angle direction 0 tamping | | I transition The compound of gold tincture M1 is preferably selected from the group consisting of: titanium halide, halogenated beforehand _ 1 titanium VC 1 3, VC 1 4 Λ V0C13, vanadium halide. K 1 Among the hafnium-titanium compounds, T iC 1 4, T i C 1 3 and chemical formulas are preferred. The formula is Ti (OR 1) m Xr α, where RI is 1- 12 1 I sulfonic hydrocarbon group or -C0R I group, X is halogen, and 1 I (ΗΪ + η) is the valence of titanium. -1 1 The catalyst component (i) is preferably used in the form of spherical particles, and its average diameter is between about 10 and 150 cm. A suitable method for preparing this spheroid into 1 I parts can be found in European patent application EP-A -3 9 5 0 8 3, 1 1 EP -A -5 5 3 80 5 and EP-Α-5 The content described in No. 5 3 8 0, which is about 1 [the narrative content of the preparation method and product characteristics is here and referred to herein.] Examples of the internal internal compound are ether, ester, and polycarboxylic acid. Ester-Class 1 1, Amines, Ketones and European Patent Applications EP-A-3 6 1 493, EP--1 1 A- 3 6 14 94, E-A- 3 6 2 7 05 and EP -A -4 5 1 645 The 1,3-di1 ethers mentioned in the above description 0 1 I Alkyl-aluminum compounds (通常) are usually selected from trialkyl aluminum, such as triethyl-1 Ϊ aluminum, Triisobutyl-aluminum, tri-n-butyl-aluminum λ tri-n-hexyl-aluminum and 1 1-n-octyl-aluminum. Trialkyl--9-aluminum and alkyl-aluminum halides can also be used. 1 1 1 1 1 This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm). Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Print A7 B7 V. Description of the invention (Xuan), a mixture of alkyl-aluminum hydride or alkyl-aluminum sesquigas, such as AlEt2 C1 and Al2 Et3 Cl3. The external donor may be the same as or different from the internal donor. When the internal donor is an ester of a polycarboxylic acid (such as phthalic acid), the external donor is a silicon compound selected from the chemical formula Ri R2 Si (OR) 2 Preferably, Ri and R2 are an alkyl group, a cycloalkyl group or an aryl group having 1 to 18 large atoms. Examples of such silanes are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane, methyltert-butyldimethylsilylsilane, and dicyclopentyldimethoxysilane. The transition gold 羼 M compound used in process step (b) is selected from the group consisting of titanium, vanadium, tungsten and a given compound having at least one 値 M-π bond. Such a compound preferably contains at least one fluorene ligand L, which has a monocyclic or polycyclic structure containing a conjugated π electron, and is coordinated on top of the golden ridge M. The titanium, vanadium, zirconium or a given compound is preferably selected from components having the following structure: CptMR ^ R ^ (I) Cp'Cp ^ R ^ R ^ (II) (Cp'-A.-Cp ^ MR'.R2 ,, (HI) where M is titanium, vanadium, junction, or hafnium; Cp1 and Cp11 are the same or different, and are cyclopentadienyl or substituted cyclopentadiene groups. Two or more fluorene substituents on a pentadiene group may form one or more rings having 4 to 6 sulfonic atoms; R1, R2, and R3 may be the same or different, and are hydrogen, halogen, and 1- 2Q sulfonyl alkyl or alkoxy group, aryl group with 6-20 master atoms, alkaryl group or aralkyl group, 1-20 -1 0-one gutter (please read the note on the back first ^ /, Fill in this page) A paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A7 B7 V. Description of the invention (9) The tritium radical of all atoms, allyl, containing a silicon Atom substituents; A is an alkenyl bridge or a group having the following structure: R1jM1——R1 112 R——M——RI 1 2R'— c tn I o ·-1 1 2 RIM — R t 0 1 1 1 2 RI M-RI 112 R 1 Mir

R1 1 A -Ge-, -Sn-, -0-, -S-, = S0, = S02,: Yang ,, where mi is silicon, germanium or tin; 1 and 1? 2, same or different, Is an alkyl group having 1-4 nitric atoms or an aryl group having 6-10 fluorene atoms; a, b, and c are each independently an integer from 0 to 4; e is an integer from 1 to 6, and R1 There are two or more ridges in the basic garden of R2, R2 and R3 to form a ring. If the Cp group is substituted, the substituent is preferably an alkyl group having 1 to 20 値 硪 atoms. Examples of compounds with chemical formula (I) include: ---------- Package-Ink--(Please read the notes on the back first and fill out this page) -8 (Me5Cp) MMe3, (Me5Cp) M ( OMe) 3f (MesCp) MCl3, (Cp) MCl3, (Cp) MMe3, (MeCp) MMe3, (Me3Cp) MMe3 / (Me4Cp) MCl3f (Ind) MBenz3, (H4Ind) MBenzj, (Cp) MBu3. It has the chemical formula ( II) Examples of compounds include: (Cp) 2MMe2, (Cp) 2MPh2, (Cp) 2MEt2 / (Cp) 2MC.l2 / (Cp) 3M (OMe) Λ > (Cp) 2M (OMe) Cl, (MeCp) 2MCl2, (Me5Cp) 2MCl2, (Me5Cp) 2MMe2, (Me5Cp) 2MMeCl, (Cp) (Me5Cp) MCl2, (l-MeFlu) 2MCl2, (BuCp) 2MCl2, (Me3Cp) 2MCl2, (Me4Cp) 2MCl2 / (Me4Cp) 2MCl2 / 2M (OMe) 2, (Me5Cp) 2M (OH) Cl, (Me5Cp) 2M (OH) 2 / (Me5Cp) 2M (C6Hs) 2, (Me5Cp) 2M (CH3) Cl, (EtMe4Cp) 2MCl2, -1 1 -This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm)-Line-Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs and printed by the Consumer Standards of the Central Standards Bureau of the Ministry of Economic Affairs. Printed A7 B7 5. Description of the invention (· °) [(C6H5) Me4Cp] 2MCl2 / (Et5Cp) 2MCl2, (MesCp) 2M (C6H5) Cl, (Ind) 2MCl2, (Ind) 2MMe2, (H4Ind) 2MCl2, (H4Ind) 2MMe2 / {[Si (CH3) 3] Cp} 2MCl2, {[Si (CH3) j] 2Cp} 2MCl2, (Me4Cp) (Me5Cp) MCl2. Examples of compounds with chemical formula (melon) include: C2H4 (Ind) 2MCl2, C2H4 (Ind) 2MMe2, C2H4 (H4Ind) 2MCl2, C2H4 (H4Ind) > MMe ,, Me2Si < Me4Cp22SiCl, Me Me4Cp) 2MMe2, Me2SiCp2MCl2, Me, SiCp2MMe ;, Me2Si (Me4Cp) 2MHeOMe, Me2Si (Flu) 2MC12; Me2Si (2-Et-5-iPrCp) 2MCl2, Me2Si (H4Ind) 2MCl2, Me2Si (H4Flu) 2MC Ind) 2MCl ,, Me? Si (2-Me- H * Ind) 2MCl2, Me2Si (2-MeInd) 2MCl2 / Me2Si (2-Et-5-iPr-Cp), MCl ?, Me2Si (2-Me-5 -EtCp) 2MCl2, Me2Si (2-Me-5-Me-Cp) 2MCl2, Me, Si (2-Me-4,5-benzoindenyl> 2MC12, Me2Si (4,5-benzoindenyl) 2MC12 , Me: Si (2-

EtInd) 2MCl2f Me2Si (2-iPr-Ind) 2MCl2 / Me2Si (2-tert-butyl-Ind > MCL, Me2Si (3-perse-butyl-5-MeCp) 2MCl2, Me2Si < 3-to-butyl -5-MeCp) 2MMe ”

Me2Si (2-MeInd) 2MCl2 / C2H4 (2-Me-4,5-benzobenzoyl)> 2MCJL2, Me2C (Flu) CpMCl2, Ph2Si (Ind) 2MC12 / Ph (Me) S i (Ind) 2MC12 / C2H4 (H41nd) M (NMe2) OMe, isopropylidene- (3-tert-butyl-Cp) (Flu) MCl2, Me2C (Me4Cp) (MeCp) MCl2, MeSi (Ind) 2MCl2, Me2Si (Ind) 2MMe2, Me2Si (Me4Cp) 2MCl (〇Et), C2H4 (Ind) iM (NMe2) 2, C2H4 (Me4Cp) 2MCl ?, C2Me4 (lnd) 2MCl2, Me2Si (3-Me-Ind) 2MCl2, C2H4 (2-Me-Ind ) 2MCl2, C2H4 (3-Me-Ind) 2MCl2, C2H4 (4,7-Me7-Ind) jMCl ?, C2H4 < 5,6-MP2-IncihMCM2, C2H4 (2f 4,7- Me3Ind) 2MCl2, C2H4 (3 , 4,7-Me, Ind) 2MC12 / C2H "2-Me- H41nd > zMCl " C2H4 (4,7-Me2-H41nd) 2MC12, C2H4 {2,4,7-Me3-H4Ind) jMC 12,

Me2Si < 4,7-Me2-Ind) 2MCl2, Me2Si < 5,6-Me2-InclhMCl2, Me2Si (2,4,7-Me,-H4lnd) 2MClz. _I2- This paper size applies to Chinese National Standard (CNS) A4 Specifications (210XW7)

