TW309522B - - Google Patents

Description

309522, A / --------B7 Printed by the Central Sample Bureau of the Ministry of Economic Affairs, the Consumer Labor Cooperative Fifth, Invention Description (I) f This application is for green cuisine • Prior to the application on August 2, 1994 Part of the US Patent Application Serial No. 284,79 " 7 is part of a continuous application. Invention range 1 • The present invention relates to a method for manufacturing polydienes in a gas-phase reactor. More specifically, the present invention relates to a method for manufacturing polybutadiene in a gas-phase fluidized bed reactor. The method of olefin and polyisoprene, inventing the back octapolydienes' such as polybutadiene and polyisoprene, has been manufactured for many years, it is by solution polymerization, and has recently been borrowed from agglomerates Or oligomeric polymerization method 5 Regarding the polymerization of butadiene, especially i, 3 _ butadiene polymerization, various catalytic solutions and sizing or agglomeration methods are known in this art to be suitable for producing high content 1,4 -cis unit polybutadiene, which is particularly suitable for the manufacture of tires, belts and other molded or extruded rubber or other elegant objects. In solution polymerization, butadiene is polymerized in an inert solvent or diluent. The solvent will not enter the structure of the formed polymer, or will not adversely affect the formed polymerization ball. Such solvents are usually aliphatic, aromatic and cycloaliphatic hydrocarbons, such as pentacle 'hexane, gengkeng, stupid' toluene, cyclohexane, etc. 5 solvent / single skull «product ratio can be changed in a wide range . In the polymerization reaction, the reaction medium 1Γ basically contains no solvent and is used as a diluent. The gas-phase fluidized bed and the stirred-out reactor method can be used to manufacture polymerization snakes, especially polyolefin polymerization reactors. This discovery makes it possible to manufacture a wide variety of novel gas-phase processes with high expectations and improved properties, especially such gas phase methods, especially -4- < 妗 " " Page) 300522 a? 1 -___ B7 Ministry of Economic Affairs, China, Ministry of Economic Affairs, Ministry of Economic Affairs, Du Yin ¾ V. Description of the invention (2) It is a gas fluidized bed method used to produce a polymer, which should be used in conjunction with other conventional polymerization methods. In the pan-comparison, it provides a sudden reduction in capital investment costs and attracts people; Wang Yi I saves energy and uses f to make a polymer method β. In the conventional Qiliyuanyi bed method, it will contain-or a variety of single skeletons The gas stream 'passes through the fluidized bed reactor containing a bed of growing polymeric smilax particles in the polymerization reaction zone' simultaneously or intermittently introducing polymerization catalysts' into the polymerization reaction zone. The desired polymerization product Self-polymerization zone Take out, degassing, stabilizing and packing for transportation, all by the Jizhi Street. Since this polymerization reaction system is exothermic, it is necessary to remove the calorific heat generated in the polymerization reaction zone to prevent the over-ripening and melting of the polymerized snakehead particles. This is achieved by removing unreacted hot gas from the polymerization zone continuously, and replacing the hot gas from the polymerization zone with s that is replaced by a cooler air trap, which is constricted, Cooled in the heat exchanger, supplemented with an additional amount of single skulls to replace the single rituals that have been polymerized and migrated in the reaction zone, and then recycled into the bottom of the reactor. The order of achieving β compression and cooling in the multiple heat exchanger companions is a matter of design choice, but it is usually preferred to provide the compression squirrel inflow and the rate of flow through the reactor before it is provided. Maintaining the level of vegetable seeds so that the polymerized particle bed system remains in a fluidized state. The manufacturing of the polymerized snakehead system in a stirred bed reactor is very similar. The difference is that the mechanical stirring device is used to help maintain the polymerization bed. It is in a fluid state or other well-mixed state. Conventional gas-phase flow || Resin bed resin preparation method is very well known in this technology, for example, it is presented in US Patent Nos. 4,379,758, 4,383,095, and -5- f — — _____1 4 ^ · ii H --—? . **-·· 7 The standard of this law is applicable to SS home kneading 3 · CNS) A4 specification (mm) Ministry of Economic Affairs Central Kneading Bureau shellfish consumer cooperation · Du printed version 5. Invention description (3) 4, Nothing in the disclosure of 876,320, which is hereby incorporated by reference. 02m gas: the method of preparation in a stirred reactor, is also the skill of this technique. Zhongsuo =, ':: presented in US Patent 3, 2 5 6 , 2 6 3 ... the one with the blessing of the equipment. Recently, in U.S. Patent Nos. 4,994,5 3 4 and 5,3〇4,5 8 8 stated that the knee adhesive polymerization technology, including polybutadiene rubber, can be made in a fluidized bed reactor, which is tied to the touch In the presence of medium ', in the polymerization reaction above the adhesive polymerization temperature, it is carried out in the presence of inert particulate material. This catalyst is preferably a transition metal catalyst. The catalysts used in the examples are based on titanium- and vanadium- (catalyst systems, which also include auxiliary catalysts and, where appropriate, use-promoting chemistries made in this gas-phase process. , Is a granular, mixture of rubber and erotic substances, where the core contains most of the rubber 'and the shell contains most of the dependent substance β. U.S. Patent 5,3 1 7,0 3 6 discloses The gas-phase polymerization method utilizes uncatalyzed soluble catalysts, such as transition metal coordination catalysts. These catalysts are introduced into the reactor in the form of a liquid, such as a fluidized bed. The prepared polycockrole hydrocarbons may contain diphenols. The European Patent Ε Ρ 〇6 4 7 6 5 7 A 1 discloses a rare earth catalyst that has undergone hydration and is used for gas-phase polymerization of conjugated dilute compounds. The clamp mistakenly believes that allowing any type of liquid snake to enter the polymerization reaction area of the gas phase reactor will inevitably lead to the aggregation of resin particles, the formation of large polymerization lumps, and finally completely shut down the reactor. Concerns, causing the gas-phase polymerization manufacturer to carefully avoid entry Dun loop should then cooled to a temperature of the gas stream is less than the polymerization reaction is the use of any single technique -6- (Fathers aphid count read back cloud early injection refill item Ma - p)

WCX Consumer Cooperation of the Central Falcon Bureau of the Liji Ministry · 14 Printing 309522 y Β7 —____--看 _ι ^ ______ ________ V. Description of the invention (4). / Condensation temperature, ../ Comonomers, such as hexene -1〆-methyl-pentene and octene-1, which are especially paid for the production of ethylene copolymers. These high-carbon alpha olefins have a relatively high coagulation β in the polymerization zone of concern. The liquid single species will lead to point polymerization, agglomeration and finally shut down the reactor, so the production rate depends on the rate at which the heat is removed from the polymerization zone. It is severely constrained by the needs of recognition and knowledge. The temperature of the circulating gas stream entering the reactor is safely maintained above the condensation temperature of the highest boiling single snakehead present in the circulating gas stream. Even when performing polymerization in a stirred reactor, exercise caution, · Maintaining the resin bed temperature above the condensation temperature of the recirculated gas stream components 0 To maximize heat removal, it is not unusual to spray or inject the liquid into the polymerization bed or the bed. Dew to hotter recirculation airflow It immediately boils into a gaseous state. With this technology, a limited amount of cooling effect can be achieved through the Joules-Thompson effect, but it will not cool the recirculated gas stream to the extent that condensation may occur. 3 This route is typically sand and A labor and energy waste approach is required, which is to cool a part of the circulating airflow separately to obtain a liquid single skeleton for storage, and then to introduce it into or into the polymerization bed separately. An example of this procedure can be found in U.S. Patent Nos. 3,254,070; 3,300,457: 3,652,527 and 4, 〇12,573 »It has been found later that contrary to the belief that the presence of liquid in the circulating gas stream will cause cohesion and reactor closure for a long time, it may in fact be Cooling the entire circulating air flow up to a large amount of monomers will cause condensation, when these liquid snakes are introduced into the reactor and are in temperature balance with the recirculating air flow, there will be no __- 7 · __ This paper size is used Chinese gg home standard technology (CNS) A4 * Jt grid (2l0x297 public goods · »'~ (points. 35 銮 背 5 之; ± intentions then fill ^:-this page) — (装 丨 —1Γ --- --- ¢: gas Λ " Β7 Ministry of Economic Affairs Central Sample Standard wa; industrial and consumer cooperation. Social seal-V. Description of the invention (5). It is expected that the "spring will occur. Cooling the entire circulating air stream" will produce two phases Qi Li-Li Li ;, the compounds are in temperature balance with each other, so that the liquid technology contained in the air stream will not be immediately coated with steam. Instead, a substantially larger amount of cold occurs. However, because of the full mass of gas 'Liquid' is at a temperature substantially lower than previously thought possible, entering the polymer In the reaction zone, this method will lead to a substantial improvement in the yield of polymerization rituals produced in the gas phase, especially in the case where the co-prostitutes used are condensed at relatively low temperatures. 3 This procedure is often referred to as Condensation mode " Operation, which is detailed in U.S. Patent Nos. 4,5 4 3,3 9 9 and 4,5 8 8,7 9 0, and is provided for reference herein 3 In Condensation Mode Operation, Enters the Polymerization Reaction Zone The two-phase gas-liquid complex in the belt is heated very quickly, and once it enters the polymerization zone, it is completely vaporized within a very short distance. "Even in the largest commercial reactors, it enters the polymerization Soon after the reaction zone, all liquids have been vaporized, and the temperature of all subsequent gaseous circulating gas streams in JL is substantially improved by the exothermic nature of the polymerization reaction. The ability to operate gas-phase reactors in condensation mode, prestige It is possible that this is due to the rapid heating of the two-phase gas-liquid flow entering the reactor, accompanied by the effective fluidized back-mixing of the fluidized bed, without leaving the liquid skeleton in the polymerization bed. Short distance, higher than the two-phase gas The degree of entry of liquid recirculation flow "We have now found that liquid monomer can exist in the entire polymerization bed, provided that the liquid monomer present in the bed is adsorbed on the solid particulate material present in the bed Or be absorbed in it, for example, the polymerized ft or fluidization aids made are present in the bed, as long as there is no large amount of free liquid single skeleton. 3 This discovery makes it possible to produce polymerized snakeheads in gas-phase reactors. , ___-___ —-8 _ Xu-Xian \ ^ Read the intentions of the back of the cloud and fill in the page! I! I-(buckle ^.) --------_____ " δ 卜 、 · · II III ^ 八 · 5- ·. III II «—1. T---...... 1 1i_t-