Printed by A7 B7, Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of Invention In the above shorthand chemical formula, the symbols represent the following meanings: Me = methyl, Et = ethyl, iPr = isopropyl, Bu = butyl, Ph = phenyl, Cp = cyclopentadienyl, Ind = indenyl, H4 Ind = 4,5,6,7-tetrahydroindenyl, Flu = fluorenyl, Benz = benzyl, M = Titanium, knots, or hafnium, preferably knots. Compounds such as Μ θ 2 Si (2-M0-Ind) i Z r C 1 2 M e 2 Si (2-Me-H4 Ind) 2 ZrCl2 and the preparation method thereof can be referred to the European patent application EP-, respectively. It is described in A-485822 and 485820, and its narrative content is hereby incorporated by reference. For example, Me2 Si (3-tert-butyl-5 MeCp) 2 Zr C 1 2 and Me2 Si (2-Me- Compounds such as 4,5-benzyl group) 2ZrCl2 and the methods for their preparation can be found in U.S. Patent No. 5,132,262 and European Patent Application EP-A-549900, respectively, the description of which is here Listed for reference. The first polymerization step (A) may be carried out in one or more reactors in a liquid phase or a gas phase. The liquid phase can consist of an inert hydrocarbon solvent (suspension method) or one or more olefins CH2 = CHR (liquid phase monomer method). The gas-phase polymerization can be carried out using a known fluidized bed technique, or the reaction bed can be mechanically stirred. The treatment step (B) is preferably divided into two parts. (A) First, the polymer produced in the polymerization step (A) is contacted with a compound which can deactivate the catalyst used in the step (A), and then (b ) Contacting the product obtained in (a) with a solution of the transition metal M formed in a hydrocarbon solvent (such as benzene, toluene, heptane, hexane, liquid propane, etc.). It can be used in the treatment step (a). Examples of compounds can be selected from the chemical formula -1 3- I ---- ^ ----- ^ pack --------- order ------ line * ·-ί-| (Please read first (Notes on the back fill in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (—) Rx-i XH Compounds wherein R is hydrogen or a hydrocarbon group having 1 to 10 large atoms, X is gas, nitrogen or sulfur, and y is the valence of X. Non-limiting examples of such compounds are alcohols, thiols , Mono- and di-alkyl amines, amines, water, and hydrogen sulfide. Preferred compounds are those in which X is a gas, and among these compounds, water is also used. Other examples of compounds that can be used in process step (a) are CO, COS, CS2, CO2. 002 and alkynes or allene compounds β deactivation compounds and compounds of transition metal M 1 The better Moore number is to ensure the deactivation of the catalyst in step (A). This ratio is preferably greater than 50, more preferably greater than 150, and more preferably greater than 250. Step U) Pseudo-contacting these deactivating compounds with the polymer produced in step (A) can be performed in a number of different ways. One way is to contact the polymer with a solution, suspension, or dispersion containing a deactivating compound (using a hydrocarbon as the solvent) for 1 minute to several hours. An example of a deactivating compound dispersion in a hydrocarbon solvent is represented by humidified hexane. At the end of step (a), the liquid is removed and the polymer is used for step (b). Treatment step (b) is preferably carried out using a solution of a compound of transition metal M in a hydrocarbon solvent, and the hydrocarbon solvent contains a dissolved alkyl-aluminum compound such as triisobutyl-aluminum, Triethyl-aluminum and / or an alumoxane, such as poly (methylaluminoxane) (MA0), tetraisobutylalumoxane or tetra (2,5-dimethylhexyl) -alumoxane. The molar number ratio of the alkyl-aluminum compound to the transition gold compound is greater than 2 and preferably between 5 and 1,000. This processing step (b) can be borrowed from -1 4-(Please read the note on the back first to fill in this page). Binding. Dimensions The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Central Ministry of Economic Affairs Printed by the Bureau of Consumers of the Standards Bureau A7 B7 V. Description of the invention (0) It is carried out by suspending the polymer obtained in step (a) in a hydrocarbon solvent, and the hydrocarbon solvent contains Compounds of transition gold, and optionally containing alkyl-aluminum compounds and / or alumoxanes. Generally, the working temperature of the processing step is between Q and 100 ° C, and between 10 and A temperature between 60 ° C is preferred, and the solvent must be removed at the end of the processing step. Alternatively, the polymer (dried) obtained in (a) may be contacted with a solution of the compound containing a minimum amount of a solvent, and the amount of the solvent is sufficient to maintain the compound in the solution. The treatment step (B) may also be carried out in a loop reactor in the gas phase, wherein the polymer strips produced in the first polymerization step are circulated by a stream of inert gas. A solution of the deactivation compound and the compound of the transition metal M is sent to a loop reactor in the gas phase by, for example, a sprayer, and at the end of the processing step, a free-flowing product is obtained. Prior to step (b), the product may be treated with a compound capable of removing impurities from the system, such as an alkyl-aluminum compound. In the product obtained in the processing step (B), the amount of the compound of the transition metal M (expressed as the amount of the metal) contained in the product can be varied within a very large range. The relative amount of product to be produced in each step is determined. Usually this amount is between IX 10-7 and 5X10-3 grams of metal per gram of product, preferably between 5X 10-7 and 5X1Q-4 grams of metal per gram of product, and preferably between IX 10 -6 and IX 10-4 grams of gold tincture per gram of product is more preferred. The second polymerization step (C) can be performed in one or more reactors in the liquid-1 5- -----: ----- loading-* 'test (please read the precautions on the back I -彳 Fill in this page), 1T line paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297mm) Printed by Ai B7, T7 Engineering Cooperative Cooperative of Central Standards Bureau of the Ministry of Economy Or the reaction is carried out in the gas phase. The liquid phase can consist of an inert hydrocarbon solvent (suspension method) or one or more olefins CH2 = CHR (liquid phase monomer method). The gas-phase polymerization can be carried out in a reactor having a fluidized bed or a mechanically stirred bed. In this step (C), an alkyl-aluminum compound may be sent to the polymerization reactor, and such alkyl-aluminum compounds are all selected from trialkylaluminum, wherein the alkyl group has 1-12 sulfonium atoms; And linear or cyclic aluminoxane compounds containing repeating units-(R4) A10-, where R4 is an alkyl group having 1-12 large atoms or a cycloalkyl or aromatic group having 6-1D large atoms This aluminoxane compound contains 1 to 50 値 repeating units. In general, when the processing step (b) in step (B) is performed without an alkyl-aluminum compound, the alkyl-aluminum compound will be sent to the polymerization step (0.) The advantage of the method is that it takes into account the quality of the final product and the flexibility of the production method. In fact, the processing step (B) can make the polymerization steps (A) and (C) use different catalyst systems. In particular, when no processing is used In step (a), a large amount of polymer must be produced in step (A) to consume the activity of the catalyst itself at this stage. However, this will cause too many products from this step. As a result, this method The final product derived from step (A) accounts for the vast majority, or the final product derived from step (A) and step (C) is balanced, but the size of the polymer particles is improper. Method of the invention It can be used to prepare many kinds of olefin polymer compositions. In addition, the method of the present invention is particularly suitable for preparing highly impact-resistant polypropylene (heterogeneous copolymer of propylene). In this case, all -1 6------------ seed coat ------ ir ------ #---1 '(Please read the note on the back first / fill in this page ) This paper size applies to Chinese National Standard (CNS) A4 (2 丨 〇 X 297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention ((V) 1 1 Very long identical act carcass CIO is very early, so it is possible to obtain 1 1 copolymers with fairly good elastic properties 0- 1 I In fact, the present invention also includes heterogeneous copolymers 1 for preparing propylene | ί-I The method of the method is to read 1 I read 1 (A) __ ^ polymerization step 9 where propylene may be ethylene and / or 1 I or one or more olefins CB 2 = CHR II (where R 11 is 2 -10 hydrocarbon groups of 1 _ | meaning I m atom) > polymerized in one or more reactors, the matter of which is pseudo --- Compound, selective-a kind of electron donor 4 Filled with a reaction product of a body compound (external donor) and a solid component. This page contains 1 bm polymerization in the presence of a catalyst 9 and the solid component contains up to 1 I less— »compounds of transition metal M1 without M1-K bond (selected from 1 | titanium or vanadium) 9 —- active halogenated m and a selective 1 1 electron donor compound (internally It can obtain a kind of porosity. (Ordered as a percentage of voids) olefin polymers greater than 10, 1 I derived from white ethylene and / or CH 2 = c HR II ene smoke units with less than 1 1 2 0% by weight 9 and the pre-doped content of derivatized white propylene is greater than 80% by weight 1 1 and the insolubility in xylene is greater than 60%; line (B) is a treatment step > wherein in this step (A) The obtained product 1 will be (the order is not ΙΤΠΟ) • 1 (a) and __. Species Contact the catalyst deactivated compound 1 1 present in step (A) with 9 1 I (b) in contact with a compound of a transition metal, and optionally I with an alkyl-aluminum compound , Ίϊί ΪThe transition metal M image 1 1 Select white titanium, vanadium, knots and bonds containing at least one tilt of the M-π bond; | -1 7-1 1 1 1 This paper size applies to Chinese National Standard (CNS) A4 Specifications (210X297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) (C) A second polymerization step in which one or more dilute ®CH2 = CHR, where R is hydrogen or It is a radical, cycloalkyl or aryl group having 1 to 10 nitrate atoms, polymerized in one or more reactors, and the polymerization reaction is performed in the presence of the product obtained in step (B) to obtain The amount of the amorphous olefin (co) polymer is between 20 and 80 wt.31 compared to the total amount of the polymer produced in steps (A) and (㈧). In this first polymerization step ( Α) place The resulting polymer is preferably a propylene homopolymer with a high isotacticity index, or a propylene copolymer with a crystalline content in which the unit content derived from ethylene and / or * ^ 2 " ^ 1 ^ 1 is less than 1 〇wt%. Non-limiting examples of amorphous olefin (co) polymers that can be prepared in step (C) are elastomeric copolymers of ethylene and propylene and elastomeric terpolymers with a small proportion of ethylene and propylene, which contain derivatives derived from The unit content of ethylene is between about 30 and 70% by weight; the elastomeric copolymers of ethylene and butadiene, and the elastomeric terpolymers of ethylene, butene, and propylene 'contain ethylene-derived unit content between Between about 30 and% by weight; high molecular weight random polypropylene (7 > 1). Examples of these copolymers can be found in European patent applications EP-A-586658 and EP-A-604917, and Italian patent applications MI-93A000943, MI-93A001405, MI-93A 001406, MI- The contents of 93A001960 and MI-93A00963, and the characteristics of the product and the catalyst used in its preparation method will be listed as reference content. Polymerization step (A) can be carried out in liquid propylene in one or more loop reactors, or in the gas phase, with one or more streams having a flow _ 1 8 _ ------ -——_— ^ ------ tT ------ lacquer, *-· '* ί (Please read the notes on the back ^ —fill out this page first) This paper size applies to Chinese national standards (CNS) A4 specification (210 × 297 mm) A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (17) It is carried out in a reactor with a solidified bed or a mechanical stirred bed. The gas-phase reaction technology of a fluidized bed is a better choice. The polymerization step (C) is preferably carried out in the gas phase in one or more reactors having a fluidized bed. Other techniques can also be used (e.g. suspension polymerization or gas phase polymerization in a mechanically stirred bed). The porosity of the polymer produced in the first polymerization step (A) (which is expressed as a percentage of voids) is preferably greater than 15%, and more preferably greater than 2G%. Distribution of pore radius It has a porosity of more than 40%. It is caused by pores with a diameter of more than 10,000 angstroms. For high values of porosity, a porosity of 90 ¾ or more is preferred. It is caused by pores with a diameter of more than 100 G The amount of the polymer produced in the polymerization step (C) relative to the total amount of the polymer produced in the steps (A) and (C) is between 25% and 75% by weight as Better, and more preferably between 35% by weight and 65% by weight "The best case is: this method can be continuously operated, and in the polymerization steps (A) and (C), both gas The phases are carried out in a fluidized bed reactor, and the step (B) of glass-treatment is carried out in a loop reactor in a gas phase. The polymerization step (A) is preferably carried out in a pre-polymerization step, in which propylene Or its mixture with ethylene and / or olefins CH2 = CHRI] [the catalysts mentioned in (A) Polymerization is carried out under conditions, the amount of which is between 5 and 500 grams per gram of catalyst. The following examples are used to illustrate the present invention, but not to add the invention to this. --- Equipment-* ^. (Please read the notes on the back and fill out this page)