The Ministry of Economic Affairs of the Central Standards Bureau of Labor and Economic Cooperation of the People's Republic of China. The company's seal V. Description of the invention (6) i The single hip used has a condensing temperature much higher than the temperature of manufacturing conventional polyassociated hydrocarbons in gas-phase reactors. One way to observe this discovery is to be able to use easily condensable single snakes (eg, 1,3-butane 2) in gas-phase reactors under conditions where they are expected to exist as liquids. Alkene, which has a normal minus point of -4.5. (:), manufactures polymeric cockroaches. Furthermore, a gas phase method for producing polymerization rituals using some or all monomers having a low to moderate coagulation temperature previously has been Not practical, because at all monomer concentrations with a condensation temperature lower than the temperature in the polymerization zone, the amount of polymerization produced by each catalyst particle is too low. Now, the discovery of the present invention makes it economically and practically useful A polymer is produced by using a monomer having a condensation temperature higher than the temperature in the polymerization reaction zone, so that the liquid monolayer is present in the entire mixed bed, provided that the liquid is present in the bed. , Department Adsorbed on or absorbed in solid particulate material, polymerization bed and / or the polymerizing uranium product present in the polymerization reaction zone of the reactor. The present invention makes it previously impossible to use a continuous gas phase method It is possible to manufacture the gas phase of the Zhao type of polymerization. Another benefit of the present invention is to use the single pith that has been dissolved in the polymer and exists in the liquid snake, and use the undissolved single skeleton. That is, compared with the operation of the monomers only in the gas phase, a larger concentration is obtained at the position of the active medium. This should maximize the productivity of the catalyst used to manufacture the polymer. Yet another benefit is that the heat transfer within the polymer particles should be improved. This is due to the heat being removed by the evaporation of the monomer. This is the same as using the undissolved Shanyi, meaning that it only exists in the air Comparing the operation of the single shot in the phase, it should lead to a more uniform aggregate particle size '-9--•••; the father reads the notes of the back cloud and fills in {:'-. Winter page)

This is the standard scale of the general application Sg family castellation (CNS) Αί charge • grid (: 10Χ: 9 · 公 慎>) Ministry of Economic Affairs Central Department-Industrial and Consumer Cooperative Indica 309522 Λ.

A I < _____ B? Five 'Description of the invention (7) More uniform polymerization, snakehead properties, less polymer fouling, and possibly improved polymerization morphology s

• The present invention provides a method for manufacturing polybutadiene or polyisoprene in a stirred bed or a gas-liquid-liquid polymerization reactor with a polymerization zone under polymerization conditions. This method includes : (0 In the presence of an emotive particulate material and at least one inert gas used as appropriate, introduce butadiene or isoprene monomer into the polymerization zone containing the bed of growing polymerized snakeheads; ( H) In the polymerization reaction zone, continuously or intermittently introduce a polymerization catalyst containing metal components of nickel, cobalt, titanium or a mixture thereof, a catalyst promoter and an accelerator used as appropriate: ( iii) From the polymerization zone, continuously or intermittently withdraw polybutadiene or polyisodioxide products: and (iv) from the polymerization zone, take out unreacted butadiene or isoprene, press · Shrink and cool the dioxin or isoprene and the inert gas (when present), while keeping the temperature in the polymerization zone below the dew point of the single species present in the polymerization zone. The invention also Provide granular particles "Articles made with such particles" attached a brief description of a fluidized bed reaction system particularly suitable for the production of polybutadiene and polyisoprene, which is shown in this appendix ® s It is not limited to any specific type or kind of polymerization, but the present invention is -10- ij i- -I- I ---- i (^ 衣-i --1 -I {烧 残 ^^^ = --- --¾ ^^^^ ¾ ^), τ ut! B? Five particularly well-returned to the polymerization reaction, which involves relatively easy to condense to the homopolymerization and copolymerization of the skeleton, such as poly two and poly Isoprene. Higher boiling point or easily condensable monomers that can undergo olefin polymerization, examples of which are as follows: A · Higher molecular weight alpha olefins, such as decene_ 丨, dodecene · 1, isobutylene, styrene "Cockroaches, etc." "B. Dienes, such as hexadiene, vinyl cyclohexene" dicyclopentadiene, butadiene, isoprene, ethylidene proborne, etc. C. Polar vinyl mono Li's such as propylene, maleic acid, vinyl acetate, acrylic esters, 'methacrylic esters', vinyl three-year-old silanes, etc. ~ ~ These are more likely to have boiling points or easier The condensed monomers can be homopolymerized according to the present invention, which uses a kind of inert gas skeleton as the gaseous component of the two-phase gas-liquid mixture circulating through the reactor. Suitable inert substances for this project include nitrogen, Argon and residual hydrocarbons, which are still gaseous at temperatures lower than the temperature selected to be kept in the polymerization zone, are printed at the higher boiling point or easily Condensed monomers can also be copolymerized with one or more lower boiling points, such as ethylene 'propylene and butene, and other higher boiling points, such as those indicated above, the only requirement is that there are Sufficient air snakes are present in the circulating air flow to allow continuous operation in a steady state. Therefore, according to the method of the present invention, styrene and butadiene can be copolymerized to produce styrene-butadiene rubber (SBR). According to the present invention, a single heel with a higher boiling point or easy to coagulate can be directly introduced- 11-This paper is a standard for fast leisure in the Mingya family dish (CNS i Μ specifications ί mm wing jibe central sample quasi-martial ordnance consumer cooperation 枉 印 brake < Fifth, the invention description (9 f into the polymerization baseband ' Or use a recirculated gas stream to bring it into the polymerization zone or both (joining. In a preferred embodiment, the temperature in the polymerization zone is kept lower than that present in the polymerization zone In the reaction zone, the condensation temperature of Shanyi (for example, 丨, 3-butadiene or isoprene), in another example: the state of being in the polymerization reaction zone (for example ^ Temperature, pressure, single snakehead concentration) is such that substantially no liquid skeleton exists in the polymerization reaction zone, so that it is not adsorbed on the solid particulate matter κ is absorbed in it, or 'in the polymerization reaction zone The state of "is maintained" so that in a part of the polymerization zone The monomer is a liquid skeleton absorbed in the solid particulate matter. 9. The implementation of the invention is not limited to any specific type of catalyst. Any catalyst that can be used for gas-phase polymerization can be used in this In the practice of the invention, it has been previously used in the higher boiling point or easy to condense single snakehead (for example, = dihedron or isoprene) in the 'liquid or whole Zhao polymerization reaction ^ catalyst' can also be used in In the present invention. * Conventional Zlegler_Nana catalyst is used, which means that it is formed by the reaction of a metal argon compound and a transition metal compound, and it is preferably used in the tube of the present invention. Β is through aluminum alkoxide and the periodic table It is particularly useful for the people from the first to the 111th group into the reaction. Zhiwei can be used as a catalyst in the implementation of the present invention, and its description is as follows. A. $ Touch on To RCT ^ ^ (珠 Ϋ 如 在 吴National Patent 4, 3 7 6. 4, d79, 758., B. Chromium-based media, as stated in U.S. Patent 3,709 9853.:, 709,954: and 4,077,904. -12 (^ -ν: " ^,-·-·-^^-1 " ^ ··-" ^)

The Ministry of Economy and Economic Development of the Ministry of Economic Affairs of the Ministry of Economic Affairs and Consumer Affairs Indo A7 _-__; slave. D. Metal Shuangwuyuan catalyst, as described in U.S. Patent Nos. 4,530,9M: 4,665,047; 4,752,597: 5,218,071: 5,272,236:. And 5,278,272 "E. The cationic form of metal halides, such as aluminum trihalide. F. Cobalt catalysts and mixtures thereof, such as those described in U.S. Patent Nos. 4,472,559 and 4,182,814. Nickel catalysts and their complexes, such as those described in U.S. Patent Nos. 4,155,880 and 4,102,817. The transition metal catalyst used in the method of the invention can have a metal component, a catalyst promoter, and an accelerator used as appropriate. This metal component may be a transition metal compound or a compound of two or more transition metal compounds. Generally speaking, the transition metal component of this catalyst may be soluble or insoluble, after being supported or not. Supported, or spray dried in the presence or absence of fillers. Alternatively, the polymerization catalyst may be introduced into the polymerization zone in the form of a pre-polymerization ceremony using techniques known to those skilled in the art. When the metal component is formed into a support, typical supports may include, for example, silica and carbon black , Porous cross-linked polystyrene, porous cross-linked polypropylene 'oxide, oxidation, oxidation or money function (for example, gasification money) broadcast materials. Crushed stone, carbon black, and alumina are the preferred materials. Silica and hard black are the best materials for enamels. Typical silica or alumina is a solid, particulate, and porous material that is basically susceptible to polymerization. It is used in the form of dry powder. The powder has an average particle size of about 10 to 2:> 0 microns, and preferably about 30 to about 100 microns: the surface area is per gram __ -13- (Poetry first smell please back 5 · Please fill in this page for more details.-(Pretend ------, 17 ------ The skill of the line-up technique is standard; ilogg's home sample stands <CNS) -ΆΙ 格 （2iOx2? 7 Gong Cheng) A 7 B7 V. 309522 Description of the invention (11 at least 200 square meters, and preferably at least about 25 50 square meters per gram: and the pore size is at least about 100 angstroms' and preferably At least about 200 angstroms. In general, the amount of use of the Lu skeleton is to provide about 0.001 to about 10 millimolar-ear transition metal per gram of support. In a preferred embodiment, two A type of carbon black is used as a skull. DARCO G-60 (pH value of water extract = 5) is used as a dry bath powder, which has a surface area of 505 square meters per gram, an average particle size of 100 microns, and pores Degree per丨 .0 to 15 cubic centimeters. NORIT A (pH value of water extract = 9 · 11} used as dry powder, which has a surface area of 720 square meters per gram and an average particle size of 45 to 80 This metal component is impregnated on the support by conventional means, for example, in the presence of eaves material, the metal compound is dissolved in a solvent or diluent, such as hydrocarbon or tetrahydrofuran, and then evaporated, for example under reduced pressure, Remove the solvent Pang thinner. Alternatively, the transition metal component can be dissolved in a solvent or diluent, such as hydrocarbons or tetrahydrofuran, and spray dried to produce a well-formed catalyst precursor, which has very little or No silica or other inorganic solid content if necessary, the preferred transition metal compound for the production of polybutadiene and polyisoprene is a compound containing nickel, titanium and cobalt, of which cobalt and nickel The best catalyst for the compound "Medium compound, which is a component, is an organic front compound containing a single-or double-dentate organic coordination carbohydrate containing up to the back atom. &Quot; Matching ^ ^ h \ meaning to be bound To the ugly Xianxian was integrated into the gold exhibition Or the oligomer or molecule on the ion a monodentate coordination skeleton means that there is a position through which a covalent or coordination bond with the metal can be formed: Shuangzihe 14 CNS &gt; Grid Uurx 297 $ ) Binding