1T line This paper size applies to Chinese National Standards (CNS) A4 specifications (210 × 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (β) Restrictions. The properties described are measured in accordance with the following methods:-Porosity and surface area measured by M nitrogen: determined in accordance with the Beta E method (using instrument: SORPTOMATIC 1 8 0 0 manufactured by Carlo Erba) 0 -Particle size of catalyst: Its image is measured by a method based on the principle of optical emission of monochromatic laser light, using an instrument "M a 1 ve I * η I nstr 2 6 0 0". The average size is Loaded with P 5.-Melt state. Index E (Μ IE): Determined according to the method No. 431-1-0 123 8.-Dissolved state. Index F (M IF): According to ASTM-D 1238 No. method F. -Cycle 1. Ratio (-F / E): Ratio between the melting index F and the melting index E. -Solution: state index L (ΜIL): in accordance with ASTM-D 1238 No. method L.-Mobility: refers to the time it takes to flow 10D grams of polymer through a funnel. The diameter of the discharge port of this funnel is 1.25 cm, and the wall of the funnel is inclined 20 ° from the vertical direction. -Dense linen: DIN 531940 — Morphology and particle distribution of polymer particles: ASTM-D 1 9 2 1-6 3 〇1 Dissolved_Sulfur Dimethylbenzyl: Dissolve the polymer in After cooling down to 25 ° C, determine the amount of undissolved residue for measurement.-The content of monomer: Determine the weight of comonomer by infrared spectrum -2 0-- -------- Installation-. * I (Please read the notes on the back to fill in this page first) The paper size of the booklet applies the Chinese National Standard (CNS) A4 (210X 297 mm) Central Standard of the Ministry of Economic Affairs A7 B7 printed by the Bureau ’s Consumer Cooperatives V. The percentage of invention (G). Percentage of Effectiveness: ASTM-D 7 9 2 0 Porosity-Porosity: Porosity 傺 is expressed as a percentage of voids, which is determined by mercury The absorption under pressure is determined. The volume of mercury absorbed is equivalent to the volume of the pores. In order to measure the porosity, a calibrated dilatometer (3 mm diameter) CD 3 (C ar 1 ο E rba) is used , It is connected to a mercury storage tank and a high vacuum pump (lx 1G_ 2 mbar). The weighed sample (about 0.5 g) is placed in the dilatometer. The device is then placed in a high vacuum environment (≪ 0.1 mmHg), and then maintained in this state for 10 minutes . Then connect the dilatometer to the mercury storage tank and allow the mercury to flow slowly until the mercury reaches the dilatometer scale at 10 cm. The valve connecting the dilatometer to the vacuum pump is closed and pressurized with nitrogen. This device (2.5 kg / cm²). Under the effect of pressure, mercury penetrates into the pores, and due to the porosity of the substance, the mercury level begins to drop. Once the position of the mercury level measured by the dilatometer is stable, the volume of the cavity can be calculated by the equation V = R2 · π · ΔΗ, where R is the radius of the dilatometer, and ΔΗ is the initial and final mercury in the dilatometer. The liquid level difference in cm. By measuring the weight of the dilatometer, dilatometer + mercury, dilatometer + mercury + sample, the value of the apparent volume Vi of the sample before it penetrates into the hole can be calculated. The volume of the sample can be calculated by the following formula: V 1 = [P 1-(P 2-P)] / D where P is the weight of the sample (in grams) and Pig dilatometer + -2 1------- ---- Equipment-*. (Please read the notes on the back ^ Μ 彳 to fill out this page), 1T line paper size is applicable to China National Standard (CNS) Α4 size (210 × 297 mm) Employees of the Central Standards Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative A7 B7 V. Description of the invention (W) Mercury weight (in grams), P2 is dilatometer + mercury + sample weight (in grams), D is mercury density (at 25 ° C (The density is 13.54 6 g / cm3). The percentage of porosity can be obtained from the relation of X = (100 ¡V) / Vi. -Intrinsic viscosity (IV): measured in a tetrahydrogenation solution at 1 3 5 ° C. Example 1 Example 1 (for comparison) Step (A): Polypropylene homopolymer was prepared in a glass flask with a volume of 50 ml, and a solid catalyst component of 0.0161 g (according to European Patent Application EP- A-395Q83 was prepared according to the method of Example 3), and 0.799 g of triethylaluminum (TEAL) and 0.31 g of cyclohexylmethyldimethoxysilane (CMMS) were previously contacted in 8 ml of anhydrous hexane. This mixture was then placed in a 4.25 liter pin-pressure autoclave, which was rinsed in advance, first with 80 ° C hexane for one hour, and then with 80 ° C propylene gas. One hour. Then 1752 grams of liquid propylene at 3G ° C was passed along with 982 milliliters of hydrogen. The temperature was raised to 7Q ° C, and the polymerization reaction was carried out for 18 G minutes. As a result, 248 g of a homopolymer having the following characteristics were obtained: IV = 1.55 dl / g; xylene-insoluble matter = 96% by weight. Step (C): After removing the propylene and propylene, 50Q grams of liquid propane at a temperature of 5 ° C and a pressure of 19.5 bar are passed into the same reactor. Then 7 millimoles of M-MAO (dissolved in ISOPAR C), and this mixture is in contact with the polymer for 10 minutes at a temperature of 5Q ° C. At a temperature of 50 °°, -22- --------- -Installation-. -I (please read the notes on the back I 孑 fill in this page) The size of the paper of the booklet is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). Cooperative printed A7 B7 5. Description of the invention (>) Propane is evaporated and removed, and it is washed several times with gaseous propylene at 5G ° C to eliminate residual propane. In the same reactor At a temperature of 5 ° C., 19.3 g of ethylene and 41.6 g of propylene were added to the obtained polymer. Polymerization was carried out by passing two monomer mixtures containing 60% by weight of ethylene. At temperature The copolymerization was carried out at a temperature of 50 ° C and a pressure of 9 bar for 120 minutes. As a result, 276 g of Polymers, whose emblems are shown in Table 1. Example 2 (for comparison) Step (A): Polypropylene homopolymer was prepared as described in step (A) of Example 1 to prepare a catalyst and Homopolymer of propylene. Polymerization was performed using 0.0132 g of solid catalyst component. As a result, 209 g of a homopolymer having the following properties was obtained: IV = 1.57 dL / g; Insoluble in xylene = 96.1 5 ％。 Weight%. Step (B): MRBTHT-7, rf: l7 to carry out the riley step (h > after removing propylene, 500 g of a temperature of 50 ° C and a pressure of 19. 