X Liji Ministry of Central Affairs

AB? V. Description of the invention (12. The coordination bait really has two positions, through which it can form a compensatory or coordination bond with the metal. The organic nickel compound is usually soluble in the soluble two. Therefore ' Any salt or organic acid containing approximately 1 to 20 carbon atoms can be used. Representative examples of organic nickel compounds are nickel stupate, nickel acetate, nickel cyclohexanecarboxylate, nickel octoate, and neodecanoate , 2-Ethylhexanoic acid nickel, bis (redundant-allyl nickel), bis 〇 · cyclooctyl · 1,5 · diene) 'bis (especially allyl nickel trifluoroacetate), bis (α- Furanyl di)) nickel 'nickel nickel palmitate, nickel stearate, nickel acetopropionate nickel, willow nickel, bis (liquid) ethylenediimide nickel, bis (cyclopentyl ping) chain The preferred components of sleeping cyclopentadienyl iron and Sigui baseline 3 containing wires are nickel salts of carboxylic acids or organic complex compounds of nickel. Co-catalysts that can be used with nickel-containing components, including triethyl Aluminum (TEAL ·) 'triisobutyl benefit (ΤΙΒΑ), gasified diethyl Ming (deac), partially hydrolyzed gasified diethyl aluminum (DEAC 0), methyl aluminum oxide pit (MAO), Or by Modified methylaluminoxane (MMAO) »When MAO or MMAO is used as a cocatalyst, it can be one of the following-Ministry of Economic Affairs, Shenyang-like Huai Bureau, shellfish consumption, including printing for the company ^ Interpretation of the meaning of the cloud ^ fill ^ this education) Κ: (a) branched or cyclic oligomerized poly (oxyalkyl aluminum), which contains the general formula-(A1 (R ...) 〇)- Heavy enthalpy unit, where R ... is hydrogen 'alkyl group containing 1 to about 12 atoms, or aryl group, such as substituted or unsubstituted phenyl or yl; ] [BR * 4-] Ionic salt 'where A + is a refractory Lewis acid or Bronsted acid capable of extracting alkyl, functional or gas from the transition metal component of the catalyst, B is boron, and R • is a substituted aromatic hydrocarbon, preferably perfluorophenyl; and (c) a boron pit compound with the general formula BR β 3, where R * is as defined above》 Aluminoxanes are this technique Known in, and including the following formula Table-15- A7 B7 Fifth, the invention description (13) shows the oligomeric paint · 'Tiger-based oxygen burn · ·

And the following oligomeric cyclic alkyl alkane: /-Al-Ο- \

.I \ R &quot; '/ p. ·' Where ^ _ · is 1 to 40, preferably 10 to 20; £ _ is 3 to 40, preferably 3 to 20: and R '' 'is An alkyl group containing 1 to 12 carbon atoms is preferably a methyl group or an aryl group, such as a substituted or unsubstituted phenyl group or a substituted group This technique known by the artist 'uses C 2 to C! 2 base trapped, preferably using isobutyl' instead of 2 〇_ 8 0 heavy f% methyl formed. Accelerators that can be used with this nickel-containing component include argon fluoride (H F), trifluoride (B.F3), or ethers of HF and / or BF3. The Ministry of Economic Affairs Central Bureau of Sampling and Ordnance Consumption Cooperation. Du Yinqu 1 .......... H! 1: 1 .....-Shi Yi, _ 1 (min. 5C first reading back £- Of; 1 content and fill in too. Page} The titanium compound (titanate) can be TiCl4, TiBr4, Til4 or Ti (OR) 4, where R is an alkyl group. It can be used as a catalyst promoter with titanium-containing components , Including TEAL, TIBA, dialkyl aluminum iodide, and MAO »Promoters that can be used with titanium-containing ingredients, including Angstrom and organic mysteries For isoprene, TiCl4, TIB A, and DPE are used together (二 笨 眯) • 16- A 7 B7 30S522 V. Description of the invention (Μ) Any organic compound whose name is cobalt compound neodymium, such as aluminum salts of organic acids, cobalt compounds and their analogs. Self-comprising copper-copper compounds' such as ethyl acetoxypropyl cuprate (II) and acetylacetonate cobalt (III) :; cobalt; 5-ketoester complexes, such as cobalt acetate acetonate Ethyl ester complexes; cobalt salts of organic carboxylic acids with <5 or more carbon atoms, such as cobalt octoate, cobalt cyclohexanecarboxylate, and cobalt benzoate: and cobalt complexes such as gasification Cobalt and pyridine complexes; Gasified cobalt-ethanol complex, and a cobalt complex coordinated with butadiene 'such as (1,3-butadiene) [1-(2-methyl-3-butenyl) -7Τ- Allyl aluminium 'can be made by, for example, mixing a cobalt compound with an organoaluminum compound, an organic compound or an alkylmagnesium compound and 1,3-butadiene: the other typical cobalt compound is cobalt jasmine , Cobalt adipate, 2 · ethylhexanoic acid, stearic acid, and the organic part of the molecule contains about 5 to 20, preferably 8 to 18 carbon atoms, and contains one or two Similar compounds with carboxyl functional groups, and ethylpyruvate, co-catalysts that can be used together with the starting ingredients, including ethyl aluminum sesquichloride (EASC) 'ethyl aluminum dichloride (EADC), DEACO, ΜΑΟ and their mixtures' If necessary, a small amount of water can be used together with the metal component containing cobalt, as an accelerator. The fluidization aid that can be used in the present invention is a solitary particulate material. It is chemically inert to this reaction. Examples of such fluidization aids include black black, silica, clay and other similar substances such as slip aOrganic polymeric snakes can also be used as flow aids. Carbon black and crushed stone are the best fluidization aids, of which carbon black is the best carbon black material used, with 17-paper Once again, I use the Sig family dish a (CNS) A4 (210 X 297 mm (please first read the notes of the poem and then fill in the page)-^ 装 ------ 定

K. The Ministry of Economics has a sample of squeezing out another work to eliminate poverty, including Zuosha. A. V. Description of the invention (15) There are primary particles that are as small as about 10 to 100 nanometers, and the gathering ceremony (primary structure) The average ruler is about 0.1 to about 10 microns. The specific surface area of the rear fog is about 30 to 1,500 square meters per gram, and this carbon black chelate shows that the absorption rate of dibutyl phthalate (DBP) is about 80 to about 3 5 0 (: &lt; : / 1〇〇grams. The available materials are: The stone is amorphous and has a main particle size of about 5 to 50 nanometers, and the average size of the aggregate is about 0-1 to 10 microns. The average size of the material is about 2 to about 120 microns. The crushed stone used has a specific surface area of about 50 to 500 square meters per gram, and the dubenzyl dimethacrylate (DBP) absorption rate is about 100 to 400 Cc / 100 g. The clay that can be used according to the present invention has an average particle size of about 0.01 to about 10 microns and a specific surface area of about 3 to 30 square f / g s. 100 grams to about 200 to about 100 grams. Organic polymer ft materials that can be used, including ethylene, propylene, butylene and other 4 hydrocarbon polymerization ceremony and copolymer, and polybenzyl, known Paragraph 0 Mining Shapes "These organic polymeric materials have an average size of" T / Private "in the range of about 0.01 to 100 microns, preferably 0.01 to 10 microns. ... Yan, Liuli The amount of additives used is usually based on the consumption and cooperation of the Ministry of Economic Affairs * and the Central Falcon Bureau. The printed version of the company and the type of polybutadiene or polyisoprene produced are different. When Linghei or crushed stone is used as a fluidization aid, it is used. / 〇 to about s 0% weight ratio, preferably &lt; κ ^ A -9 'I right to live from about 5% to about 60% , 1 0 0 / 〇 to about 4 5 〇 / 〇, based on the weight of the final β „1 degree of intersection (polybutadiene Λ® isoprene) as a standard β, typically +: δ used β 土 或 济 = When used as a fluidization aid, the content range can be. ^ ^ ^ Ma, J% to about 80%, based on the weight of the last 4 produced, which is more commonly referred to as weight I is about 12 % To 75% weight ratio β organic -18, send to 1f gg family standing at each Bianstone scale (C \ S Α4 specifications