5 in the same reactor Bar of liquid propane. Then 0.005 g of £ 81 '} 11-21' (; 12 (pre-contact with 11.7 millimoles of Fu-ΜΑ0 at a temperature of 25 ° (: for 10 minutes in ISOPAR C) The mixture was allowed to contact the polymer for 10 minutes at a temperature of 5D ° C. At 50 ° C, the propane was evaporated to remove it, and at 50 ° C, several times with gaseous propylene. Rinse to remove residual propane Step (C): Copolymerization reverse film of ethylene and propylene Copolymerization was performed according to the procedure described in step (C) of Example 1 It should take 240 minutes to obtain 381 g of copolymer. Its characteristics are shown in Table 1-2-(Please read the note on the back #Fill this page first). Binding. The paper size of this book applies Chinese National Standard (CNS) A4 specifications (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (~). Example 3 Step 鼸 (A): Preparation of polypropylene homopolymer according to the examples Catalyst and propylene homopolymer were prepared as described in step (A). Polymerization was performed using 0.014 6 g of the solid catalyst component. As a result, 186 g of a homopolymer having the following characteristics were obtained: IV = 1.55 dL / g; insoluble matter in xylene = 95.9% by weight. Step suspicion (B): Promote cleanliness by water (a), Yori MRRTHT-Zr [»9 Who will do it? (H) After removing propylene gas, pass 1GQ0 into the same reactor Ml of hexane humidified with 0.051 3 g of water. It was exposed to nitrogen for 30 minutes at 50 ° C with the polymer. The liquid was removed by siphoning, and was cleaned several times at room temperature in a vacuum / krypton cycle. Then 500 g of a temperature of 50 ° and a pressure of 19. 5 bar were passed into the same reactor. Liquid propane. Then pass 0.005 grams of £ 81111-21 '(: 12 (pre-contact with 11.7 millimoles of ΜΑ0 in ISOPAR C for 10 minutes at a temperature of 25 °) ^ let this mixture with the polymer at 5Q ° Contact at 10 ° C for 10 minutes. At 5Q ° C, the propane is evaporated to remove it, and at 50 ° C, it is rinsed with gaseous propylene several times to eliminate residual propane. Step (C ): The copolymerization reaction of ethylene and propylene was carried out for 5Q minutes according to the procedure described in step (C) of Example 1. As a result, 256 g of a copolymer was obtained. -2 4-(Please read the note on the back f to complete this page)

• The paper size of the 1T line is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7. 5. Description of the Invention (W) Example 4 (for comparison) Zhu Su (A): Polypropylene homopolymer was prepared in a glass flask with a volume of 50 ml, and 0.0187 g of a solid catalyst component was prepared according to the method of Example 3 of European Patent Application EP-A-395G83. ) Was pre-contacted with 1.48 g of triisobutylaluminum (TIBAL) and 0.0706 g of cyclohexylmethyldimethoxysilane (CMMS) in 8 ml of anhydrous hexane. This mixture was then placed in a 4.25 liter steel autoclave, which was subjected to continuous rinsing in advance, first with 8ITC hexane for one hour, and then with 8 ° C propylene gas for one hour. Then 1286 grams of liquid propylene was passed in at 30 ° C. The temperature was raised to 70 ° C and the polymerization was carried out for 120 minutes. As a result, 32 grams of a homopolymer having the following characteristics were obtained: IV = 5.68 dl / g; insoluble Substance in xylene = 89.7% by weight. Step (C): copolymerization of ethylene and propane After removing propylene gas, 500 g of a temperature of 50 ° C and a pressure of 500 g were passed through the same reactor. 19.5 bar liquid propane. Then pass 9.38 mmol of TIBOA (dissolved in cyclohexane) and contact this mixture with the polymer at a temperature of 50 ° C for 10 minutes. At 50 ° C The propane was evaporated and removed at the temperature of 50 ° C, and was washed with gaseous propylene several times at a temperature of 50 ° C to eliminate residual propane. In the same reactor, at a temperature of 50 ° C , Adding 33.8 grams of ethylene and 72.9 grams of propylene to the resulting product Medium. The composition of the copolymer was maintained constant by introducing two monomer mixtures containing 60% by weight of ethylene. The copolymerization reaction was performed at a temperature of 5 Q ° C and a pressure of 15 bar 2 4 5- 2 5-(Please read the note on the back Is-i first to fill out this page)

Line 1T This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm). Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. A7 B7 5. Explanation of the invention (4) minutes. As a result, 3 to 15 g of a copolymer was obtained, and the signs are shown in Table 2. Example 5 (for comparison) Step (A): Polypropylene homopolymer was prepared in accordance with the procedure described in Example 4 Step (A). The catalysts and propylene homopolymers are prepared as described. The polymerization reaction was carried out using 02 g of a solid catalyst component, and as a result, 69 g of a homopolymer having the following characteristics was obtained: IV = 4.6 9 dL / g; insoluble matter in xylene = 82 weight 35. Step (B): WRBTHT-Zr> C! 9 to carry out the rationale (h) After removing the propylene gas, 500 g of a liquid at a temperature of 50 ° C and a pressure of 19.5 bar are introduced into the same reactor. Propane. Then pass in 0.004 g of £ 81 ^ 1-〖] ^ 12 (pre-contact with 9.38 millimoles of TIBAL in cyclohexane at a temperature of 25 ° (: for 10 minutes) β Let the mixture with the polymer in 5 G ° C for 1 G minutes. At 5 Q ° C, the propane is evaporated to remove it, and at 5Q ° C, it is rinsed with gaseous propylene several times to eliminate residuals. Step (C): #Polymerization of ethylene and propylene The copolymerization reaction was carried out for 54 minutes according to the procedure described in step (C) of Example 1. As a result, 353 g of a copolymer was obtained. Shown in Example 6. Step (A): Polypropylene homopolymer: > 靱 The catalyst and propylene homopolymer were prepared by following the procedure described in Step 4 (A) of Example 4. 0.0414 g of solid catalyst was used Ingredients to carry out the polymerization reaction, as a result, 170 g of a homopolymer having the following characteristics were obtained: IVM. 4 dL / g; -2 6--------- 1--pack-(please read the back first (Notes to fill in this page) The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) A7 B7 V. Description of the invention () Insoluble in xylene Substance = 85.3% by weight. Training step (B): Promote Kangchong rice step with water (a) »# 日 MRRTHT-ZrfMo Step by step reasonably push the body gas allyl after the same phase into the pass device Remove the gas in the 6 J ο thing ο 经 经 聚 中 中 and the mid-circle ring 0 in which to let ο hexane of the wet tide water g will be used as a siphon by borrowing ο minutes ο 3 Ms contact temperature ° c Enter B for TT-style square grams] 8 of the 4 ring 1. Circulate the gas into the nitrogen \ The device should be in the same temperature phase chamber in the next and then merged, wash off and remove the secondary body The number of liquids and the degree of activity of Wink are mixed with Wuhe 50 to dissolve.