Ar B7 Wingji Ministry of Central Prototyping Bureau ordnance elimination dream cooperation red seal complex five, description of the invention (1δ) After the gift quality is aggregated-the angle is from about 0.1% to about 5% by weight, preferably about 0 . 1% to about 10%, based on the weight of the final polymer product produced. .Optional flow of the auxiliaries at or near the top of the reactor, at the bottom of the reactor, introduced into the reactor, or led to the bottom of the loop line and introduced into the bottom of the reactor 1 The best case is The carmine additive is introduced at or near the top of the reactor or above the fluidized bed. Preferably, before entering the reactor, the fluidization aid is processed to remove traces of moisture and oxygen. This can be achieved by purging the substance with nitrogen and heating it by conventional procedures. The fluidization aid can be individually Add 'or add it in combination with one or more single gifts or with a soluble and non-contaminated catalyst. This fluidization aid is preferably added separately. 3 A fluidized bed reaction system which is particularly suitable for the production of polymeric skull materials according to the present invention is shown in the appendix. Reference this figure, reactor! 〇Including reaction zone 12 and velocity reduction zone 14 »Generally speaking, the height to diameter ratio of the reaction zone can be changed in the range of about 2.7: I to about 4.6: 1. This paradigm can of course be changed to a larger or smaller ratio, and it depends on the desired production capacity. The cross-sectional area of the β-velocity reduction zone 1 4 is typically multiplied by about 2.6 to about 2.8 The reaction zone 12 is within the range of the lake's cross-sectional area. 3 The reaction zone 12 includes growing polymer particles, formed polymer particles, and a small amount of catalyst particles. The bed is formed by supplementary feed and recirculation streamlines. The continuous flow through the polymerization of the reaction zone and the change of the gaseous components is streamlined. In order to maintain a usable bed, we will go through the table of this bed (Ki first read the Vi notes on the back and then fill out this page) ---- .Γ 丨! 1 19-A7 B7 V. Description of the invention (I?) The gas velocity exceeds the minimum flow required for fluidization and is preferably at least 0.1 ft / sec above the minimum flow rate. Usually, this surface air velocity If the benefit does not exceed 5.0 ft / s, and usually not more than 2.5 ft / s, it is sufficient. -------- The Ministry of Economic Affairs Shenyang Rubbing Bureau Ordnance Industry Consumer Cooperatives instructed that this bed must always contain Particles to prevent the formation of local "hot spots" and to capture and divide the catalyst in the entire reaction zone. "When the test is run, a bed of particulate polymerized snakehead particles is often added to the reactor. Such particles are inherently compatible with The polymeric smilaxes to be formed are the same, or they can be different. When they are different, they are taken out together with the desired formed polymer particles as the first product 3 and finally / replaced by the fluidized bed of the desired polymerized particles Partially or completely activated precursor combinations used in the fluidized bed of the test bed β and / or catalysts are preferably stored in the storage tank 16 for use. Substances are covered by a petitioning gas, such as nitrogen or argon β flow It is achieved by the high velocity flow through the bed, which is typically about 50 to about 150 times the feed rate of the supplemental streamer. This fluidized bed has individual moving particles. The general appearance of the dense trapped block, which is caused by the percolation of the gas courtesy of the bed. The drop through the bed is equal to or slightly larger than the weight of the bed divided by the cross-sectional area s. Therefore, it depends on the reactor The geometric shape depends on the supplementary flow snake can be put into the bed at point 18 3 The composition of the supplementary liquid flow is determined by the gas snake analyzer 21. This gas skull analyzer measures the composition of the circulating liquid flow, and according to This adjustment replenishes the composition of the liquid flow to maintain the base in the reaction zone. The composition of the gas skeleton is in a stable state. This gas ritual analyzer is a conventional gas technology f analyzer, which is based on the conventional method -20-3? Printed by the Ministry of Central Government ’s Bureau of Ordnance and Consumers ^ 30Q522 V. Description of the invention (is) _ / Operation, to measure the proportion of circulating liquids. This equipment can be obtained from a wide variety of sources: feed liquid Flow, typically placed on the proper position # 鳢 Analyzer 2 1.1. M between the heat exchanger 24 R gas ft. 4 lowering h can bring higher boiling point monomers to 夂 # Shi 4. In various ways to introduce polymerization reaction including passing nozzles (not shown in the figure ~ "中 十 U ，， A〆 / 二-山J Chang, Wang enters the bed 'or after passing through the bed, it is gnawing (not π out), loyal, and second spray on the top of the bed I, which can help to recycle the gas π &lt; knowing turn = Fang Zaojun feeding The rate is relatively small, the heavier balls can be easily introduced into the polymerization zone by shooting a Α u 甙 甶 suspend ΛΤ in the circulating gas flow into the bottom of the reactor. To ensure complete fluidization Therefore, the recirculating liquid flow, and if necessary, a part of the replenishing liquid flow, passes through the recirculating line 22, and is returned to the reactor at a point 2 6 below this bed. Preferably, it is above the recovery point , There is a gas heterogeneous transfer plate 28 to facilitate the fluidization of this bed => when passing through this bed, the recirculating liquid stream will absorb the reaction heat generated by the polymerization reaction. The part of the fluidized liquid stream that is not reacting in this bed is moved away from the polymerization zone. Preferably, it is allowed to pass into the velocity reduction zone 14 above this bed, and the particles transported can Here it is lowered back into the bed. The recirculating liquid stream is compressed and contracted in the compressor 30 and then passes through the heat exchange zone before returning to the bed, where the heat is removed. The heat exchange zone is typically a heat exchanger 24, which can be of horizontal or vertical type 9. If needed, a number of heat exchangers can be used to reduce the temperature of the circulating air flow in the dark section. The ink shrinker can also be set at Downstream of the heat exchanger, or in the middle of several heat exchangers. ¾ »After cooling, make the recirculating liquid flow back to -21 at the bottom of its 2 6-Ben H and again * 3L. : CNS) A4 sand grid (210X3 mm) ·? ΊΑ · κ reading back l; 11 meanings ^ refill 2: 'big two more')

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The Ministry of Economic Affairs, Central Bureau of Standards, Ordnance Industry Consumption Cooperation II, SL A7 ____ __B: V. Description of the invention (l9) / Return to the reactor + V, the ash passes through the gas II distribution plate 2 8 and returns to the fluidized bed e gas deflection The reactor 32 can be installed at the entrance of the reactor to prevent the polymer particles contained in it from settling out and sticking together to form solid lumps, and to prevent the accumulation of liquid snakes. At the bottom of the reactor, it helps to contain The procedure between the liquid skeleton and the procedure without the liquid trap is easy to change, and vice versa. The description of the gas-cargo deflector suitable for this project is the device described in US Patent 4,933, 149. The selected bed temperature is maintained at a substantially constant temperature under steady state conditions by continuously removing the reaction cooked. No significant temperature gradient appears in the upper part of the bed. A temperature gradient can exist in the bed bottom (about 5 to 12 inches), which is between the inlet fluid temperature and the temperature of the rest of the bed. Good gas chain distribution 'in the operation of the reactor, It plays an important role. The fluidized bed system contains growing and formed particulate polymer particles, as well as catalyst particles "When these polymer particles are hot and may be active, 'it must be prevented from settling'" If the shackles are allowed to exist, any active bracelet media contained in them may continue to react and cause bismuth synthesis. Therefore, at a rate sufficient to maintain the flow of the skull on the entire bed, the Retaki Circulation Ceremony is diffused It is very important to pass this bed. The gas distribution plate 28 is a better device to achieve good gas distribution, and can be a screen, a long eye sieve, a porous plate, a bubble cover type plate, etc. The components can be all fixed, or the plate can be the mobile type disclosed in US Patent 3,298,792. Regardless of its design, it must be at the bottom of the bed to allow the recirculating fluid to diffuse through the particles to keep the bed in fluid_-22 -This , Degree of Qiqig family 糅 忮 (CVS) A4 specifications (:; 0χ2? 7 male cage) {-** ·; · .fric read back cloud of ;; x 意 事 if. Then fill out this page) 裒. * -* Central Ministry of Economic Affairs, Employee Consumption Cooperation. Co., Ltd. Printed A? B7 V. Description of the invention (20), change the state to reflect the resin particle bed used when the reactor is not operating * The preferred type of gas S distribution plate 28 is metal, and it has accumulated over it. The holes distributed on the surface 5 These holes usually have a diameter s of about 1/2 English leaf. These holes extend through the plate. A triangular angle iron with a crushing heat of 3 6 is placed on the hole. It is loaded on the plate 28. This isometric iron is used to distribute the flow of flow, along the surface of the plate to avoid solid stop. Net zone. In addition, when the bed axe is stopped, it will prevent the polymerization from flowing through the Confucian Temple: any fluid that is inert to the mandarin medium and the reactants can also be present in the recirculating liquid stream * an activated sword compound 'if used, A better technique is to add the reaction of the downstream of the hot father device 24. This is not the case; in the brother, you can activate the activated metal from the distributor 38 through the line 40 to the recycling system and pregnant women. In the real family of the present invention, the operating temperature can be extended to the range of about _100, C to about 丨 5〇 C. Among them, the range of degrees is from about 20. (: To about}, 〇.c 比 传 _ This flow ft bed reactor can be operated at a pressure of up to about i 〇〇〇- H slr, and is preferably operated at a sign force of about 100 psi to about 600 psi Operation under high power extraction is conducive to heat transfer, because the increase in pressure will increase the heat capacity of the unit of the skull: the precursor composition and the 4 catalysts that are partially or fully activated (the total is later used as the contact) ⑽ It is injected into the bed at the point 42 above the Fenwei board 28 at a rate equal to its consumption. 3 The best case is to 'inject the catalyst in the bed and the well-mixed point. The catalyst is at high Note on the distribution plate: It provides satisfactory operation of the fluidized bed polymerization reactor. Bracelet, 1, like the area of the distribution plate, can cause the polymerization reaction to open at this location = 23-r {CNS 5 (;! 0X297 ^ J5 ·, (X-- (discuss the first 55 items on the back of the ··· / * meaning * item and fill in too. Page) Order k A * Ministry of Economic Affairs Central Sample Agency Bureau of Consumer Engineering Co., Ltd.印 袈 309522 ____ V. Description of the invention (21) It caused a lack of distribution branches. Direct injection into the fluidized bed helps to distribute the catalyst evenly throughout the bed, and it is easy to avoid high catalysts The local point of the temperature is formed, otherwise it may cause the formation of M hot spots &quot;. The catalyst is injected above the bed. The reactor may cause excessive migration of the medium into the circulation line, where polymerization may occur, and Lead to blockage of pipelines and heat exchangers = For the catalyst that has been integrated, it can be injected into the reactor by various techniques. However, it is preferable to use a catalyst feeder to continuously feed the catalyst into the reactor , Such as disclosed in U.S. Patent No. 3, 777, 712. For catalysts in the form of solutions, liquids or slurries, it is preferred to base them on U.S. Patent Nos. 5,317,036 and 1995 issued to Brady et al. US Patent No. 4 1 4, 5 2 2 filed on March 31, 2014, whose title is &quot; Methods for controlling particle growth during the manufacturing period of adhesive polymeric snakes &quot; All are listed here for reference. Preferably, the catalyst is fed into the reaction at a point away from the reactor wall by 20 to 40% of the reactor diameter, and at a height of about 5 to about 30% of the bed height "In the device" is better to use the qi skeleton which is emotional to the catalyst, For example, nitrogen or argon is used to transport the catalyst into the bed. The production rate of the polymerization snake in the bed is determined by the catalyst injection rate and the concentration of single ft in the reactor. The production rate can be conveniently borrowed easily. Adjust the catalyst injection rate to control it. Because any change in the catalyst injection rate will change the reaction rate and therefore the rate of heat generation in the bed, the temperature of the recirculating liquid stream entering the reactor ' It is adjusted up and down to comply with any change in the rate of heat generation: this ensures that a substantially constant temperature in the bed is maintained "Flowing and Flowing-24-(surprise · κ ·? ·» '' '' Notes on the back ¾ Fill in too much page}

This is the reason for the adoption of the SS Jiapi Note (CNS; (2 丨 0X297mm) B7 B7 in the Nuji Ministry of the Central Sample Falcon Bureau for male workers' consumption cooperation. Zhuangyin Change V. Description of the Invention (22) Bed and Recycling The complete instrument configuration of the liquid Ά cooling system can, of course, be used to detect any changes in the degree of bed, so that the operator or the conventional automatic control system can properly adjust the temperature of the recirculating liquid flow. • In a specific set of operating conditions Under, the fluidized bed is kept at a substantially constant height by forming a part of the bed as the product at the rate of formation of the particulate polymerized snakehead product. The rate of heat generation is the rate of product formation It is directly related, so the measure of the temperature rise of the lepidoptera across the reactor (the difference between the temperature of the inlet stream and the temperature of the outlet stream), if there is no or negligible evaporable liquid exists in the inlet stream, It is a characterization of the rate of formation of a specific polymerization skull at a constant fluid velocity. When the microparticle polymerization product is discharged from the reactor 10, it is generally desirable and better to separate the fluid from the product and make The body is returned to the recirculation line 22. There are many ways known in the art that can be used to achieve this operation = a preferred system is shown in the drawing, therefore, the fluid and product leave the reactor at point 4 1 0, and enter the product discharge tank barrel 4 6 through the valve 4 8 'The valve can be a ball valve, which is designed to have a minimum flow when opened. System = located above and below the product discharge tank barrel 4 6 , Is a conventional valve 50, 52, where the latter is suitable for providing a pathway for the product to enter the product surge adjustment tank 54. The product surge adjustment tank 54 has an aeration device shown by line 56, As shown in the gas ritual entry device, the gas squirrel entry device shown in the pipeline 5 8 is also located at the bottom of the product surge adjustment tank 54. It is the discharge valve 6 〇 When it is in the open position, the product will be discharged. Transported to storage. Open 5 0 will release the streamer to the surge adjustment tank 6 2 when in the open position. The stream snake from the surge adjustment tank 6 2 is guided through the filter -25- (装 ----- -ir --------- (Poetry first &quot; Reading the background of the cloud-intention to fill in the page too) Central Standard of the Ministry of Economic Affairs Ordnance Consumer Cooperative Seal-A7 ______ V. Description of the invention (23) »-Absorber 6 4,> The plate passes the compressor 66 and enters the recirculation line 2 2 through line 68» In a typical mode of operation, the valve 4 The 8 series is opened and the valve 5 0 '5 2 is closed. The closed position * product and fluid enter the product discharge tank barrel 4 6 »Valve 4 8 is closed and the product is allowed to sink: the hall is in the product discharge tank 4 6. Then Open the valve 50, allowing the stream snake to flow from the product discharge tank barrel 46 to the surge tank 62, where it is compressed back to the recirculation line 22. Then the valve 50 is closed and the valve 5 is closed 2 Open, and let any product in the product discharge tank 4 6 flow into the product surge regulator 5 4 * Then, close the valve 5 2. The product is washed with an inert gas, preferably nitrogen, which enters the product surge adjustment line 54 through line 58 and evacuates through line 56. The product is then discharged from the product surge tank 54 through the valve 60 and sent through the pipeline 20 to storage. The specific timing sequence of these valves is achieved through the use of conventional programmable controllers, which are known in the art. Furthermore, these valves can be kept substantially free of cohesive particles, The way is to direct the gas flow through these valves and back to the reactor periodically. Another alternative product discharge system is better, which was revealed and requested to be applied by Robert G. Aronson on July 28, 1981. For 2 8 7, 8 1 5, JL, whose title is M fluidized bed discharge system &quot; co-pending US patent application (currently US Patent 4,621,952) "This system uses at least one pair ( (Parallel) tank, which includes a settling tank and a transfer tank. After the _ ringworm rids and makes the separated gas phase, it returns from the top of the settling tank to the point in the reactor near the top of the fluidized bed. An alternative and better product discharge system is to exclude the re-pressing pipeline 6 4, 6, 6, 6 8 * 26-Ben Rongtou once again made the SS house beetle (CNS) AUt grid (two plus public) &quot; --- st, -1-i ml it i ill. --- I-I-1 I----Ϊ- II-1-. I-. ·, ^- -i 0-1:! .II—! i I,-&quot; ^ {碕 first ¾ read the back of the back of the apple and then fill in the cover page} The Ministry of Economic Affairs Central Falcon Bureau negative labor consumption cooperation th seal-V. Invention Explain the requirements of (24), as shown in the system of r mask S. This fluidized bed reactor is equipped with an appropriate exhaust system (not shown) to allow exhaust of the bed during start-up and shutdown. This reactor does not require stirring and / or wall friction. The recirculation line 22 and its components (condenser 30, heat exchanger 24) should be smooth and free of unnecessary obstacles, so as not to hinder the flow of recirculating fluid or particles transported = according to this Invented polymer, for example, the following polyisoprene polystyrene polybutadiene SBR (copolymer of butadiene and styrene) ABS (polymerization of propylene, butadiene and styrene Body) Nitrile rubber (polymer of butadiene and acrylonitrile copolymer) Butyl rubber (polymer of isobutylene and isoprene copolymerization) EPR (polymer of ethylene and propylene copolymerization) EPD Μ (ethylene and propylene And polyene copolymerized with a dip such as hexadiene, dicyclopentadiene or ethylidene borneol) polybutadiene rubber (polychloroprene) polysiloxane (poly Dimethylsilazane) Copolymer of ethylene and vinyl trimethoxysilane Ethylene and one or more propylene · Guai, maleic acid i§, stearic acid ethylene, acrylic acid and methyl malonate, etc. Copolymer = When you want to use one or more of the following monomers to make polymers or copolymers At this time, all of these simple wines have a relatively high boiling point or are easy to condense, and they are applicable to the SS home standard (CNS; about the specifications (n〇x29 has a public f, ~~ ^ { Surprised first brother Qi Qiyun ... \ | Important Wang ^^ trvr-A) *-° .-ο A: B1 5. Description of the invention (25) According to the present invention, the H-phase fluidized bed M is better Under the conditions of $ and pressure, it is better to use a kind of inviting substance, which is still in a gaseous state under the conditions selected for polymerization in the fluidized bed. It is suitable for this purpose. The system is erotic qi etiquette, such as nitrogen, argon, neon, krypton, etc. It can also be used for shaving and hydrocarbons, such as ethane, propane, butyrate, etc., and replaced by pixels ..., such as gas. Other materials, such as carbon dioxide, can still be used under the required conditions, as long as the base is as conductive as possible and does not affect the performance of the catalyst. Nitrogen, due to its physical properties and relatively low cost, is the It is a single gift of self-admiration. For example, stupid ethyl acid, &amp; materials, methyl methacrylate: _ 馼 甲 s purpose, etc. It is a better medium for rituals. It keeps a gaseous state at a relatively low temperature, such as W and ㈣, which is also preferred. 3 The conventional skills for preventing reactor fouling and polymer adhesion can be used in the present invention. The implementation of v L, _ 1S · This illustrative example of t technology is the introduction of subdivided 2L pepper particle material, ^ r, Wan Zhi cohesion 'as in US patents 4,994,534 and 5 π® Xunmen f ^ 〇, _ , Described in: Adding will produce a negatively charged chemical. Mouth, in order to level the voltage in the hemp, or add a chemical that will produce a positive charge, to Ningyunbei potential, 4, Ding Rushi Wu Guo Patent 4, S 0 3, 2 5 1 The arsenic s can also add antistatic substances γ kg ~ a ^ ^ ^ * Tea theory is continuous intermittently to prevent 戋