It is pressure and the pressure in the alkane and propionate liquid in P is 2 minutes. 2 ° C at the lower temperature (please read the precautions on the back first to fill in this page). 2 in

Bis in the TI amalgamation with the 9: • 6 6 mixed with this minute ο IX contact with the alkyl hexane ring in the let

p ο 5 at 0 minutes ο 11 contact temperature P degree alkane temperature P of P left 50 residues in the elimination and elimination and washing with washing to wash off and then steaming to give alkallylic allyl In the state, the temperament is warm, and the next step is ΠΛ musk anti-copolymerization of allyl and ethylene anti-neutron dimerization. The order is as the emblem, the process of the process is described in the克 ο C 6 y '2 The results were obtained in 1 step, and the results were real. According to the 81st line, the paper printed by the Central Consumers ’Cooperative of the Ministry of Economic Affairs prints this paper. The paper size is applicable to the Chinese National Standard (CNS) A4 (2 丨 0 X 47 mm) A7 B7 Preparation of the invention 5. Description of the invention (4) Table 1 Characteristics of the copolymers of Examples 1-3 Example 1 2 3 EPR% by weight 2 1.4 53.8 40.2 DSC melting point * oc 118 116 — DSC melting point * oc 167 164 166 soluble in xylene % By weight 12.9 43.9 42% by weight of xylene-insoluble material 87. 1 56.1 58 IV deciliter / g of homopolymer 1.55 1.57 1.55 Final IV deciliter / g 2.77 2.71 1.24 -28- binding-binding线. /-· Ί., {(Please read the precautions on the back J to complete this page) This paper size applies to China National Standards (CNS) A4 specifications (210 × 297 mm) A7 B7 V. Description of invention (w) Characteristics of the copolymers of Examples 4-6 Example 4 5 6 EPR% by weight 90 82 35 DSC melting point * oc 116 113-DSC melting point * ° c 158 156 159% by weight xylene soluble matter 53.2 58. 4 41.1% insoluble xylene 44.7 39.8 57.9 IV deciliter of homopolymer per gram 5.68 4.69 4.4. Final IV deciliter of gram per gram 8.81 6.35 2 .96 * Its m detects heat between 1 0-1 8 D ° C Painting, in which propylene homopolymers and semi-crystalline parts of rubber (if produced) can exhibit melting point spikes. -29- This paper size applies to China National Standard (CNS) A4 (2 丨 〇 X 297 mm)

Claims (1)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, Α8 Β8 C8 ____08_, ------- VI. Patent Application Range | $ 3. H],,,: No. 84110856 "Used for olefin (co) polymerization Method of Action J Patent Case (Amended in September 88) Jieshenyu Patent Fanyuan 1. A method for polymerizing one or more alkane with the formula CH2 = CHR, where R is 氲 or has 1-10 値 硪Gardenia alkyl, which is to be prepared, comprises: (A) a first polymerization reaction step, in which one or more olefins of this type are polymerized in one or more reactors, which is like an alkyl-aluminum compound Polymerization in the presence of the catalyst of the reaction product of the solid component and the solid component includes a group selected from the group consisting of titanium halide, titanium alkoxide, VCla, VCI *, V0C13, and halogenated vanadium 龌The transition metal M1 compound is produced in the form of a halogenated hafnium in an active form to produce an olefin homopolymer or copolymer; (B) a processing step in which the product obtained in the first polymerization step (A) ψ Order: (a) with one that makes it appear The catalyst-deactivated compound in this step (A) is then contacted; (b) in contact with a compound of a transition metal M, and optionally in contact with an alkyl-aluminum compound, and the transition metal M 金属(C) a second polymerization reaction step, in which one or more of these paper sizes are applicable to Chinese National Standard (CNS) A4 specifications (210X297) (Public information) I-: f equipment ------ Ί1Τ: ----- γ 1 (Please read the note on the back ^ η before filling in page t) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, Α8 Β8 C8 ____08_, ------- VI. Scope of Patent Application | $ 3.h] ,,,: No. 84110856 "Method for the Polymerization of Olefins (Co) J Patent Case (Amended in September 88 ) Jieshenyu Patent Fanyuan 1. A method for polymerizing one or more alkane hydrocarbons having the formula CH2 = CHR, wherein R is a fluorene or an alkyl group having 1-10 fluorene, and the following features include: (A) a first polymerization step in which one or more of these olefins are polymerized in one or more reactors, Polymerization is in the presence of a catalyst containing a reaction product of an alkyl-aluminum compound and a solid component. The solid component includes a material selected from titanium halides, titanium alkoxides, VCla, VCI *, V0C13 and A group of transition metal M1 compounds composed of halogenated vanadium vanadium is a kind of olefin homopolymer or copolymer in an active form of halogenated hafnium; (B) a processing step, wherein in a first polymerization step (Α ) ψ The product obtained will be in any order: (a) contact with a compound capable of deactivating the catalyst present in step (A); (b) contact with a compound of transition metal M, and Is selectively contacted with an alkyl-aluminum compound, and the transition metal M 僳 is selected from the group consisting of 一个, 、, 键, and 含有 containing at least one 14-71 bond; (C) a #second polymerization reaction step, wherein One or more of these paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210X297 male) I-: f installed -------- Ί1Τ: ----- γ 1 (Please read the note on the back first ^ η items, then fill in page t) Or more polymerization reactors, which is based in the case of a polymerization reaction product of this process step (B) obtained in the present. (Please read the precautions on the back before filling this page) 2. For the method of the first patent application, the porosity of the polymer generated in the first polymerization step (A) is expressed as the percentage of voids Time is greater than 5¾. 3. The method according to item 1 of the patent application range, wherein the porosity of the polymer produced in the first polymerization step (A) is greater than 10 »when expressed as a percentage of the void :. 