Neutralization of static charge generates s qr1 10000 A. The granular polybutadiene-connected &amp; * ^ and / or Qi isoprene elasticity ft of the present invention can be combined with a &lt; -Ding Erxi rubber release, (letter 1, /, ethylene · propylene-diene rubber, reinforced filler, such as carbon 28- {妗 先 ¾¾ .. Note on the back then fill out this page) Installed by the Ministry of Economic Affairs Industrial and Consumer Cooperatives 袈 袈 ^ · έ. &Amp; {CNS 'Λ4ί, ί_ &gt;$.; 1 〇 · &lt; ::? Mm 309522 Λ &quot; B? Ministry of Economic Affairs' Central Bureau of Psi -1〇 &gt; &lt;; 97 g; $) Li, invention description (26) f black, silica; know, X auxiliary: anti-degradation agent: and vulcanizing agent, use equipment and technology familiar to this artist The method is carried out together. In this kind of ingredients, compared with what can be achieved with conventional polybutadiene or polyisoprene in the form of solid bales, this initial granular form of polybutadiene Or polyisoprene can be allowed to mix more closely with other elastomers. It is usually desired that the elastomer compound is intimately mixed to optimize the mechanical properties of the sulfide: Furthermore, Fang is used as an auxiliary agent to maintain granularity during the polymerization process and after the reaction. Inventive particles are also found to be reinforcing fillers (eg, carbon black) for this ingredient. It requires only a short mixing time to disperse the filler on the ingredients. This is because before the filler can be dispersed, it usually must first be debonded in the mixing process, and in this case, it is Mixing procedure for deagglomeration and dispersion that is substantially de-aggregated = 1v. Compared with the package form, prepared from granular, relatively self-flowing polybutadiene and / or polyisoprene as described in the previous paragraph Associated elastic species ingredients can be used as components of pneumatic tires if you do n’t hear them. For example, in radiant automobile tires (in manufacturing, specially formulated elastic species ingredients can be extruded to produce treads for sidewalls of tires and fillers The strips used by the strip assembly-or produce sheet material for air retention, other special materials can be calendered on the fabric or curtain fabric to produce ^ fabric reinforced sheet material for supply Tire cord ^ The surrounding belt components or unvulcanized tires are constructed in the following manner, except that each piece of belt ⑽ except the belt and the tread) is assembled on the surface of a drum on the surface of the drum Axial compression of this assembly, with vocalist to do all n recognition benefit (eN.s) 7 ^ Γ7 ~: -----.----- "&gt; c · ------ order --- --11 ^ (Poetry first flashing the note on the back of Ling Xiang Yi Yi Xiong Tai page) V. Description of the invention (27) か 牛 扃 I Gong Consumer Cooperative Society of the Ministry of Economic Affairs printed ¾ shape 'and then k. # 与 tread The components are placed in place 2 around the circumference of the circular line. Finally, the raw tire is vulcanized by using high-pressure steam to bulge against the inner surface of a closed, heated aluminum mold. At the early stage of this vulcanization process, when the various elastic skull ingredients are still flexible and flowable, the pressure of the tire against the internal surface of the mold will produce the final precise shape of the tread pattern, side wall printing, and the plutonium mark 3. Later, in this vulcanization process, the heat-activated cross reaction will occur in various elastomer ingredients 'so that when the mold is finally opened', each ingredient has been cross-linked to a degree that is basically most suitable for the intended purpose When used as a component of tire ingredients, the granular polybutadiene of the present invention particularly imparts abrasion resistance, fatigue crack resistance, low heat generation, and low rolling resistance. The granular polyisoprene of the present invention particularly imparts forming adhesiveness and raw rubber strength, which facilitates the forming and processing of green tires, and resistance to tearing and cutting = in the gas phase method of the present invention The granulated 'free-flowing polybutadiene and polyisoprene' can also use techniques known to this artist, and be used in other molded and extruded objects. The granules made by the gas-phase method of the present invention, “relatively free-flowing sbr, use the technique known by this artist” to be used in the molded or to-be-made objects. The following examples are used To illustrate the invention. '_Example 1 In an example of the method of the present invention, ~ ~ ^ ^ Alpha α: «〇 decoction fluidized bed reaction; r, the system' operation as described below, _ I 乂 manufacturing ethylene- Propylene is associated with M. This polymerization technique is made under the following anti-riding parts: 4 〇 (Xu Xian &quot; Xingbei * :; i, please fill out this page) vm nn i tn ^ --1- Μ eC reactor temperature, And 290 psia reactor reputation in the reactor -30-table. ¾¾ feet · degree speed application Shen SS home cicada a (CNS) / ^ shift_ grid (210X297 public change 300522 Λ7 male Ministry of Economic Affairs Central Bureau of Samples Yinxian Cooperative Society Chapter 5. The description of the invention (π) The partial pressure (dew point) of single snakes and comrades is 90 psia for ethylene and 198 psia for propylene. The partial pressure of argon is 2_〇psiae. ENB was injected into the reactor at a rate of 0.53 lb / hr. The volume of the reactor was 55 ft. 3: The weight of the resin inside the reactor was 1 12 lb. The catalyst system used in this example is vanadium acetonyl pyruvate, using diethylaluminum chloride as a cocatalyst, and trigas ethyl acetate as an accelerator. The production rate is 20 lbs / hour 》 The product has a Muni value of 5 5 »The injected ENB ', of which 75% is deposited into the polymer by polymerization; the rest of the unreacted ENB is dissolved In the polymerization ceremony, it is equal to 0.66% of the weight of the polymer = there is 112 pounds of resin in the reactor. Therefore, all unreacted ENB is 0.74 pounds. "If the unreacted ENB is completely evaporated in the reactor, then Its partial pressure will be 0.67 6 4 psia »At 40 eC, the saturation pressure of ethylene is 2 1 8 7 7 psia, propylene is 337.1 psia, and ENB is 0.262 psia» due to ethylene and propylene in the reactor The internal partial pressure is much lower than its saturation pressure, so there is no condensed ethylene or propylene. However, the calculated partial pressure of unreacted ENB inside the reactor is much higher than its Bao and pressure * Therefore, ENB is inevitable It remains liquid and has been absorbed by the polymerization snake. Example 2 Ethylene-propylene triad ternary polymerization ceremony is produced in the fluidized bed reaction system as described above under the following reaction conditions. 4 0 ° C reactor temperature and 363.4 psia reactor pressure, the partial pressure of single ft and total single ft inside the reactor, 90 psia for ethylene and 198.2 -31-f loop for propylene --- --- -'4 309522 A 7 B7 Red Stamp of the Consumer Labor Cooperation of the Central Prototype Bureau of the Ministry of Economic Affairs-Description of Invention (2 9 ί psia = argon's partial pressure is 2.2 psia, and the partial pressure of nitrogen is 72.6 »Inject ethylene borneol (ENB) at a rate of 0.53 lb / hr into the reactor for polymerization In the reaction zone, the volume of the reactor is 55 ft 3; the weight of the resin inside the reactor is 112 lbs. The hard media used in this example is not ethoxypropylpropanoic acid. It uses vaporized diethyl chain as a catalyst promoter 'and digaseous ethyl acetate as a promoter. The production rate is 20 pieces per hour. The product has a Muni value of 55. Where: The main input is £ NB, 75% of which is retained in the polymer by polymerization, and the remaining ENB that is not reacted in the polymer is dissolved in the polymerization snake, and is equal to 0.66% of the weight of the polymerization ceremony. Since there are 112 pounds The resin is inside the reactor, so all unreacted ENB is 0.74 pounds. If the unreacted enb completely evaporates inside the reactor, its partial pressure will be 0.67 6 4 p s i a.于 40. The saturation pressure of ethylene is 2187 7 psia, the diene is "7.1 psia" and the ENB is 0.262 psia »Because the partial pressure of ethylene and propylene inside the reactor is much lower than its saturation pressure, there is no condensed ethylene or Propylene. It is the calculated partial pressure of unreacted ENB inside the reactor, which is higher than the rest and the pressure. Therefore, ENB must be kept at m and has been absorbed by the polymerization a. Example 3-1 0 Example 3- 10 is in the form of table 1177 in the operating conditions for manufacturing a variety of different polymerization ft according to the present invention. 9 is a description of the implementation of the present invention using different catalyst systems and circulating gas composition. __ 《装 ------ 1Τ- ----- f {discuss ¾ read the precautions on the back and then fill out this X) B7 5. Description of the invention (30) Example number 3456 Product: Polybutadiene SBR ABS Polystyrene Association Economic Department_Ministry of Central Standards Bureau Industry Consumer Cooperation, Social Printing-Reaction Conditions: Temperature &lt; TC) 40 40 40 40 Pressure (psi) 100 110 200 100 Surface Speed (ft / s) 1.75 2.0 1.5 1.5 Production Rate 30 25 20 40 (crushed / hour ) Total reactor volume 55 55 55 55 (sq. 3) Reaction zone with pike volume 7.5 7.5 7.5 7.5 (sq. 3) Height (feet) 7.0 7.0 7.0 7.0 Bed diameter (sigh) 1.17 1.17 1.17 1.17 Bed weight (hours) 112 112 112 112 Circulating clam composition: N: 20 27.3 58.0 99.7 Butadiene 80 72.5 39.9 — Phenylene — 0.2 0.15 0.3 Propylene Moon Paste-1.95 — Catalyst: Co (acac) 3 * Co (acac) 3 * Co (acac) 3 * Cp2ZrMe2, 5! Cocatalyst: Heavy single ft feed rate triethyl aluminum triethyl Triethylaluminum MAO *** (lbs / h) Butadiene 46.2 9.62 2.46 — Styrene-20.83 15.33 44.4 Diene riding — 7.08 — Polymeric zipper composition · Butadiene 100 25 8 · · Styrene 75 69 100 Propylene Yueqing — 23-· * Cobalt triethylacetonate pyruvate θ dicyclopentadienyl zirconium dimethyl *** methylaluminoxane • 33-as long as possible, meet 3; in the gg family purulent CNS) Αί 蚬 珞 (210x29 ·? Mm '^ --- I— ______ {-A &quot; B *