4. The method according to item 1 of the patent application, wherein the active form of the magnesium halide is M g C U. 5. The method according to item 1 of the patent application, wherein the titanium compound is selected from the group consisting of: TiCU, TiCl3, and a halogen alcoholate having a chemical formula of TUOR1 ^ Xn, where R1 is a hydrocarbon having 12 sulfonic atoms Is a -C0R1 radical, X is halogen, and U + n) is the atomic number of titanium. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 6. As in the method of applying for the scope of patent application item 1, wherein the solid content used in the first polymerization step (A) is an average diameter between 10 and 150 Cherm Between spherical particles. 7. The method according to item 1 of the patent application range, wherein the compound of transition gold 羼 M contains at least one ligand L coordinated on gold 羼, the ligand has a monocyclic or polycyclic structure containing a conjugated π electron . 8. If the method of the 7th scope of the patent application, in which the transition metal M is reduced -2- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 Is selected from compounds having the following structure: (I) CpkpMR1 ·! ^ (II) (Cp ^ A.-Cp ^ MR'.R2 ,, (III) where M is titanium, vanadium, junction or rhenium; CP and Cp are the same Or different, is a cyclopentadienyl group, or a substituted cyclopentadienyl group; two or more substituents on the cyclopentadienyl group can form one or more having 4 to 6 Master atom ring; R1, R2 and R3 may be the same or different, and are hydrogen atom, halogen atom, alkyl or alkoxy group with 20 sulfonic atoms, aryl group with 6-20 sulfonic atoms, fluorene Or an aralkyl group, a fluorenyloxy group having 1-20 master atoms, an allyl group, a substituent containing a silicon atom; A is a pivalenyl bridge or a group having the following structure: I:? Packing ---------- r ----- 7 1 (Please read the notes on the back before filling this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs 111 RIM _R R1—-MIR 2 R1—M, lR2 Rl— Ml— R2 I R1—c—R2 1-ο R- " '— R2 = BR1 / AIR · —Ge— / —Sir Standard Moderate National Standards Moderately Used-Ruler Zhang Shiyi 4 centimeters 7 9 2 A8 B8 C8 D8 VI. Patent application scope -S-, = S0, = S〇3, iRi, = P1U and = 和 (0) 1? 1, where Mi is silicon, germanium or tin; Ri and 1 (2, the same or different, are an alkyl group having 1-4 fluorene atoms or an aryl group having 6-10 fluorene atoms; a, b, and c are each independently an integer from 0 to 4; e It is an integer from 0 to 6, and two or more dimples in the base painting of R1, R2, and R3 can form a single ring. 9. The method of item 7 in the scope of the patent application, wherein the compound of the transition metal is like Selected from compounds having the structure: (Me5Cp) MMe3, (Me5Cp) M (OMe) 3, (Me5Cp) MCl3, (Cp) MCl3, (Cp) MMe3, (MeCp) MMe3 / (Me3Cp) MMe3 / (Me4Cp) MCl3, (Ind) MBenz3, (H4Ind) MBenz3 / (Cp) MBu3., 10. The method according to item 7 of the patent application, in which the compound of the metal is like a compound having the following structure: <. ( Cp) 2MMe2 / (Cp) 2MPh2 / (Cp > 2MEt2, (Cp) 2MCl2, (Cp) 2M (OMe) 2f < Cp > 2M < OMe) Cl, (MeCp) 2MC12, (Me5Cp) 2MCl2 / (MesCp) 2MMe ,, (Me5Cp) 2MMeClf (Cp) (Me5Cp) MCl2 / (l-MeFlu) 2MCl2 / (BuCp) 2MCl3, ( Me3Cp) 2MCl2 / (Me4Cp) 2MCl2 / (Me5Cp > ^ (OMe) 2, (Me5Cp) 2M (OH) Cl, -4 _ This paper size applies to China National Standard (CNS) A4 size (210X297 mm) (Please (Please read the notes on the back before filling this page.) _, Tr Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperatives of the Ministry of Economic Affairs Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economics, printed by A8 B8 C8 D8 々, patent application scope (Me5Cp) 2M (OH ) 2 / (Me5Cp) 2M (C6H5) 2 / (Me5Cp) 2M (CH3) Cl, (EtMe4Cp) 2-2MC12, ((C6H5) Me4Cp) 2MCl2, (Et5Cp) 2MCl2 / (Me5Cp) 2-M < C6H5) .Cl, (Ind) 2MCl2, (Ind) 2MMe2 / (H4Ind) 2MCl2, (H4Ind) 2MMe2, ([Si (CH3) 3] Cp) 2MCl2 / {[Si (CH3) 3] 2Cp} 2MCl2, (Me4Cp) (Me5Cp) MCl2. 11. The method according to item 7 of the scope of patent application, wherein the compound of Yudu Jinyu is selected from compounds having the following structure: C2H4 (Ind) 2MCl2, C2H4 (Ind) 2MMe2, C2H4 (H4Ind) 2MC12 ffC2I ^ (H4Ind) 2, MMe2, Me2S i (Me4Cp) 2MC12,. Me2S i (Me4Cp) 2MMe xf Me2SiCp2MCl 2 / Me2SiCp2MMe2 / Me2Si (Me4Cp) 2MMeOMe, Me2Si (Flu) 2-HC12 / Me2Si (2-Et-5-iPrCp) 2MCl2 / Me2Si (H4Ind) 2MCl2, Me2Si- (H4F1u > 2MC12, Me2SiCH2 (Ind) 2M i (2 -Me-H4 Ind) 2MC12, Me2S i (2 -Me Ind) 2MC12, Me2Si (2-Et-5-iPr-Cp) 2MCl2 / Me2Si (2-Me-5-EtCp) 2MCl2f Me2Si (2- Me-5-Me-Cp) 2MC12, Me2Si (2-Me-4,5-benzoindenyl) 2MC12, Me2Si < 4,5, benzoindenyl > 2MC12, Me2Si (2- EtInd) 2MCl2 / Me2Si (2-iPr-Ind) 2MCl2 / Me2Si (2-ter-butyl-Ind)> MCl2, Me2Si (3-ter-butyl-5-MeCp) 2MCl2, Me2Si (3-ter-butyl-5-MeCp) 2MMe2, Me2Si (2-MeInd) 2MC12, C2H4 {2 -Me-4,5-benzoindenyl > 2MC12, Me2C (Flu) CpMCl2, Ph2Si (Ind) 2MCl2, -5- This paper size applies to Chinese national standards (CNS) Α4 specification (210 × 297 mm) l _-------- installation ------- order ^ ----- ~ · ΊΊ (Please read the precautions on the back before filling this page). i · »· AO ii 'D8 6. Scope of patent application (please read the notes on the back before filling this page) Ph (Me) Si (Ind) 2MCl2 / C2H4 (H4 Ind) M (NMe2) OMe, isopropyl fork ≪ 3-To-butyl-Cp) &F; Flu) MCl "Me2C (Me4Cp) (MeCp) MC l ,, MeSi (Ind) 2MCl2, Me2Si (Ind) 2MMe2 / Me2Si (Me4Cp) 2MCl (OEt), C2H4 (Ind) 2M (NMe2) 2, C2H4 (Me4Cp) 2MCl2 / C2Me4 (Ind) 2MCl2, Me2Si (3- Me-Ind) 2MCl2, C2H4 (2-Me-Ind) 2MCl2, C2H4 (3-Me-Ind) 2MCl2, C2H4 (4 / 7-Me2-Ind) 2MCl2 / C2H4 (5,6 -Me2-1 nd) 2MC12 , C2H4 < 2,4,7-Me3Ind) 2MCl2, C2H4 (3,4,7-Me3Ind) 2MCl2, C2H4 (2-Me- H4Ind) 2MCl2, C2H4 (4,7-Me2-H4Ind〉 2MCl2, C2H4 (2 , 4,7 -Me, -H41 nd) 2-MC1 " Me2Si (4,7-Me2-Ind). 2MC12, Me2Si (5 / 6-Me2-Ind) 2MCl2i He2Si (2,4,7-Me3-H4Ind ) 2MC12. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 12. The method of claim 1 in the scope of patent application, wherein the catalyst used in the first polymerization step (A) contains an alkyl-aluminum compound, an electron The reaction product between a donor compound (external donor) and a solid component which includes at least one selected from the group consisting of titanium halide, titanium halide, VCU, VC14, V0C13, and fermented vanadium Group of transition metal M1 compounds, magnesium halides in active form, and an electron donor compound (internal donor). 13. 