The Ministry of Economic Affairs of the Ministry of Economic Affairs of the Ministry of Economic Affairs under the negative consumer cooperation. She printed 5L V. Description of the invention (31) An example 7 In an example of the method of the present invention, is to press the fluidized bed reaction system as described above ' Operate as described to produce polybutadiene. This polymerization ceremony was made under the following reaction conditions: 5 5 ° C reactor temperature and .100 psi 1 a total reactor pressure, and the partial pressure of butadiene monocalves inside the reactor was 80 psia 'nitrogen The point is known as psia. The catalyst system used in this example is ginseng (ethylpyruvate) cobalt. It can be supported on silica or made into a solution in methane. Use methylaluminoxane as a cocatalyst. The catalyst and catalyst-assisted feeds are adjusted to obtain a ratio of 4 0 0: 1 molar ratio Α1 to C 0. Under stable conditions, put Shanli into the reaction system at a rate of 47.8 pounds per hour, and put it in the system. Put the dry N_65 carbon black at a speed of 20 pounds per hour into the reactor. The butadiene monocarbo exits the reactor at 5 pounds / hour in the exhaust stream. After being adjusted for the carbon black content, the production rate is 〇0 d / hour for the polymerization snake, and the product has a Muni viscosity Ml. (i + 4 @ 100 ° C) is 5 5. Other conditions regarding Example 7 are shown in the table. β under steady state 'total silver butadiene of 47.8 lb / hr into the reactor t' and It is calculated that a total of 45 lbs / h leaves the reactor with a gas skeleton in the exhaust stream or as a polymerization gift. The difference of 2 · 8 lbs / h must be the unreacted liquid butadiene monole, which is left in In the polymer of the reactor, the polymerization ceremony discharged is the same as the polymerization technique in the bed, so the polymerization ceremony in the bed must contain the same proportion of liquid single prostitute, which means it must be 1.04 pounds of dissolved liquid The single heel is in a 112-pound polymerization ft bed. The reactor volume is 55 suction 3. At a partial pressure of 80 psia, there are 37.6 broken butadiene in the reactor gas phase. All of the appliances are not aggregated

• 34-

The Ministry of Economic Affairs, Central Bureau of Industry and Consumer Cooperation Du Yin-_B7_ V. Description of invention (32) r Butadiene, because 'Λ48 · 0 pounds (= 37.6 + 10.4). If all of this dilute is in the gas phase of this reactor, it has a fraction of 10 4 psia and its condensation temperature is 6 1 ° C = Therefore, the reactor at 5 5 ° C is Operation below the condensation temperature of the monomers present in the polymerization reaction zone. Furthermore, the presence of this liquid monolith in the gas phase reactor does not cause cohesion of the polymer. (ί ···-一> τ ^ Notes on the back of the cloud vf- &quot;-··: &quot; Page 35 Dong Changle once again spent this dish leather (C,: s) Α · ί Hang grid; :: 0Χ 297 mm) 309522 A: B · V. Description of the invention (33) Example number product:

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9 ABS 10 Polystyrene • Ministry of Economic Affairs Central Bureau of Rectification and Negative Second Consumption Cooperation Yu Yin-Reaction conditions: Polybutadiene temperature fc) 55 55 55 65 • Pressure · Pressure (psi) 100 110 200 100 Surface speed (feet / Sec) 1.75 2.0 1.5 1.75 Production rate 30 25 20 30 (hours / hour) Total reactor volume 55 55 55 55 (ft3) Reaction zone zone volume 7.5 7.5 7.5 7.5 (ft3) Bed height (ft) 7.0 7.0 7.0 7.0 Bed diameter (suction) 1.17 1.17 1.17 1.17 Bed weight (accumulation) 112 112 112 112 Circulating air snake composition (mol%): n2 20 27.3 58.0 70 Styrene 80 72.5 39.9 — Phenylene— 0.2 0.15- -Acrylonitrile — 1.95 — Isoprene — 30 catalyst: Co (acac) 3 * CpTiCl3 CpTiCl3 TiCl4 Cocatalyst: MAO *** MAO *** MAO *** TEAL * single skeleton Feed rate (lb / h) Butadiene 47.8 9.62 2.46 — Styrene— 20.83 15.33 — Propylene cyanine — 7.08 — Isoprene — 35.4 Total single-bones exhaust rate 15 1 1 2 (Lb / h) Polymerized It composition (wt%): Butadiene 100 25 '-36-' 8 Too long method and abalone = SS Jiayiyang (CNS) A ·! Specifications (2 ! 0 &gt; 〇9 has a millimeter 'I "--- • -tl 100 V. Description of the invention (34 Styrene 1 Acrylic acid isoprene * Cobalt triethylacetate pyruvate ** is also diphenyl silver carp *** Methylaluminoxane 75 69 23 WC industrial consumption cooperation of the Central Bureau of Economic Development of the Ministry of Economic Affairs ¾ Example 1 1 Maintain at a temperature of 22. (: add 4 in the mixed bed reactor) Continue dry bath Break the black powder to make it flow as a chemical agent. Add ∣ (1) lbs. Of semi-gasified ethyl aluminum (EASC). Then add 0.6! Lbs. J 3 • butene and enough nitrogen to make the silver carp react The pressure of the device reaches 315 psia. 'Open two amounts of money into the C〇Cl2 (, than 4 catalysts, start at the beginning: the amount of 10% by weight of the gasified ethyl aluminum catalyst solution (in The feed was adjusted in isopentane to obtain a 15: 1 Mo 4 ratio A1: c. During the 2 2 hour polymerization reaction, a total of 6.84 pounds of additional butadiene was added to replace the polymerized and excluded I butadiene. A small amount of exhaust gas leaving the reactor, during the polymerization reaction: removes a total of 0.22 pounds of butadiene, in the polymerization of two bundles $, that is to stop the catalyst and catalyst feed s will The reactor relieves the pressure and causes The reactor contents were flushed with nitrogen to remove residual butadiene. Discharge the polymer skeleton from the reactor = the product does not contain any agglomerates, the agglomerate means that there has been a point of polymerization = on the contrary 'this product is a free-flowing, fine, granular powder. "Open the reactor and clean it, In order to ensure that all products are recovered, the total weight of the recovered solid product is adjusted for the initially added black. The rest (5.73 pounds) is the amount of butadiene polymer I formed during this batch, and it is present in the reactor when the reactor is closed.甴 于 -37-Try to eat ft ruler home material (CNS) A4 material UlQx: 9 ---- (¾ 17 ------ (Μ Ministry of Economic Affairs Central Standards Bureau Ordnance Industry Consumer Cooperatives Insignia A / ___________B7_ 5 3. Description of the invention (35) A total of 7.45 pounds of g.84 + 〇_6i) butadiene was added to the reactor, and a total of 5.95 pounds (= 5.73 + 0.22) of butadiene has been used as a polymer The moraine exhaust stream leaves the reactor, so when the polymerization reaction is terminated, there must be .1.5 lbs of butadiene monomer in the reactor. When the moss removes pressure and flushes the contents, this single snake will move The reactor's slow accumulation is 61.7 liters (or 2.18 cubic meters). At 22 aC, the vapor pressure of Ding Erqi is 35 psia. 9 is present in the reactor as the mass of butadiene that is in the air. , So it is 0.73 words. At the time of the stop, it was confirmed that the total I_ 5 0 broken unpolymerized butadiene in the reactor was confirmed. Among them, at most 0.73 pounds may have been in the vapor phase, and the rest (077) It must have been present in the condensed phase ', for example, after being dissolved in the polymer. Therefore, this reactor is operated at a temperature lower than the existing condensing temperature of Shanli. 5. 7 3 pounds of polymerized skull combined 0.7 7 pounds of liquid single snakehead, equivalent to 134 pounds of condensed butadiene monomer per 10,000 broken polybutadiene. Furthermore, the liquid monomer Existing in the gas-phase reactor will not cause the cohesion of the polymer skeleton 9 to give further details about the pan example. Example 1 2 · 1 8 is carried out according to Example 1 1, but the changes are shown in the table 0 Shi 2 made by the eaves catalyst catalyst in a 500 ml flask was flushed with dry nitrogen, add 3 9 g of gypsum (60 (TC activated) and 7,2 72 g C〇Cl2 (pyridine) 4. Add 15 mL of CH2CI2 to it »Stir the slurry several times, and then remove the dissolved sword in the air. _ -38-Dong Shi Le Duo Du Lu 1 China S Jiazai at (CNS) A4 煶 格(210X297mm) Please pay attention to the precautions of the first K reading back »and then fill out this page) Ό 人 * ------- v 丨

AT AT, Ministry of Economic Affairs, Central Bureau of Industry and Commerce, Male Workers ’Consumer Cooperative Indy B7 V. Description of the invention (36) Example 18 Preparation of solution-liquid-kneading medium In a flask cleaned with dry nitrogen, add 1.648 g of samyl Cobalt pyruvate. To this was added 100 mL of anhydrous CH2C12 »This mixture was stirred for several minutes, added to a pressurizable metal cylinder, and the silver solution was introduced into the reactor. (&quot; Precautions on the back of Yuanwen Reading vfH &quot;, --Page ♦ -0 κ, τ -39- Example No. Product: 11 Polybutadiene 12 Polybutadiene 13 Polybutadiene 14 Polybutadiene Catalyst | Cobalt Dioxide Cobalt Dichloride-Cobalt Dichloride · Acetyl Propylene Cobalt Dichloride-«Bidian at 17 to bite on cobalt keto acid to bite on silica on silica on silica on silica Catalyst 10% EASC 15% DEACO 10% EASC 10% MA 〇In isopentane in toluene in isopentane in methyl pentoxide in the treatment conditions reaction reaction degree fc) 22 23 20 20 BD partial pressure (psia) 30 30 30 30 Polymerization protocol produced 5.7 6.3 5.4 5.8 Reaction time 2 hours 10 minutes 3 hours 2 hours 15 minutes 1 hour 20 minutes Product analysis 0 Mechanical black N-650 analysis 44 38 44 45 Average particle size 0.016 0.019 0.015 0.034 Borrow Sieve analysis (inches) Aluminum / catalyst feed ratio * 15 28 11 607 Cobalt content at 55 81 94 19 Polymerization ceremony (^) Contrast 1.5 1.0 1.0 3.6 Viscosity (divide / g) Muni viscosity 42% cis- 1,4 93 92 * The molar ratio of AI to transition metals in continuous feed is better than 92 98.4, and the head scale is suitable for 1S Jiayu standard (C,: s) A4 specification (: I0x: ^ Public Love) 5. Description of the invention (37 A 'B · 17 Polybutadiene Example Number Product ·· 15 Polybutadiene 16 Polybutadiene 18 Polybutadiene Catalyst Details Catalyst Digas Cobalt-Cobalt Dioxide · Propylpyridinium Caprylate · ΓΡΡΓ) + Cobalt Ketoate on Silica Diamine on Silica on Aluminium Gas on the Silica Auxiliary Bracelet Media 10% MAO 15% DASC 15% DEACO 10% DEAC treatment conditions in toluene in toluene in toluene in isocyanate reaction temperature fc) 20 20 20 20 BD subscribing (psia) 30 30 30 25 polymerization gift (pound) 4.2 6.5 6.8 5.7 reaction Time product analysis 1 hour 4 hours 30 minutes 3 hours 10 minutes 4 hours 30 minutes% carbon black Ν · 650 analysis 56 44 41 44 Average particle size by sieve analysis (inches) Aluminum / media feed ratio * Ming content in polymerization Lizhong φρπή 0.036 385 45 0.016 62 84 0.013 10 195 Size not measured 45 45 Contrast 1.0 1.1 1.0 0.7 Viscosity (units / g) Muni viscosity 40 ML (1- + 4 @ 1003C)% Shun-1, 4 95.7 96 Π 鋹 1 + N-isopropyl-N1 · phenyl · p-phenylenediamine, with 90 * per ear for the transition of A1 pair in continuous feed Genus molar ratio off ears present on the catalyst "(&quot; - Father Interview Goes back of the note ^ will do ^ - ^ clever too p) f f i - Ministry of Economy * husband like crimson shut body of work disappear back Cooperatives printing equipment

309522 at B7 5. Description of the invention (38) Example number 19 20 21 Product: polybutadiene polybutadiene polyisoprene catalyst details catalyst tricyclohexyl nickel trichloride TiCl4 / pentadiene titanium diphenyl · Base bond promoter 10% MAO 10% TEAL TIBA in toluene 10% BF3 etherification treatment conditions reaction temperature fc) 50 50 50 single points. Pressure &quot; (psia) 60 60 25 Watts should be time for product analysis 2 hours 4 hours 4 hours 0 money black 40 40 40 N-650 analysis assistant catalyst / ¾ medium 500 60 10 Feed ratio * * Mol ratio of A1 to transition metal in continuous feed (Xu Xian «. Please back; 5. What happens.-?-Fill in Taixiong page) Eight ", eight,-. • e ______ {Ministry of Economic Affairs Central Standards fS Bureau we industrial and consumer cooperation cooperation insignia-41-

Claims (1)

A8 B8 C8 D8 No. 84109831 Application for Patent Application Application for the Amendment of the Patent Fan Garden (February 86). For the scope of the patent application, please read the precautions and then 1. A type with a polymerization zone under polymerization conditions A method for manufacturing polybutadiene or polyisoprene in a stirred bed or gas fluidized polymerization reaction vessel. This method includes: (i) in the presence of an inert particulate material and at least one inert gas selected Isoprene monomer is introduced into the polymerization reaction zone containing the bed of growing polymerized particles; (η) In the polymerization reaction zone, 'continuously or intermittently introduces a compound containing thread, aluminum, titanium or a mixture thereof Metallic polymerization catalyst, a catalyst promoter and an optional accelerator; (ui) from the polymerization zone, continuous or intermittent removal of polybutadiene or polyisoprene products; and (iv) From the polymerization zone, take out unreacted butadiene or isoprene, compress and cool the butadiene or isoprene and inert gas when present, while maintaining the polymerization zone · A temperature below the dew point is present in the reaction zone in the polymerization of a single ceremony. 2. The method according to item 1 of the patent application scope, wherein the temperature in the polymerization reaction zone is kept below the coagulation temperature of the monomers present in the polymerization reaction zone. Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 3. According to the method of item 丨 in the patent application scope, where the conditions in the polymerization reaction zone are such that substantially no liquid exists in the polymerization reaction zone. That is, it is not adsorbed on or absorbed in the solid particulate matter. 4. The method according to item 1 of the patent application scope, wherein the conditions in the polymerization reaction zone are such that at least a part of the monomers are not absorbed in the solid particles -42- 309522 A8 B8 C8 D8 VI. Scope of patent application The liquid in the sub-substance imprinted by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. According to the patent application section! The method of item, wherein the polymerization method is performed in the presence of an inert particulate material. The reactive particulate material is selected from the group consisting of carbon black, silica, talc, clay, and mixtures thereof. 6. The method according to item 5 of the patent application park, wherein the inert particulate material is carbon black, tapping stone or a mixture thereof. 7. The method according to item 1 of the patent application scope, wherein the polymerization catalyst contains a nickel metal component; the auxiliary catalyst is selected from the group consisting of triethylaluminum, triisobutylaluminum, gasified diethylming, and the Ministry of Economy Partly hydrolyzed gasified diethylaluminum, methylaluminum pits, modified methylaluminoxane and mixtures thereof; and the promoter is selected from etherification including gasified argon, boron trifluoride, hydrogen fluoride, Ethers of boron trifluoride, and mixtures thereof. 8. The method according to item 1 of the patent application scope, wherein the polymerization catalyst contains a metalogenic component; the cocatalyst is selected from the group consisting of triethylaluminum, triisobutyl · aluminum, Qihua Dipokishao, A Base aluminoxane, and mixtures thereof; and the selected accelerator is iodine, organic etherate or mixtures thereof. 9. The method according to item 丨 of the patent application scope, wherein the polymerization catalyst contains a cobalt metal component; the auxiliary catalyst is selected from the group consisting of sesquigasified ethyl aluminum, digasified ethyl alcohol, and partially hydrolyzed Gasified diethylaluminum, gasified diisobutylaluminum, partially hydrolyzed gasified diisobutylaluminum, fluorided diethylaluminum 'methylaluminum oxysulfonate and their mixtures. 10. The method according to item 9 of the patent application scope, wherein the polymerization catalyst additionally contains water as an accelerator. U. According to the method of item 1 of the patent application scope, in which the polymerization catalyst is in silicon, please read the note on the back. Meal binding 烺 Η -43 * π, the scope of applying for patents, ~ the printed stone of the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs, 砇 黑 'porous cross-linked polyphenyl ethyl #, porous cross-linked polypropylene, alumina, cymbals, Zirconium oxide, vaporized magnesium or a mixture thereof is supported. 12. According to the method of patent application item No. 1, the catalyst is supported on silica or carbon black. According to the method according to item 1 of the patent application, the butadiene or isoprene series is continuously introduced. Η. According to the application. Please apply for a patent model group! The method of item 1, wherein the method is carried out in the presence of a medicament or device for controlling the electrostatic content in the reactor. 5 'The method according to item 丨 of the patent application scope, wherein the static voltage in the reactor remains substantially neutral. 6. The method according to item 1 of the patent application scope, wherein the inert gas system is nitrogen gas. Π. According to the patent application section! Item method, wherein the polymerization catalyst is spray dried. 18. According to the method of patent application item 1, wherein the polymerization catalyst is introduced into the polymerization zone as a prepolymer β 19 ‘according to the scope of the patent application! The method of item 1, wherein the polymerization catalyst introduced into the polymerization reaction zone is a liquid, solution or slurry. 〇. A method for producing polybutadiene or polyisoprene in a stirred bed or a gas fluidized polymerization reaction vessel with a polymerization reaction zone under polymerization conditions. This method includes: (〇inert particulate matter and In the presence of at least one inert gas selected to introduce butadiene or isoprene monomer into the containing growing polymer -44- this paper € milk) 84 specifications (210 to 297 mm) 309522 A8 B8 C8 D8 patent application scope Central Government Bureau of Economics, Ministry of Economic Affairs, Staff Consumption Cooperatives, particle bed, polymerization reaction zone; (ii) In this polymerization reaction zone, a continuous or intermittent introduction of a nickel-containing, Polymerization catalysts of metal components of cobalt, titanium or mixtures thereof, a catalyst promoter and an optional accelerator; (iii) Polybutadiene or polyisoprene is continuously or intermittently taken out from the polymerization reaction zone Associated products; and (iv) from the polymerization zone, remove unreacted butadiene or isoprene, compress and cool the butadiene or isoprene and inert gas when present. 21. A method for producing styrene-butadiene rubber in a stirred bed or gas fluidized polymerization reaction vessel with a polymerization reaction zone under polymerization conditions. This method includes: (i) inert particulate matter and selection In the presence of at least one inert gas, introduce styrene and succinyl sulfide into the polymerization zone containing the growing poly-ideal particle bed; (Π) in the polymerization zone, continuously or Intermittently introducing a metal Shuangwuyuan polymerization catalyst, a cocatalyst and an optional accelerator; (iii) from the polymerization zone, continuously or intermittently withdraw the stupid ethylene-butadiene rubber product: and (iv) Take out unreacted butadiene and styrene from the polymerization zone, compress and cool the butadiene and styrene and when present. Relief gas Zhao 'while maintaining the polymerization zone The temperature is below the dew point of at least one monomer present in the polymerization zone. 22. According to the method of claim 21 of the patent application scope, in this polymerization reaction zone -45 paper scales are applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm). Please read the note of Λ I Book Travel 1 309522 A8 B8 C8 D8 6. The temperature within the patent application zone is kept below the condensation temperature of at least one monomer present in the polymerization zone. 23. The method according to item 2 of the patent application scope, wherein the conditions in the polymerization reaction zone are such that substantially no liquid exists in the polymerization reaction zone, meaning that it is not adsorbed on the solid particulate matter or Not absorbed in it. 24. The method according to item 21 of the patent application park, wherein the conditions in the polymerization reaction zone are such that at least a part of the monomer is a liquid that is not absorbed in the solid particulate matter. 25. The method according to item 2 j of the patent application scope, wherein the polymerization method is carried out in the presence of an inert particulate material selected from the group consisting of blackened silica, silica, clay, talc and mixtures thereof; and wherein The catalyst promoter is methyl-oxygen pit. Please read the notes first. I t ί Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 46-