'The method according to item 12 of the application, wherein the electron donor compound (external donor) is pseudo-selected from the group consisting of: a silicon compound of the formula Ri R2 Si (0R) 2, where Ri and | { 2Same or different, is an alkyl, cycloalkyl or aryl group with 1-1 to 8 fluorene atoms, and -6- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 8 8 8 8 ABCD 6. The scope of patent application and R is an alkyl group having 1 to 4 master atoms. (Please read the precautions on the back before filling this page) 14. For the method of the first scope of the patent application, the compound that can deactivate the catalyst used in step (A) is selected from the group consisting of: CO, COS, CS2, C02, 〇2, alkynes, allene compounds and compounds of the chemical formula Ry-i XH, where R is hydrogen or a hydrocarbon group having 1 to 10 master atoms, (for Gas, nitrogen or sulfur, and y is the atomic valence of X. 15. As in the method of claim 1 of the scope of patent application, wherein the compound capable of deactivating the catalyst present in step 8R (A) is water. 16. For example, the method of the first patent application, wherein in step ((B), the product obtained in the first polymerization reaction step (A): (a) with aliphatic hydrocarbons containing deactivated compounds The solution, suspension or dispersion is contacted, and the amount of the deactivated compound is such that the molar ratio of the compound to M1 is greater than 50; printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (b) The compound and a solution of a hospital-aluminum compound are processed, the A fluorenyl-aluminum compound is derived from a trialkylaluminum, in which the alkyl group has 12 mega atoms; and a straight or tan-like aluminoxane compound containing a repeating unit-(IU) A10-, where R4 is B. A 12-atom alkyl group or a fluorenyl or aryl group having 6 to 10 sulfonic atoms, the aluminoxane compound contains 1 to 50 fluorene repeating units. Method, in which the polymerization step is carried out. The paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm)? 8? 8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ___ D8 VI. During the scope of patent application (C), At least one hafnium reactor is equipped with the product obtained in process step (b), and is simultaneously or separately charged with an alkyl-aluminum compound selected from trialkylaluminums in which the alkyl group has 1-12 ha Atoms; and linear or cyclic aluminoxane compounds containing repeating units-(1U) A 10-, where R4 is an alkyl group having 12 iodine atoms or a cycloalkyl group having 6-10 large atoms Or aryl, the aluminoxane compound contains 1 to 50 掴 repeating units. The method of claim 1, wherein the polymerization step (A) is performed in a liquid phase, and the liquid phase is composed of a hydrocarbon solvent or one or more CH 2 = CHR olefins, and the polymerization reaction therein Step (C) is carried out in at least one gas phase reactor having a fluidized bed or a mechanically stirred bed. 19. The method according to item (1) of the patent application, wherein steps (A) and (C) ), The polymerization reaction is carried out in a gas-phase reactor with a fluidized bed or a mechanically stirred bed. 20. The method according to item 1 of the patent application, wherein the treatment step (B) is pseudo-radon The phase was carried out in a tritium reactor. 21. The method of claim 1 in which the amount of polymer produced in step (A) is between 10 and 90 weights X of the total polymer produced in steps (A) and (C). between. 2 2. The method according to claim 1 of the patent application, wherein the amount of polymer produced in step (A) is between the polymer produced in steps (A) and (C). China National Standard (CNS) A4 Specification (210X297mm) -------- \ Equipment ----- 1 Order Γ (Please read the precautions on the back before filling this page) Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs A8 B8 C8 D8 printed by a consumer cooperative 6. The number of patent applications ranges from 20 to 80% by weight. 23. —A method for preparing heterogeneous propylene copolymers, the special excitement of which includes: (A) -The first polymerization reaction step of fluorene, in which propylene may react with ethylene and / or one or more olefins having the formula CH2 = CHRI: [, wherein R11 is a hydrocarbon group having 2-10 fluorene atoms in one or more Polymerization in a reactor, which is carried out in the presence of a catalyst comprising an alkyl-aluminum compound, optionally an electron donor compound (external donor), and a solid reaction product, and the species The solid content includes at least one kind of titanium halide, titanium halide, VCla, VCU, V0C13 and A group of transition metal M compounds consisting of halogenated vanadium, an active form of magnesium halides, and optionally an electron preorthodontic compound (internal preorthodontic) · and «to obtain a porosity, expressed as a percentage of voids An olefin polymer greater than 10 × contains less than 20% by weight of units derived from ethylene and / or CIUeCHR11 olefins, while the content of units derived from propylene is greater than 80% by weight and has insolubility in xylene greater than 60 *; ( B) a hydrazone treatment step, wherein the products obtained in this step (A) will be in any order: U) a compound capable of deactivating the hydrazone present in step (A); (b) Contact with a compound of transition metal M, and optional -9-This paper size uses the Chinese National Standard (CNS) A4 specification (210X2517 cm) (please read the note on the back before filling this page), vs ... Α8 Β8 C8 D8 is patented for connection with an alkyl-aluminum compound, and the transition metal M is selected from titanium, vanadium, a junction and rhenium containing at least one 値 Mι bond; (C) a The second polymerization step In this step, one or more olefins CHa = CHR, wherein R is hydrogen or an alkyl group having 1 to 10 fluorene atoms are polymerized in one or more reactors, and the product of fluorene obtained in step (B) exists In the case of polymerization, an amorphous hydrocarbon (co) polymer is obtained in an amount of 20 to 80% by weight compared with the total amount of the polymer generated in steps (A) and (c). between. Please read the notes on the back first, and then print it by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs.