TW387903B - Vapor phase synthesis of rubbery polymers - Google Patents

Abstract

By utilizing the vapor phase polymerization techniques of the present invention, numerous distinct and highly beneficial advantages are realized. For instance, cis-1, 4-polyisoprene rubber and high cis-1,4-polybutadiene rubber having a consistent and controllable molecular weight can be easily and practically prepared without utilizing a solvent. The subject invention more specifically discloses a method for vapor phase polymerizing isoprene into cis-1,4-polyisoprene in a process comprising the steps of: (1) charging into a reaction zone said isoprene and a preformed catalyst system which is made by reacting an organoaluminum compound with titanium ttrachloride, preferably in the presence of at least one ether; wherein the isoprene is maintained in the vapor phase in said reaction zone by a suitable combination of temperature and pressure; (2) allowing said isoprene to polymerize into cis-1,4-polyisoprene at a temperature within the range of about 35 DEG C to about 70 DEG C; and (3) withdrawing said cis-1,4-polyisoprene from said reaction zone. It has been determined that gel formation can be reduced by conducting the polymerization of isoprene monomer in the presence of a diarylamine, such as para-styrenated diphenylamine.

Description

Made by the Central Bureau of Standards of the Ministry of Economic Affairs, and co-produced by Du Du A7 ____B7___,, V. Description of the Invention (1)-, 1 Background of the Invention Various types of polymerization methods are used to prepare synthetic polymers. For example, the polymerization of monomers into polymers can be carried out in a variety of different types of reaction systems, including suspension polymerization systems, emulsion polymerization systems, non-aqueous dispersion polymerization systems, solution polymerization systems, monolithic polymerization systems, and gas phase polymerization systems. Each of these systems has certain advantages and disadvantages. 0 In a suspension polymerization system, the initiator (catalyst) is dissolved in the monomer, the single system is dispersed in water, and the dispersant is incorporated to form The suspension is stabilized. All suspension polymerization methods use a certain type of surfactant, to keep the monomer pellets dispersed during the reaction to avoid polymer agglomeration and cohesion. This suspension stabilizer will not only affect the particle size and shape. ' , And will affect the transparency, transparency and film-forming properties of the polymer formed. There are a variety of dispersants, including water-insoluble, subdivided: inorganic and organic substances, depending on the monomer to be polymerized, have been used as dispersants β. Therefore, for example, talc, barium, calcium and magnesium carbonates, silicic acid Salts, phosphates and sulfates, as well as salts of poly (vinyl alcohol), styrene-acrylic acid-maleic anhydride copolymer, ethyl acetate-maleic anhydride copolymer, starch, gelatin, pectin, seaweed Acid salts, methyl cellulose, carboxymethyl cellulose, bentonite, limestone and alumina have all been used as suspending agents. The main advantage of suspension polymerization is that it is known in the form of small beads of polymerization products. 'It is easy to pass; consider, wash, and dry. Due to cost and low reactivity, water systems are more desirable than most organic solvents. Diluent and heat transfer medium. However, in certain polymerization processes, the presence of water is highly undesirable. For example, 'In the preparation of cis-1,4 · polyisoprene with a titanium catalyst system, do not _-4- _ ^ _ This paper size is applicable to China National Standard (CNS) A4 (210 × 297 mm) ~ S • —I- 1 -1 V---*-=. II-! 11 — ^ 1 II--ms rf · < Λ ί Please read the notes on the back ¾ and then fill out this page} 〆 Ministry of Economy The Central Government Bureau of Quasi-Bureau Consumption and Cooperation of Shellfishers printed A7 --------------- B7., V. Description of the invention (2) " — A large amount of water is allowed. Another example in which the presence of water is a highly undesired polymerization is to synthesize very high cis-1,4-polybutadiene using a nickel catalyst system. Therefore, the suspension polymerization in an aqueous medium, for the use of titanium Catalyst systems for synthesizing cis-polyisoprene or nickel catalyst systems for synthesizing high-cis-1,4 · polybutadiene are not effective methods. The emulsion polymerization method is considered to be a three-phase reaction system, including large droplet monomers, an aqueous phase containing a dissolved initiator, and colloidal particles of a monomer-swelled polymer. Although the emulsion polymerization method has the economic advantage of using water as an emulsifying base ', not all polymerization methods can tolerate the presence of water. Use of a titanium catalyst system to polymerize isoprene to cis_14_polyisoprene, and a nickel rejection catalyst system to polymerize 1,3-butadiene monomer to extremely high cis ^, ' This is the case for polybutadiene. In order to recover the dry polymer made by emulsion polymerization, of course, the rubber must be agglomerated from the latex. The β agglomeration effect is usually achieved by adding a combination of salt and it to the latex. This results in the formation of wastewater, which may present environmental problems. In solution polymerization, an organic solvent capable of dissolving monomers, polymers, and polymerization catalysts or initiators is used. Since the polymer is soluble in the organic solvent used, the viscosity of the solution tends to increase as the molecular weight of the polymer increases. If it continues for a normal time, the solution becomes too viscous to be handled in conventional polymerization systems unless the solid content is limited to a low content. In commercial polymerization methods, it is generally desirable to obtain polymer agglomerates with a high concentration of solid polymer, and at the same time contain materials that are easy to handle and do not stick to the walls of the reaction vessel used. This polymer solution is usually stripped by steam. 'To remove solvents and unreacted monomers. Usually it is ______ of broken rubber -5- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) f. Read the precautions on the back before filling out this page > 3. Description of the invention (3) Α7 Β7 t Aqueous slurry printed by Shelley Consumer Cooperative of Zhongli Standard Bureau of the Ministry of Economic Affairs is pumped to the skimming tank, hydro-spiral dehydrator and press dryer to remove water. Steam stripping and drying operations consume a lot of blame energy. A preformed titanium catalyst system was used to polymerize the isoprene monomer solution into cis-1,4-polyisoprene rubber, which is described in US Patent 3,386,983. A catalyst system containing a phosphonium organoaluminum compound, (2) an organic nickel compound, and (3) a hydrogen fluoride complex was used to polymerize a 1,3-butanefluorene monomer solution into a high-cis-1,4-polybutadiene rubber It is described in US Patent No. 4,155,880. In the non-aqueous dispersion polymerization, an organic medium is used, which is a very poor solvent for the polymer to be manufactured. The # powder is used in organic media to disperse the formed polymer throughout the media. The dispersant (dispersion stabilizer) used in this kind of non-aqueous dispersion polymerization is usually a polymer material, which can be a block copolymer, an random copolymer or a homopolymer. The non-aqueous dispersion polymerization system is described in U.S. Patent No. 4,098,980 and U.S. Patent No. 4,452,960. The "non-aqueous dispersion polymerization method" provides several significant advantages over solution polymerization and emulsion polymerization. These include improved heat transfer, Higher polymer concentration in the media, increased production capacity and energy savings. Monolithic polymerization is the direct conversion of a liquid monomer into a polymer. Such monolithic polymerization is usually performed by adding an initiator to a homogeneous homogeneous system containing one or more monomers. The polymer made by the whole polymerization of this bamboo shoot can be (but not necessarily) soluble in its own monomer, and it is actually used as a reaction medium. For example, polyisoprene is quite soluble in isoprene, and polyprene is quite soluble in 1 > 3-pentadiene, but high cis-i, 4_polybutadiene is Will not be extremely soluble in 1,3_ butadiene mono Zhao β

(#Please first read the notes on the back and then fill out this page) ______h

Explanation of IT line invention (4 Synthesis of polystyrene by adding a free radical initiator to styrene monomer 'is a very common good example of whole polymerization. 0 The main advantage of the overall polymerization method is that no solvent is used. β Therefore, the cost of solvent recovery and recycling is waived. One disadvantage of the polite polymerization reaction is that it is difficult to control the reaction temperature during the polymerization reaction. In fact, attempts to polymerize many types of Shan Zhao as a whole have caused uncontrolled Due to this difficulty, the reaction β is not widely used in the commercial preparation of synthetic rubber. The overall polymerization eliminates the need to use a solvent, which must be separated from the rubber and recycled or otherwise Disposal. The cost of solvent recovery and recycling will make the cost of rubber to be greatly increased, and may cause certain environmental problems. Recovery and separation of rubber from solvents also require other treatment and equipment, all of which Will further increase the cost of rubber. Purification of recycled solvents may also be extremely expensive, and always has the following dangers The solvent may still remain impure, which will poison the polymerization reaction catalyst. The concept of preparing synthetic rubber by using Zhao polymerization was formulated by the Sinopec Junbei Shellfish Consumer Cooperative, and it is not new. Diene monomers have been known for many years. The polymer can be polymerized into synthetic rubber in the absence of solvents. In fact, Germany and Russia used alkali metal catalysts to synthesize polybutadiene and polydimethylsiloxane in a batch process during the First World War. Polybutadiene. Polybutadiene has also been made by adding a catalyst to a small polymerization bottle containing butadiene monomer. Due to the highly exothermic nature of this whole polymerization, it is used in these small scales. It is not unusual for the polymerization bottle to explode, which is not unusual at all. Since this overall polymerization reaction is basically uncontrollable, the polymer uniformity is extremely poor, gel formation is often a problem, and molecular weight control is extremely Difficult. Therefore, the overall polymerization of isoprene monomers becomes 7- This paper size applies the Chinese family standard (CNS) Αvision (210 > < 297 public director A7 B7 central standard of the Ministry of Economic Affairs) Printed by the Bureau ’s Consumer Cooperatives 5. Description of the Invention (5) Cis-1,4-polyisoprene has not been widely considered commercially viable. A device for cooling the reaction zone has been proposed to Control the overall polymerization by controlling evaporation and removing a portion of the liquid reactants from the reaction zone. This technique is sometimes referred to as self-cooling. The description of tidy polymerization using self-cooling is presented in the United States Patent No. 3,458,490. In the technology disclosed therein, the solution of polybutadiene in Dingyihaodan Zhao is prepared in a solution polymerization reactor, which is stirred in a spiral manner. However, only 35% of The butadiene feed monomer is converted to a polymer. It uses steam stripping to remove unreacted monomers from the formed polybutadiene product.. Uses self-cooling to control foaming. A monolithic polymerization process is described in U.S. Patent 3,770,710. In the technology disclosed therein, a method is employed that includes first preparing a polymer-monazine solution having a solids content of only 20 to 40 percent at a polymerization temperature that does not substantially exceed about 50 " c 'and In a subsequent reactor, the polymer-monomer solution was continuously polymerized at a temperature ranging from 50 ° C to 150eC. A catalyst-containing system is used in the method described therein, in which the Muni viscosity of the polymer formed increases with the polymerization time. Canadian Patent No. 1,284,545 discloses a method for neatly polymerizing ι, 3_butadiene to high cis_1,4_polybutadiene in a continuous process, which includes: (1) adding the 1,3-butadiene; catalyst system containing rhenium organoaluminum compounds, (b) compounds containing soluble nickel, and (c) fluorine-containing compounds; (2) polymerizing the 1,3-butadiene into high-cis Formula 4,4-polybutadiene, up to at least -8-m Lang ruler Newcai ® Home County (CNS) A4 ^ (21 () > < 297 male thin (Fang first read the precautions on the back and then (Fill in this page) ------- Γ Setting line V. Invention description (6 A7 B7 The consumption cooperation stamp of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China restricts the conversion rate of 60%, while using the following conditions, here Under the conditions, there is sufficient evaporative cooling effect in the reaction zone to keep the temperature in the range of 13 (TC;) and (3) continuously take out the high cis_1Λ polybutadiene from the reaction zone. Canadian patent Application 2 133,526 discloses a catalyst system and technology for gas-phase polymerization of conjugated diene monomers, such as butadiene monomers, into polymers. However, this Canadian patent Any polymerization reaction that makes isoprene into polyisoprene is not disclosed. Beta catalyst system disclosed by Canadian patent application 2 133 526, which contains rhenium rare earth metal component, rhenium organoaluminum compound,-(c) Louis Acrylic acid composition and (d) emotional fine particles of inorganic solids. This gas phase method is reported to provide environmental benefits that can be attributed to the fact that no solvents are used, thereby reducing emissions and wastewater pollution. US Patent 5 317 〇36 discloses A method and equipment 'uses unsupported soluble transition metal coordination catalysts to gas phase polymerize olefin monomers into polymers. SUMMARY OF THE INVENTION With the gas phase polymerization method of the present invention, there are many significant and highly advantageous advantages All are achieved. For example, a high cis-1,4-polyisoprene rubber with a relatively high molecular weight can be easily and practically made without using a solvent. It has a relatively uniform or uniform and High cis-1,4-polybutadiene rubber with controllable molecular weight can also be made easily and practically without using solvents. It can be made for specific applications that require significantly different molecular weights To make high cis-1,4-polybutadiene, it only changes the procedure to obtain the desired molecular weight without limiting the conversion rate. Since the gas phase polymerization technology of the present invention does not require a solvent, Solvent removal-9- This paper size applies to China National Standards (CNS) Α4 size (210X297 male diamond) -nr Read first * Back / i Note t / ί 1 page Λ Order __B7 V. Description of the invention (7) _ ~~ The need for steps is eliminated. Of course, the need to purchase and process solvents is also eliminated, which will reduce the cost of the overall process. After understanding the fact that high conversion rates can be obtained, volatile organic compounds such as monomers are used in The amount of rubber made is the lowest β. This is of course because the reaction medium used is solvent-free. In summary, the gas phase polymerization method of the present invention provides an environmental advantage that can be attributed to the fact that no solvent is used, and therefore reduces emissions and pollution of wastewater. It has surprisingly been found that diarylamine antioxidants, such as p-phenylethylenated diphenylamine, do not interfere with the gas phase polymerization of the present invention. It has also been unexpectedly discovered that hindered phenol antioxidants do not interfere with the gaseous polymerization of 13i butadiene monomers into cis-1,4-polybutadiene rubber. Therefore, it allows such a polymerization reaction to be performed in the presence of these types of antioxidants. This antioxidant can be pre-mixed with the catalyst, it can be pre-mixed with the formulation, or it can be added to the reaction zone as an individual ingredient. The presence of such antioxidants during the polymerization of the milk phase during the milk phase polymerization, which is printed by DuPont, the China Bureau of Standards and Technology of the Ministry of Economic Affairs, is highly advantageous, because the synthesized rubbery polymer is used in the final processing of gas-phase polymerized rubber. The high-temperature period that has been scrapped during storage is of improved stability. The problem of oxidative degradation is particularly severe in gas-phase polymerized diene rubbers because rubbery polymers are usually in finely divided form, which makes them more susceptible to degradation. This% oxidation resistance, of course, remains in the rubber subsequently 'and continues to provide a higher degree of stability to prevent oxidative degradation throughout its useful life. Diarylamines, such as p-styrylated diphenylamine, existed during the polymerization of isoprene to polyisoprene, and have also surprisingly been issued ___ -10- This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0 × 2? 7 mm)-A7 B7 V. Description of the invention (8 will now reduce gel formation. This ability to reduce gel formation has often proven highly advantageous. In the presence of diarylamines, nickel-catalyzed gas-phase polymerization of 1,3-butadiene monomer will also reduce the molecular weight of the high-cis-1,4-polybutadiene rubber produced. The molecular weight of the high cis-1,4_ polybutadiene rubber can be controlled by performing such polymerization in the presence of a specific amount of diarylamine. In other words, the molecular weight of the synthesized rubber can be determined by Performing this polymerization reaction in the presence of a small amount of diarylamine is slightly reduced 'or can be greatly reduced by performing this polymerization reaction in the presence of a relatively large amount of diarylamine. More specifically, the present invention discloses Gas phase polymerization of isoprene to cis-1,4-polyisoprene The method is performed by a procedure including the following steps: (1) adding the isoprene and a pre-formed catalyst system to the reaction zone; this catalyst system is formed by reacting an organoaluminum compound with titanium tetraoxide The preparation is performed in the presence of at least one ether; wherein the isoprene in the reaction zone is' maintained in a gas phase by an appropriate combination of temperature and pressure; (2) at about 35 C to about 70. At a temperature within the range of 9C, the isoprene is polymerized into cis-1,4-polyisoprene; and printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please fill in the precautions on the back first) (This page) Order (3) Take out the cis-1,4-polyisoprene from the reaction zone. The present invention further discloses a method for gas-phase polymerization of isoprene to cis-polyisoprene. The procedure is as follows: (1) adding the isoprene and a pre-formed catalyst system to the reaction zone, the catalyst system is made by reacting an organoaluminum compound with titanium tetraoxide; The isoprene in the reaction zone is determined by temperature and pressure A7 B7 9 5 Description of the invention (The proper combination of forces maintains the gas phase; (2) At a temperature within the range of about 0 ° C to about 100 ° C, the isoprene is polymerized into cis-1,4-polyisoprene And (3) taking out the cis-1,4-polyisoprene from the reaction zone. The present invention also discloses a gas phase polymerization of 1,3-butadiene to high cis-fluorene, 4 · polybutene The method of diene is performed by a procedure including the following steps: (1) adding the 1,3-butadiene and a catalyst system to a reaction zone, the catalyst system comprising (a) an organoaluminum compound, ( b) a nickel-containing compound and (c) hydrogen fluoride or a hydrogen fluoride complex; wherein 1,3-butadiene is maintained in the reaction zone by maintaining a gas phase by a proper combination of temperature and pressure; (2) in Polymerize the 1,3-butadiene into high-cis-1,4-polybutadiene at a temperature in the range of 10 ° C to 130 ° C; and (3) take out the high-cis from the reaction zone Formula 1,4-polybutadiene. The present invention further discloses a method for gas-phase polymerization of a conjugated difluorene monomer into an rubber and a colloidal polymer, which is performed by a procedure including the following steps: (1) adding the conjugated diolefin monomer to a reaction zone , Catalyst and arylamine antioxidant; wherein the conjugated diene monomer in the reaction zone is maintained in the gas phase by an appropriate combination of temperature and pressure; (2) the conjugated diene monomer is Polymerization into the b polymer in the reaction zone, and colloidal state (3) The rubbery polymer is taken out of the reaction zone. Brief Description of the Drawings Figure 1 is a schematic diagram of a preferred embodiment of the present invention, showing-it can be used for conjugated diene monomers, such as isomeric media ^ Qiu and 1,3-butadiene paper scales applicable to China National Standards (CNS> (210X297 public love) .I · 1. i-I -I-I!-I — ^ 1 f, (n I tf (Please read the precautions on the back before filling this page}

1, 1T printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 printed by the Shell's Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (9 appropriate combination of forces to maintain the gas phase; (2) at about 0 ° C Polymerize the isoprene to cis-1,4-polyisoprene at a temperature of about about 100 g; and (3) take out the cis-1,4-polyisoprene from the reaction zone The present invention also discloses a method for gas-phase polymerization of 13-butadiene to high-cis-polybutadiene, which is performed by a procedure including the following steps: (1) adding the 13-butadiene to the reaction zone Diene and catalyst system; ^, this catalyst system includes (a) organoaluminum compound, osmium nickel-containing compound, and (c) hydrogen fluoride or hydrogenated hydrogen complex; 1 > 3_ butadiene in the reaction zone In the middle, the gas phase is maintained by an appropriate combination of -temperature and pressure; (2) at a temperature in the range of 130 to (: the 1 > 3 · butadiene is polymerized to high cis-1,4 -Polybutadiene; and (3) taking out the high-cis, 4-polybutadiene from the reaction zone. The present invention further discloses a co-roll diene monomer gas The method for polymerizing into a rubbery polymer is performed by a procedure including the following steps: (1) adding the conjugated dioxane monomer, a catalyst, and a diarylamine antioxidant to a reaction zone; wherein the conjugate is The diene monomer in the reaction zone is maintained in the gas phase by an appropriate combination of temperature and pressure; (2) the conjugated diene monomer is polymerized into a rubber bear polymer in the reaction zone; and (3) Take out the rubbery polymer from the reaction zone. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of a preferred embodiment of the present invention, which shows a device that can be used for conjugated diene monomers, such as Isoprene and table paper dimensions are in accordance with Chinese National Standard (CNS) A4 specifications (210X297g __________ ^ 14T__ .M- Γ (read the precautions on the back before filling this page), 17 Central Bureau of Standards, Ministry of Economic Affairs Printed by Industrial and Consumer Cooperatives A7 _ _B7 V. Description of the invention () Continuous gas phase and fluidized bed polymerization of diene polymerized into rubbery polymers, such as cis 1,4-polyisoprene rubber and high cis-1 , 4-polybutadiene rubber. Detailed description of the invention In the combined reaction, the reaction zone is constructed by providing constant agitation of its contents. It is also constructed in the following manner, which will provide a sufficient cooling device to maintain the desired temperature in the reaction zone ( In the case of isoprene being polymerized, it is about 0 eC to about 10 ° C, and in the case of 1,3-butadiene being polymerized, about 10 ° C to about 13 (TC). Finally, one A device for conveying rubbery polymers from the reaction zone will be included in the design of a reaction zone, such as cis-1,4-polyisoprene or high-cis-M- Ju Ding Er Yi. -Gas phase polymerization can be carried out in a fluidized bed reactor, a stirred reactor or a paddle-type reaction system. Although the following discussion will describe the characteristics of a fluidized bed system, it should be clear that the general concept of gas-phase polymerization is applicable to a stirred or paddle-type reaction system. The invention is not limited to any particular type of gas phase reaction system. From a very general point of view, the conventional fluidized bed method for producing rubbery polymers is performed in the following manner, under reaction conditions and the presence of a catalyst, at a speed sufficient to maintain the solid particle bed in a suspended state, so that A gas stream containing one or more monomers is continuously passed through the fluidized bed reactor. The gas stream containing unreacted gaseous monomer is continuously withdrawn from the reactor, compressed, cooled and recirculated to the reactor. The rubbery product was withdrawn from the reactor and supplementary monomer was added to the circulating gas stream. A basic conventional fluidized bed system is shown in FIG. Reactor 10 series _____- 13- ______ This paper scale is applicable to China National Standard (CNS) A4 (210X297 mm) -------- (J ί-- Μ_ V .. ,, ( Read the French and Italian matters on the back and fill in the original order)

C Α7 Β7 5. Invention description (u) includes a reaction zone 11 and a speed reduction zone 12. Although the reactor type shown in FIG. 1 includes a generally cylindrical region, which covers a fluidized bed located below the expansion section, alternative types, such as including a full or partial push, can also be used. Reactor type of pull-out reactor. In this type, the fluidized bed is located in the area of the push-type reaction zone, but is lower than the larger cross-sectional area. This area is used as the speed of the conventional reactor type shown in Figure 1. Reduce the zone. In general, the ratio of the height to the diameter of the reaction zone can be changed in the range of about 2.7: 1 to about 5: 1. This range can be changed to a larger or smaller proportion, and depends on the desired capacity. The cross-sectional area of the speed reduction zone 12 is typically about 2.5 to about 2.9 times the cross-section of the reaction zone u. Area. The print zone 11 printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs includes growing polymer particles, formed polymer particles and a small amount of catalyst beds, all of which are continuously polymerizable and modified for use. Gaseous components are fluidized by inert gas and pass through the reaction zone β in the form of supplementary feed and recirculation / Wa Zhao to maintain a usable fluidized bed. The surface gas velocity through this bed must exceed the required fluidization Minimum flow rate, which is typically about 0.2 to about 0.5 feet per second (about 6 > 1 cm / sec to about 15 2 cm / sec). The surface gas velocity is preferably at least 0,2 above the minimum flow rate of fluidization. Laziness / second (6.1 cm / second), or about 0.4 laziness / second to about 0.7 laziness / second (12.2 cm / second to 2U cm / second) .. usually the surface gas velocity does not exceed 5_0 152.4 cm / s) and often does not exceed about 2_5 feet / s (76.2 cm / s). At the start, before the start of gas flow, a particulate polymer particle bed is usually added to the reactor. Such particles help prevent the catalyst from being fed -..--- ~ ---- J4- Common paper standard (CNS) for this paper standard (Congluo (210X297) Ⅴ. Description of the invention (12 Α7 Β7 ml — ^ ϋ

The Ministry of Economic Affairs and the Central Government Bureau of the Jungong Consumer Cooperative, Ltd. printed the initial location of the "hot spot", which may be the same as or different from the polymer to be formed. When it is different, it is taken out together with the newly formed polymer particles as the first product. Finally, the starter bed is replaced by a fluidized bed containing the desired polymer particles. * Fluidization is achieved by recirculating a high rate of fluid to the bed and passing through the bed, typically at the rate of feed or make-up fluid. About 50 times the spectrum. This high recirculation rate provides the necessary surface gas velocity necessary to maintain the fluidized bed. This fluidized bed has the general appearance of dense clusters of individual moving particles', such as that caused by gas percolation through the bed. After the 'pressure drop of the bed', it is equal to or slightly greater than the weight of the bed divided by the cross-sectional area. 0 The make-up gas from the make-up line 13 is fed into the recirculation line 15 at point 14. The make-up gas contains monomer and inert gas. If necessary, an inert gas such as nitrogen can be added to make the polymerization rate moderate and the composition of the recirculated gas stream is typically measured by the oxygen analyzer 16 and the composition and quantity of the supplementary gas stream are adjusted accordingly to maintain the basic The steady-state gaseous composition is in the reaction zone. The gas analyzer 16 may be placed in an appropriate position to receive the gas from the point between the speed reduction zone 12 and the heat exchanger?, Preferably from the point between the compressor 18 and the heat exchanger 17. In order to ensure complete fluidization, a further 0 loop gas stream and, if necessary, at least a portion of the supplemental gas stream, are passed through the recirculation line 15 and returned to the reactor β at point 19 below the bed. Preferably, there is one. The distribution plate 20 is higher than the return point to help the bed to fluidize uniformly, and the airflow that branches solid particles 0 upwards and leaves the bed before starting or when the system is shut down will be removed by

It, II--III I ...... IT -Λϊ γ 1. A * V '/ (#Please read the notes on the back before filling this page) Order cf 中央 Central Ministry of Economic Affairs, Central Bureau of quasi-government, shellfish consumer cooperation Du printed A7 ____ B7 _ ^ ___ 5. Description of the invention (13) The heat of reaction generated by the exothermic polymerization reaction. The part of the gas stream that flows through the fluidized bed without reacting in the bed becomes a recirculating gas stream. It leaves the reaction zone 11 and enters the speed reduction zone 12 above the bed. The transported particles fall back to the bed, thus reducing the migration of solid particles. The recirculated gas stream is then compressed by a compressor 18 and passed through a heat exchanger 17 where the recirculated gas stream is removed from the reaction heat before returning to the bed. Then, the recirculated gas stream leaving the heat exchange zone is returned to the reactor at the bottom 21 of the reactor, and passes there through the gas distribution plate 20 to reach the fluidized frame. The fluid flow turning plate 22 is preferably installed at the inlet of the reactor to prevent the contained polymer particles from precipitating and agglomerating into solid lumps-and to keep it transported or re-transported for any possible precipitation or stop being stopped. Particles or liquids carried. _ The particulate polymer product is discharged via line 23. The residual monolith is removed from the rubbery polymer product by means of a monomer separator 24. The polymer product is removed via product line 25 and the single system is returned to recirculation line 15 via monomer recovery line 26. In the specific embodiment shown in Figure 1, mixing is carried out prior to introducing the supported catalyst into the reaction zone. The supported, pre-formed catalyst system is introduced into the reaction zone 11 by feeding the catalyst into the reactor via the catalyst feed line 27 'at point 28, which is located in the reaction zone The upper part 0 is injected into the reactor through the supported catalyst, preferably in the upper part of the fluidized bed reaction zone 11 to provide a uniform distribution. Catalyst transfer and entry ____ -16- _ Zhang Zhang M is applicable to the National Standards of Ten Countries (CNS) Ya 4 threats (210X297 male thin) one ~ one --- (t read the precautions on the back before filling this page)

A7 A7

5. Description of the invention (M) The recycling line 15 is usually not an important issue, even if it is the case of injecting a supported catalyst into the upper part of the reaction zone. It is important to 'minimize the transfer of catalyst into the recycling line, because the polymerization reaction may begin and the clogging of the recycling line and the heat exchanger may eventually occur. The pipeline may cause the polymerization reaction to occur outside the reaction zone of the reactor, which may cause blockage of the recycle pipeline and blockage of the heat exchanger. However, if necessary, the catalyst can be introduced into the reaction zone at a point completely above the fluidized bed reactor, but the point is still low enough to allow any catalyst to be transferred into the recycling line. The situation is minimized. The factors to be considered are the cross-sectional area of the reactor at the catalyst injection point, the velocity of the gas flow through the fluidized bed, the entry point of the catalyst into the reactor, and the particle carrier for the catalyst. size. _ Under the set operating conditions, the fluidized bed is maintained at a substantially constant height. The method is to extract a part of the bed as a product, and the rate is basically equivalent to the formation rate of the microparticle polymerization product. As already pointed out, the temperature in the reaction zone is adjusted to the desired range by the heat exchanger 17. When the rubbery polymer leaves the reaction zone via line 25, it may generally be desirable to add polymerization stoppers, antidegradants, and / or other conventional rubber chemicals in the discharge zone '. It is usually preferred to add an antidegradant directly to the reaction zone 11. If it is desired to prepare oil-increasing rubber, such rubber chemicals are mixed into the rubbery polymer by first dissolving them in working oil or mineral oil. Triisopropanolamine can be dissolved in process oil or mineral oil and filled with ____ -17- This paper size is applicable to China National Standard (CNS) A4 (210X297 male thin) (please read the precautions on the back before filling) (Finding) Γ

• 1T & Central Laboratories of the Ministry of Economic Affairs and Labor Cooperation, Du printed A7 B7 5. Description of the invention (15) as a polymerization stopper. In the case where a tread rubber is to be prepared, about 1 to about weight percent of a process oil may be mixed into the rubbery polymer. In short, 逋 equivalent of extender oil can be added to help the process of distributing the desired rubber chemicals throughout the rubbery polymer. Β After the polymer has left the reaction zone, it may be necessary to remove it in the monomer separator 24 Volatile matter. This is usually achieved by repeatedly exposing the rubbery polymer to high temperatures and reduced pressure. This devolatilization process can be repeated as many times as needed to reduce the volatiles in the rubber to an acceptable level. However, the devolatilization effect is not required unless there is an unacceptably high content of residual-residual monomers or other volatile substances in the rubbery polymer β. Therefore, the conversion rate in mono-zhao approaches 100%, and With less than 100 ppm (parts per million) of volatile organic compounds present, devolatilization may not be needed. However, it is often desirable to reduce the amount of volatile organic compounds present below 10 ppm. Yan Pengyi, President of Gas Phase Polymerization, Central Bureau of Standards, Ministry of Economic Affairs, Esc Industrial and Consumer Cooperatives, printed isoprene monomers can be continuously gas phase polymerized using a preformed titanium catalyst system to polymerize into cis-1,4- Polyisoprene (95% or more of cis-1,4-isomeric isoprene units made by the method of the present invention_ Polyisoprene, usually having a number average molecular weight of at least ⑻, and more typically has a number average molecular weight greater than 200,000. Gas-phase polymerization of isoprene is carried out at a temperature in the range of about 0 ° C to about 100 ° C. In this gaseous polymerization, The temperature in the reaction zone is usually maintained in the range of about 35 ° C to about 70eC. In the reaction zone, it is preferred to use a temperature in the range of about 4 ° C to about 6CTC. Vapor phase -----__-__- 18-This paper size applies Chinese National Standards (CNS) A4 is now standard (210X297 public) A7 B7 Printed by the Central Laboratories and Consumer Cooperatives of the Ministry of Hydrocarbons 11 V. Description of the invention ( 16) The optimal temperature is about 45 ° c to about 50eC. The preformed titanium catalyst system is Fu is made to react with the organoaluminum compound is preferably an organic compound-based Ming malocclusion with an acid may be used a organoaluminum compound, the system having the following structural formula:. A1-R,

Xr3 is selected from the group consisting of alkyl (including cycloalkyl), aryl, aryl, arylalkyl, and hydrogen; Rz and I are selected from the group including alkyl (including cycloalkyl), aryl, and Fang Ji and Fang School * Ji. One of the organic compounds that can be used. Some representative examples are hydrogenated diethyl chains, hydrogenated di-n-propylamines, hydrogenated di_ 矣 _butylamines, hydrogenated isobutylamines, and argonized diphenylamines. , Hydrogenated di-p-tolyl, Hydrogenated diethylamino, Hydrogenated phenylethyl, Hydrogenated phenyl-n-propylpropyl, Hydrogenated p-tolylethyl, Hydrogenated p-tolyl -Propyl aluminum 'p-tolyl isopropyl aluminum argon, benzyl ethyl aluminum hydride, fluorinated n-propyl and trimethyl isopropyl, trimethyl, triethyl Trick, tri-n-propyl aluminum, tri-isopropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tripentyl aluminum, trihexyl aluminum 'tricyclohexyl aluminum, trioctyl aluminum, Triphenyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl metal, ethyl dimethyl, diethylphenyl, Ethyl p-methylbenzyl keto, diethyl benzyl and other three organic compounds. Preferred organoaluminum compounds include triethylaluminum (TEAL), tri-n-propylaluminum, triisobutylaluminum (TIBAL), trihexylaluminum and diisobutylaluminum hydride (dibA-H). The titanium bracelet media system used must be preformed "Because it is preformed,

Ms · Zhang scale applies Chinese National Standard (CNS) A4 specification (plus χ_297 ") (will read the precautions on the back before filling out this page), 1T printed by the Consumer Cooperative of the Central Government Bureau of the Ministry of Economic Affairs A7 ____ B7 V. Invention Explanation (π) ~ '~-Therefore, the catalyst system will maintain a high degree of activity for a long time. This kind of pre-formed system will also lead to the formation of homopolymer products. The formed titanium catalyst system is made in the presence of-or more ethers. The preformed titanium catalyst can be made by a batch method. In this batch method, the catalyst components are sequentially added to the reaction. In the container. The tetragas titanium component is usually added in the form of an organic solution to the reaction container. Then, the Ming component and the acid are added to the reaction container to produce a preformed titanium catalyst, which is in the form of a slurry. The pre-formed catalyst system can also be made by continuous meal order, as described in Australian Patent 582,273 ^ The content of Australian Patent 582,273 is incorporated herein by reference. Time Titanium and aluminum compounds and ether mixtures are mixed together "Titanium tetragas can be added as a solution of titanium tetragas in an inert organic solvent, or it can be added simply (not diluted in an inert organic solvent)" used in this article The term "inert organic solvent" refers to an organic solvent that is chemically inert to all catalyst components used in this method. In other words, the "inert organic solvent will not interact with titanium tetraoxide, trialkyl aluminum Compounds or ether compounds. Some representative examples of inert organic solvents include aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and mixtures of two or more of the above solvents. Hydrocarbons, including benzyl, toluene, dibenzobenzene, ethylbenzene, diethylbenzene, isobutylbenzene, and the like. Some representative examples of suitable aliphatic hydrocarbons include n-pentane, n -Jiyu •, Iso-yaki type, N-yaki-yaki, N-yaki-yaki, Iso-yaki type 'Zheng -------_? Η- ____ This paper standard is applicable to the China Standard Standard (CNS) eight specifications ( 210 × 297 mm) (Please read the back (Please fill in this page again)

• II Dimethyl butyrate 'petroleic acid, kerosene, gasoline, petroleum spirits and use :: Dioxane and methylcyclohexane are representative examples of alicyclic hydrocarbons that can be used as emotional organic solvents . Extremely sensitive to pollutants, such as oxygen, oxygen-containing compounds, and small amounts of this dye will reduce the activity of the catalyst. Because of the sensitivity, cold dyes, such as water, alcohols, alcohols, carbon oxides, age-based compounds, hydrogen sulfide, mercaptans and the like, should not be present in inert organic solvents in large amounts. . Dissolved material in inert organic solvent (milk 'should be removed before preparing a solution of osmium tetrachloride or a trisyl subtractive compound and solution. This can be achieved by spraying an inert organic solvent with a rare gas or nitrogen. The acids used in the present invention usually contain 2 to 40 carbon atoms, and preferably 4 to 20 carbon atoms. Some representative examples of such ethers include diethyl ether, dipropyl ether, diphenyl Ether, methylphenyl ether and the like. Diethyl ether is a good choice when used with triethyl aluminum, while diphenyl ether is a good choice when used with triisobutyl aluminum. Solution or simply use. The solution of titanium tetragas can be simply made in the following way. Titanium tetragas can be mixed into an inert organic solvent and printed by Shelley Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy to produce a solution containing at least 3% by weight. Homogeneous solution of vaporized titanium. In most cases, such a solution of four gasified titanium contains 3 to 25% by weight of titanium tetragasified, based on the total weight of the solution. Mixture can be made Liquid or simple use. The ratio of the chain to the trialkyl aluminum compound is usually 0.4: 1.0 to 1.2: 1.0, and the ratio of 0.5: 10 to 1.0: 1.0 is preferred. Ether solution, 21-, paper size, using Chinese National Standard (CNS) A4 specification (210 × 297 mm) V. Description of invention (19) A7 B7 The printing by the Central Labor Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, can be made in the following manner At least 3 weight percent of the trialkyl aluminum compound and at least 1.5 weight percent of the ether are mixed into an inert organic solvent to produce a homogeneous solution. In most cases, the mixture of the trialkyl aluminum compound and the ether is Contains 3 to 25 weight percent of trialkylaluminum compounds and 15 to 13 weight percent of ether. If a sufficient amount of inert organic solvent is added individually, these two ingredients can be simply added to produce a content of 1 to 13 weight Percent Tetragasification, a solution of 1 to 13 percent by weight of a trialkyl compound, and 0 to 8 percent by weight of ether. A mixture of tetratetratitanium and a trialkylaluminum compound and an ether is added in the following amount, to As a result, the molar ratio of the trialkylaluminum compound to titanium tetragas is between 0.7: 1.0 to 1.2: 1.0. The molar ratio of the trialkylaluminum compound to titanium tetragas is preferably 0.8: Between 1 and 1.1: 1, among which the best molar ratio of trialkylaluminum compounds to tetrakiscinium is between 0.85: 1.0 and 0.95: 1.0. The solution of the aluminum compound and the ether is thoroughly mixed by applying some form of vigorous agitation. Generally, this agitation is provided by rotating the blades in the reaction zone. The catalyst components are mixed and maintained at -20eC. To a temperature of 60 ° C. The catalyst system is usually preferably preformed at a temperature of -5 ° C to 50 ° C. The formed catalyst slurry is aged for 0.5 to 200 hours to form a pre-formed catalyst composition. Generally, it is preferable to age the pre-formed catalyst system for about 1 hour to about 24 hours. The system is aged for 2 to 6 hours. -·-Before the preformed titanium catalyst system is used for the gas phase polymerization of the present invention, it is recovered from the preformed catalyst slurry. This can be easily applied to the -22- Chinese paper standard (CNS) A4 size (2 丨 0'〆297mm>

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I Filling / Ordering on this page ο Printed by the Consumers 'Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _ -....... B7 _ V. Description of Invention (20)' — The following methods are achieved to make the preformed catalyst system The solvent in the solvent evaporates to produce a powder of a preformed titanium catalyst system. This procedure can be aided by the use of high temperature and / or air. It can also be done by passing an inert gas through the catalyst suspension. In the batch method, a pre-formed catalyst solution can be added to the reaction zone (reactor) 'where the solvent is removed before the monomer is introduced β. In this case, the dry catalyst system usually sticks to the reaction The solvent in the wall of the preformed catalyst solution can be removed from the outside of the reaction zone to form a powder, which can be continuously added to the reaction zone in a continuous process. Preformed titanium catalyst systems are usually best supported. The carrier may be any solid material, which is inert and does not adversely affect the properties of Shun · 1 > 4-isoprene rubber. Carbon black and silica are examples of materials that are highly preferred as a carrier. This is because carbon black and silica are often used as fillers' in rubber compounds and they are present in the rubber to be synthesized and are generally not considered harmful. In fact, carbon black and / or silica-containing cis-〗, the use of 4_ polyisoprene rubber is considered to be a beneficial β in many applications. To reduce the degree of gel formation 'Sometimes it is desirable Polymerization in the presence of diarylamines, such as p-phenylethylfluorinated diphenylamine β In general, the molar ratio of 'diarylamine to tetrakisdolinium is about 5: 1 to about 0.05: within the range of 1. The molar ratio of diarylamine to titanium tetragas is more typically in the range of about 2: 1 to about 0.25: 1. ^ The molar ratio of diarylamine to titanium tetragas is typically better. It is in the range of about 15: 1 to about 05: 1. Diarylamines are usually mixed with a preformed titanium catalyst system before undergoing skeletalization. Therefore, diarylamine is also supported by the catalyst system. The diarylamines that can be used have the general structural formula: ____- 23- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm) '" ~~ * — ^' (t 先 闻Read the notes on the reverse side and fill out this page) -------- X I-% _______ 丁. N Γ 丨 V. Description of the invention (21 A7 B7

Wherein R represents a hydrogen atom, an aryl group, an alkyl group or an alkaryl group. Para-styrylated diphenylamines' are highly preferred diarylamines. Wingstay® 29 p-phenylethylenated diphenylamine, commercially available from Godyear Tire and Rubber Company, and typically consists of several isomers, including: p-diphenylethylenediphenylamine O-, p-, p-tristyryl diphenylamine-o-, p-dibenzyl diphenylamine '. P-benzyl vinyl diphenylamine-p, p-di-epiethylenediphenylamine p-styrene Diphenylamine, also known as p-distyryldiphenylamine, has the chemical structural formula:

Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Para-phenylethylidene dibenzylamine is also sold by Lovvi under the trade name Lowinox SDA and by Mobay under the trade name Vulkanox DDA. In the preparation of a carrier catalyst system, it is generally desirable to passivate the material to be used as a carrier. This is usually achieved by treating with organoaluminum compounds by destroying the active sites on the material. This organoaluminum compound is usually the same as the organoaluminum compound used in the preformed titanium catalyst system. This catalyst dispersion was added to a support to form a slurry. Then, remove the solvent, for example -24 This paper size is applicable to China. National Standard (CNS > A4 is now (2! 0X 297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs ) If evaporation is used to deposit the preformed catalyst on the carrier, the gas phase of the butadiene β butadiene monomer can be polymerized in a continuous gas phase polymerization method using a three-component nickel catalyst system. Very high cis_; 1,4-polybutadiene (95% or higher cis-1,4-isobutadiene units) 9 This three-component nickel catalyst system contains organic compounds and soluble nickel-containing compounds And hydrogen fluoride or hydrogen fluoride complex a. In this kind of gaseous polymerization, the temperature in the reaction zone is usually maintained in the range of about 10ec to about 130eC. Β is preferably used in the reaction zone from about 209c to about 1 〇 (TC Fangu temperature. The optimal temperature for gas phase-polymerization of L3-butadiene monomer is about 35 * c to about 85X. The organoaluminum compounds that can be used have the following structural formulas ... / R1 A1-R, 'which is selected from the group consisting of alkyl (including cycloalkyl), aryl, and alkylaryl Alkyl, arylene, alkoxy, hydrogen, and fluorine; 2 and% are selected from the group consisting of alkyl (including cycloalkyl), aryl, alkaryl, and aralkyl. Some of the organoaluminum compounds that can be used Representative examples are diethyl hydride, di-n-propyl aluminum argon, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, diphenyl aluminum hydride, and di-p-toluene hydride. Aluminum, hydrogen dibenzyl aluminum, phenylethyl aluminum argon, phenyl-n-propyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-methylbenzyl n-propyl aluminum hydride, hydrogenation P ..: Phenylisopropylaluminum, sulfonylethylaluminum argon, benzyl n-propylaluminum hydride and fluorenylisopropylaluminum hydride, ethoxylated diethylaluminum, ethoxylated Diisobutyl aluminum, methoxylated dipropyl This paper is sized for China National Standard (CMS) A4 (210X 29 * 7) ^ ------- ^, ί .------ Order ------ CI ”f Z V: ν · (Please read the notes on the back before filling this page) • ______. I _______ I --------------- A7 B7 ΐ Seals of the Bayong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China 5. Description of the Invention (23) Aluminum, Trimethyl Aluminum Triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, di-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctyl Aluminum, tribenzyl aluminum, tri-p-tolyl aluminum, tribenzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl aluminum, ethyl difluorenyl aluminum, diethylphenyl aluminum , Diethyl p-tolyl aluminum, diethyl benzyl aluminum, and other triorganoaluminum compounds. Preferred organoaluminum compounds include triethylaluminum (TEAL), tri-n-propylaluminum, and triisobutylaluminum. (TIBAL), trihexyl aluminum, diisobutyl hydride (DIBA-H), and diethyl fluoride. The nickel-containing catalyst component may be any soluble organic nickel compound. These inch-soluble nickel compounds are usually nickel compounds having monodentate or bidentate organic ligands, the ligands containing up to 20 carbon atoms. One coordination system is an ion or molecule bound to and considered to be bound to a metal atom or ion. A single-dentate system means that there is one bit, which can pass through this position to form a covalent or coordination bond with the metal. "A double-dentate system means that there are two positions, which can form a covalent or coordinate with the metal through this position. Bonding. The term " soluble " refers to the solubility in succinic monomers and inert solvents ^ In general, any nickel salt or nickel-containing organic acid containing about iiZO carbon atoms can be used as the soluble nickel-containing compound . Some representative examples of soluble nickel-containing compounds include nickel benzoate, nickel acetate 'nickel naphthenate, nickel octoate, nickel neodecanoate, bis (α-furanyl bicubic). Nickel, nickel palmitate, stearic acid Nickel, Nickel Acetylpyruvate, Nickel Salix, Bis (Cyclopentadiene) Nickel, Nickel Bis (Selene) Ethylene Diimide, Nickel Cyclopentenyl-Nitrite, Nickel Bis (π-Allyl Nickel), bis (π-cyclooctyl-ΐ, 5-di 埽) nickel, bis (π- 晞 propyltrifluoroacetate nickel), and nickel tetracarbonyl. The nickel content is preferably nickel salt of carboxylic acid, or nickel. -26 This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) (read the precautions on the back before filling this page)

, 1T Printed by the Central Mongolian Bureau of the Ministry of Interest of the Ministry of Shell, Consumer Cooperation Du printed Α7 ~ _____ Β7 ~ —-_ __ V. Description of the Invention (24) Organic Complexes> Nickel naphthenate, nickel caprylate, and nickel neodecanoate. Is a highly preferred soluble nickel-containing compound. Nickel 2-ethylhexanoate is often referred to as NiOct. Due to economic factors, it is the most commonly used soluble chain-containing compound. If hydrogen fluoride is used in the catalyst system, it should be anhydrous and as pure as possible. Hydrogen fluoride can also be used as the complex in the catalyst system of the present invention. The hydrogen fluoride complex can be easily made of the following compound, which is a compound Contains atoms or groups capable of 6-electron but fluoride gas or electrons shared with hydrogen fluoride. Β- capable compounds with such associations are ethers, alcohols, ketones, esters, nitriles, water and Certain amines. The keto subgroup can be defined by the following formula.

II

R'-CR wherein R1 and R are selected from the group consisting of alkyl, cycloalkyl'aryl, alkaryl, and aralkyl, and contain 1 to about 30 carbon atoms; and wherein R, and R may be the same or different 》 These ketones represent a class of compounds having one carbon atom connected to oxygen by a double bond. Ketones useful in the preparation of the ketone · hydrogen fluoride complex of the present invention, some representative examples of which include acetone, fluorenyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone, ethyl octyl ketone, 2,4 -Glutaramidine, butylcycloheptanone ', acetophenone', pentylphenyl ketone ', butylphenyl-ketone, dibenzone, phenylmethylbenzone, quinone, and the like. It can be used to form the ketone-fluorinated hydrogenated compound of the present invention. The preferred vehicle type is a two-pit based network type, of which the acetone system is the best.

(Should read the precautions on the back before filling in this page j

The Consumer Cooperation of the China Standards Bureau of the Ministry of Economic Affairs, printed by Du Du A7 B7 V. Description of the invention (25) The nitrile subgroup can be represented by the formula RCN, where R represents an alkyl group, a cycloalkyl group, an aryl group, or an aromatic group 'Contains up to about 30 carbon atoms. These guesses contain a complete atom, which is connected to the nitrogen atom β by a reference bond. Representative examples of this guess subgroup, rather than missing, are Etchi, Dingchai, Dingchai, Benzo, Toluonitrile, "Preferred hydrogen fluoride-nitrile complexes such as phenylacetonitrile are fluorinated benzonitrile complexes. The alcohol subgroup can be defined by the formula ROH, wherein R represents an alkyl group, a cycloalkyl group, a methyl group, an aryl group, or an arylfluorenyl group, and contains about 1 to about 30 carbon atoms. These alcohols represent a genus of compounds that have a carbon atom connected to a branched oxygen by a single bond. This oxygen is then connected to hydrogen by a single bond. Alcohols that can be used to prepare hydrogen fluoride complexes are representative rather than nothing. Missing examples' are methanol ethanol, n-propanol, isopropanol, benzyl alcohol, cyclohexanol, butanol, hexanol, and pentanol. The preferred hydrogen fluoride-alcohol complex is a trihalide phenate complex. The acid subgroup can be defined by the formula R, 0R, where R and R · represent an alkyl group, a cycloalkyl group, an aryl group, an aryl group, and an aralkyl group, and contain about 1 to about 30 carbon atoms; where R and R · Can be the same or different. R can also be joined through a common carbon bond to form a cyclic fluorene, wherein the fluorene oxygen system is an integral part of the cyclic structure, such as tetrahydrofuran, furan, or dioxin. These ethers represent a genus of compounds having two carbon atoms' connected to an oxygen atom by a single bond. Examples of the ethers which can be used for preparing the fluorinated gas complex of the present invention are representative, but not exhaustive, examples of which are dimethyl ether, diethyl ether, dibutyl ether, monopentyl ether, diisopropyl ether, Tetrahydrofuran, toluene ether, diphenyl ether, ethyl methyl ether, difluorenylfluorene and the like. A preferred hydrogen fluoride-ether complex is a diethyl trihalide hydrogen fluoride 'and a dibutyl acidified hydrogen fluoride complex. (> Read the notes on the back before filling in this 1)

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， 1T V Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (26) The ester subgroup can be defined by the formula: 0 R, -cor where R and R 'are selected from the group consisting of alkyl, cycloalkyl, aromatic Group, alkaryl group, and aralkyl group contain 1 to about 20 carbon atoms, and as shown, this ester contains one carbon atom and is connected to an oxygen atom by a double bond. Representative but non-exhaustive examples of such esters are ethyl benzamate, amyl benzoate, phenyl acetate, phenyl benzoate, and other esters conforming to the above formula. The preferred hydrogen fluoride-salt complex is ethyl fluoride argon benzoate complex Γ-The complex of the present invention is generally prepared by simply bubbling gaseous hydrogen fluoride into an appropriate amount of the complex The complexing agent is, for example, ketones, ethers, alcohols or riders. It should be performed in the absence of moisture, and measures should be taken to keep the temperature from rising above about 100T (37./C). In most cases, hydrogen fluoride complexes are made while maintaining the temperature at room temperature. Another method that can be used is to dissolve hydrogen fluoride or the complexing agent in an appropriate solvent, and then;-add another component β and another mixing method is to dissolve the complexing agent in the refrigerant, and simply make the gaseous hydrogen fluoride Bubble through the system until everything goes wrong. The agents are all reacted with argon fluoride. It can be measured by weight increase or chemical titration. The three-component catalyst system used must be preformed. If this catalyst system is preformed, it will maintain a high degree of activity over a long period of time. The use of such a preformed catalyst system will also result in the formation of homopolymer products. This pre-formed catalyst system is made in the presence of multiple pre-forms. Γ Please read the notes on the back before filling out this page.) Γ ·-(Printed by A7 of the Ministry of Economic Affairs, Shenyang Bureau of Standards and Consumers Cooperatives- ----- B7 V. Description of the invention (27) "It is selected from the group consisting of monoene, non-co-dual tobacco, two-homed tobacco, general di-associated tobacco, ring non-co-consumed multi-associated tobacco, tri-associated tobacco, B Fluorenyl bonds, aromatic nitriles, and polymonoene polymers, such as polybutadiene. Pyrocarbons that can be used as preformers in the preparation of stabilizer catalysts, some representative examples are trans · 2 · Butadiene, mixed cis- and trans-2_ 戍 gui, and cis-2-pentane. Some non-conjugated diolefins that can be used as preforming agents are cis 1,4 hexaene, ι, 5 _Heptadiene, α-octadiene, and the like. Representative examples of cyclic non-conjugated polyolefins can be used, including ^ cyclooctadifluorene, 1,5,9-cyclododecatrioxane, and 4_Vinylcyclohexene. Trisene hydrocarbons that can be used as pre- or preforms, including 135_hexatriene; heptadiene, 13,6 · octatriene, 5-methyl-i, 3,6- Heptatriene and its analogs. Some representative examples of substituted conjugated diolefins include, winter diphenyl butadiene, lauryl hydrazone (7-methyl_3_ fluorenylidene · M · octadifluorene), and the like. Ethyl ethylene Basic acid and isobutylethylfluorene are representative examples of alkyl vinyl ethers that can be used as preformers. Representative examples of aromatic nitriles that can be used are benzophenones. Can be used Some representative examples of total diolefins include 1,3-butadiene, isoprene, and 13-pentadiene. A preferred preformer is 1,3-butadiene. A method for making preformed contacts The method by which the vehicle is highly active and relatively chemically stable is to add the organoaluminum compound and the preforming agent to the solvent medium before contacting them with the nickel compound. Then, the nickel compound is added To the solution, and then add the fluoride to the solution. As an alternative, the preform can be combined with a nickel compound, followed by the addition of an organic compound, followed by the fluoride. It can be used _______ -30 -__ This paper uses Chinese national standard (C NS > A4 specification (210X297 mm) (_Please read the notes on the back before filling this page)

A7 A7 Printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Economic Affairs —_______ B7 V. Description of the Invention (Contribution) He added sequence ’, but it usually produces less satisfactory results. The amount of the preforming agent used to preform the catalyst may be within a range of about 0.001 to 3 percent of the total amount of monomers to be polymerized. Expressed in terms of the molar ratio of the preforming agent to the nickel compound, the amount of the preforming agent present during the preforming step may be in the range of about 1 to 3000 times the nickel concentration. The preferred molar ratio of the pre-former to the thread is about 3: 1 to 500: 1 β. These pre-formed catalysts have catalytic activity after preparation. However, it has been found that a moderate aging period (eg, 15 to 30 knife clocks) at a moderate temperature (eg, 50 ° C) will greatly increase the activity of the preformed catalyst. If appropriate, ‘pre-formed catalysts can age for up to several days’. • To properly stabilize the catalyst, a pre-former must be present before the organoaluminum compound has a chance to react with the nickel compound or fluoride. If the catalyst system is pre-formed without the presence of at least a small amount of pre-former, the chemical action of organoaluminum on nickel compounds or fluorides will cause the catalytic activity of the catalyst to be greatly reduced, and then soon even if it is not active . In the presence of at least a small amount of preforming agent, the catalytic or shelf life of the catalyst has been greatly improved 'over a system without any preforming agent present. The two-component linear catalyst system used in the practice of the present invention is active under a wide range of catalyst concentrations and catalyst component ratios. These three catalyst components interact to form an active catalytic system. As a result, the optimal concentration of any one of the components I is extremely dependent on the concentration of each of the other two catalyst components. Furthermore, although the polymerization reaction occurs at a wide range of catalyst concentrations and ratios, the most desirable properties of the synthesized polymer are in a relatively narrow range ______f! 1 " \ * f / ... (read the notes on the back first for details)

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-C A7 Printed by the Shell Standard Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

A7 ---------— '__B7______ V. Description of the invention (30) The nature of the sound of oak. Carbon black and silica are examples of materials that are highly preferred as carriers. This is because carbon black and silica are often used as fillers in rubber ingredients and they are present in the rubber to be synthesized, and are generally not considered Is harmful. In fact, cis-1,4-polybutadiene rubber already containing carbon black and / or silica < utilization is considered to be advantageous in many applications. In the preparation of supported catalyst systems, It is desirable to passivate the material to be used as a support. This is usually achieved by treating with organoaluminum compounds by destroying the active sites on the material. This organoaluminum compound is usually the same organoaluminum compound used in a three-component nickel catalyst system. This contact dispersion was added to a support to form a slurry. Then, the solvent is removed, for example, by evaporation, so that the preformed catalyst is deposited on the carrier. Β-Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. One or more molecular weight modifiers can be added to the reaction zone. Usable molecular weight regulators include those known to be used in the solution polymerization of i, 3 · butadiene monomers. This polymerization utilizes a nickel catalyst system, such as in U.S. Patent No. 4,383,097, and South African Patent No. 83 / Na 55. 'Magic / 2557 and 83 are still revealed in 59. These molecular weight modifiers are selected from the group consisting of ethylene, α-olefins, cis-2-butene, trans-2-butene, alladiene, ι, 4-fluorenediene, ι, 5-hexadiene ' ι, 6-heptadiene, 1,2,4-trivinylcyclohexene, 1-inverse hexadiene, and 4-vinyl-μ cyclohexene. The alpha-olefins which can be used usually contain 3 to about 10 carbon atoms. Some representative examples of fluorenes available for this project include acetamidine, propane, 1-butene, 1-pentene, and 1-hexene. Ethylene is a preferred molecular weight regulator. This is because it is effective as a molecular weight regulator at low concentrations and does not poison the polymerization catalyst, even if its concentration is significantly increased. It has also been found that when diarylamines are used for the linear catalysis of 1,3-butadiene monomers, __33- ------ This paper size is applicable to the Chinese National Standard (CNS) A4 (210X297) (Mm) A7 B7 printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards and Commerce of the Ministry of Economic Affairs 5. Description of the invention (31) When gas-phase polymerization becomes cis-1,4-polybutadiene rubber, it acts as a molecular weight regulator. The use of diarylamines, such as p-styrylated diphenylamine, as the molecular weight regulator is highly preferred. The amount of molecular weight regulator that must be used will vary with the type of molecular weight regulator used, the catalyst content, the polymerization temperature, and the molecular weight required for the polymer being synthesized. For example, if a high molecular weight polymer is desired, only a relatively small amount of molecular weight modifier is needed. 'On the other hand, to substantially reduce the molecular weight, a relatively large amount of molecular weight modifier will be used. Extremely effective molecular weight regulators (such as ethylene) can be used at lower concentrations, and apparently, it will suppress the molecular weight to the same extent as more typical molecular weight regulators at higher concentrations "—in general, molecular weight regulation The agent is used in a concentration range between about 0.005 phm (parts per 100 parts of monomer) and 20 phm. The molecular weight modifier is usually preferably used at a concentration of 0.025 to 15 phm ', with the optimum concentration being between 0.05 and 10 phm. In the continuous method, the molecular weight regulator is continuously added to the reaction zone at a rate sufficient to maintain the desired concentration of the molecular weight regulator in the reaction zone. Even if the molecular weight regulator is not consumed in the polymerization reaction, a certain amount of the molecular weight regulator must usually be added continuously to make up for the loss. In the continuous method, the total amount of 1,3-butadiene monomer added to the reaction zone per unit time is basically the same as the high cis-I that is removed from the reaction zone within the unit of time. The amount of 4-polybutadiene is the same. Antioxidant Addition-The polymerization reaction of the present invention can be performed in the presence of a diarylamine antioxidant and a hindered phenol antioxidant. These specific types of antioxidants will not be used. • 34 · This paper size applies to China National Standard (CNS) A4 (2) 0X297 mm. {Please read the precautions on the back before filling this page)

* 1T (Poisoned by nickel catalyst system for making high cis-1,4-polybutadiene. Diarylamine antioxidant 'can be used with titanium catalyst system for making polyisoprene It can be premixed with the catalyst, pre-encountered with the distributor, or it can be added to the reaction zone as an individual component. In other words, these antioxidants are before the catalyst is dried into powder, when the catalyst is produced, 'Mixed with catalyst' or supported on a suitable distribution agent such as carbon black or silica. For example, the dispersion can be made dry by mixing a preformed catalyst dispersion with a solution of an antioxidant and then added Into the reaction zone to carry out the polymerization reaction. The antioxidant solution can also be mixed with carbon black and then dried to cause the anti-oxidant to be supported on the carbon black, which can be used as a catalyst support or as a distribution agent _ The diarylamine antioxidant that can be used in the gaseous polymerization of the present invention has been described above. The hindered phenol antioxidant that can be used is usually an alkyl-substituted phenol having the following structural formula: 0Η R1 I R2

Printed by the Ministry of Economic Affairs of the Central People's Government of the People's Republic of China, where R1 and R2 represent a group containing i to about 10 carbon atoms, and where R3 represents a hydrogen atom or an alkyl group containing 1 to about 10 carbon atoms. R1 and R2 usually preferably represent tertiary alkyl groups containing 4 to about 10 carbon atoms, and R3 represents hydrogen atoms or alkyl groups containing 1 to about 6 carbon atoms. Generally, about 0.25 phm to about 3 are added. Antioxidant from phm to provide-_ gg _ This paper is printed from Jingcai Guanjia County (CNS) A4 specification (21G X 297 mm) A7 B7 Printed by the Central Consumers ’Bureau of the Ministry of Economic Affairs and Consumer Cooperatives Explain (33) the rubbery polymer of the desired stability. It is generally preferred that an antioxidant of about 0.5 to 2 phm is present during the polymerization reaction. In most cases, the antioxidant is more preferably present at a level of about 1 phm to about 1.5 phm. The invention is illustrated by the following examples, which are for illustrative purposes only and should not be considered as limiting the scope of the invention or the manner in which it can be implemented. Unless otherwise indicated, the parts and percentages given are weight ratios. The molecular weight of the polymer can be dilute solution viscosity (DSV), inherent viscosity, Muni viscosity, number average molecular weight%) and weight average molecular weight (Mw ) Refers to the point of view. In the following examples, the viscosity of the dilute solution was measured at 30T in a 0.25 weight percent toluene solution. 'Example 1 In this experiment' was pure isoprene; 晞 polymerization was carried out by gas-phase polymerization in a 4-ounce (118 ml) polymerization flask. In the procedure used, the preformed titanium catalyst system was added to the polymerization flask under a nitrogen atmosphere. A dry nitrogen stream is passed through the bottle, which will remove the hexane solvent and leave the dry catalyst, deposited on the wall of the polymerization reactor. Then, tare the bottle. Next, in a nitrogen atmosphere, 20.0 g of isoprene was added to another polymerization reaction bottle. The bottle was then placed in a thermostatic bath, which was kept at 50 eC. Use a pipette needle (cannula) to connect the monomer to the catalyst bottle. Polyisoprene will slowly deposit on the wall of the catalyst bottle. The absorption of isoprene single ceremony is quite slow. After 2 hours .. ·, this catalyst bottle contains 72 grams of polyisoprene. Hexane was added to the bottle along with Iphr's Wingstay κ barrier antioxidant. Part of the polymer will not dissolve, indicating that there is one (Please read the precautions on the back before filling this page) Γ

1T A7 ___ B7 V. Description of the invention (34) Some gels are formed. "Dry this material in an air oven overnight. Dsc analysis showed that the glass transition temperature of π was -66eC, which is a typical fluorene of cis 4,4_ polyisoprene. ^ Example 2 In this experiment, the example is repeated! The procedure used in this study is that the polymerization is carried out in the presence of Wingstay® 29 p-styrylated diphenylamine and the polymerization time is only 45 minutes. Wingstay 29 p-styrylated diphenylamine was added to a preformed titanium catalyst system with a molar ratio of 14: i to titanium tetraoxide. It is added to the Poly Valley reaction flask at the same time as the titanium catalyst system. · Recovery of 2.2 grams of polyisoprene. The polyisoprene product was determined to be gel-free and had a content of 1) of 28 g / g. DSC analysis showed that the polyisoprene had a glass transition temperature of 66.c. Nuclear magnetic resonance analysis showed that its microstructure was 98%, the percentage of cis-i and the inverse percentage of 3,4 polyisoprene. This experiment demonstrates that when polymerization is carried out in the presence of p-phenylethyl fluorinated diphenylamine, a gel-free polymer is produced. Its further description indicates that the titanium catalyst system will produce cis-1,4-polyisoprene with a cis-1> 4-isomeric content greater than 97%. Because Λ'-styrylated diphenylamine does not affect the microstructure of cis'4 · polyisoprene, which was synthesized when it existed. Example 3 In this experiment, pure butane ... dioxin was polymerized in a 4-ounce (118 ml) polymerization reaction flask + 'by gas phase polymerization. In the procedure used, the preformed catalyst system was made in a vial with a magnetic stirrer. Printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, printed A7 B7 V. Description of the invention (35) 'First, add about 35 ml of hexane "and then, under vigorous agitation, add 3 ml of 17% of 3-butadiene Solution in hexane. Next, 10 ml of a 0.87 M triisobutylaluminum solution was added. Then, 4.35 ml of a 0.05 M solution of nickel octoate in hexane was added. Finally, 4.2 ml of 5.2 M hydrogen fluoride-dibutyl.acid · late solution was added. The catalyst solution was aged at room temperature for one day, and then 4.5 ml of the catalyst dispersion was added to the polymerization reaction flask under a nitrogen atmosphere. "A dry nitrogen stream was passed through this flask, which would remove the hexane solvent and leave it in The catalyst is dried and deposited on the wall of the polymerization reaction bottle. Then tare the bottle so that the exact yield f can be measured. Then, in a nitrogen atmosphere, 7.0 g of 1,3-butanedi was added to another polymerization reaction bottle. Use a pipette needle (cannula) to connect the monomer to the catalyst bottle ’Both at ambient temperature. Polybutadiene will slowly deposit on the walls of the catalyst bottle. The absorption of 1,3-butadiene monomer is quite slow. After 25 hours, the catalyst bottle contained 2.0 grams of polybutadiene. Hexane was added to the bottle with 11} 111 (parts per 100 parts of rubber) WingstayK hindered phenol antioxidant, all the polymers were dissolved, indicating no gel. This material was dried in an air oven overnight, and its DSV was determined to be 3 26 g / g. DSC analysis showed that the tf glass transition temperature was -108 «c and the melting point was · 6. The measured glass transition temperature and melting point are typical rhenium of high-cis 4,4 polybutadiene. Examples 4-9 In this series of experiments, 1,3-butadiene monomers were polymerized into high-cis.M_polybutadiene by gas-phase polymerization. .... The pre-formed catalyst system was formed in the following manner. Under nitrogen atmosphere, about 50 ml of anhydrous sintered was added to the Dongpansi (118 ml) polymerization reaction bottle, followed by adding 3 4 ml μ weight. Percentage (铕 Please read the notes on the back before filling this page) (, ιτ

Seal A7 __B7 _ ^ __ by the Central Bureau of Standards of the Ministry of Economic Affairs __B7 _ ^ __ 5. Description of the invention (36) A solution of 1,3-butadiene in hexane, and then adding 20.0 ml of 0.86M triisobutyl aluminum Solution. After about 2 minutes, 8.6 ml of a 0.05 M solution of nickel octoate was added, and after about 5 minutes, a solution of 4.1 milliwells of 10.5 M hydrogen fluoride butyl ether was added. The final volume of the catalyst solution to remove the by-product gas was 83.3 ml. This catalyst solution has a nickel concentration of 0.0052 Μ. »A similar catalyst solution was manufactured in which 4.30 grams of Wingstay® 29 p-styrylated diphenylamine antioxidant was added to the catalyst before triisobutylaluminum was added. In an alkane solution. In this case, the final nickel concentration is 0.0049M. -Gas-phase polymerization is performed in a 4-ounce (118 ml) polymerization flask. In this polymerization technique, carbon black and an antioxidant solution are added to the polymerization flask under a nitrogen atmosphere. Then, the hexane solvent from the antioxidant solution was removed by flushing with nitrogen. Then, a catalyst dispersion (or catalyst / antioxidant) in hexane was added, and the mixture was vigorously stirred. These catalysts contain 0.01 mM nickel, and further nitrogen flushing will remove residual hexane. Then, connect this catalyst vial with a hypodermic needle to another 4-ounce (118 ml) polymerization bottle 'which contains 1, 3_ Butadiene liquid. A ventilation needle was inserted into the catalyst-containing bottle, and the bottle was flushed with butadiene gas for about 2 minutes. Then remove the venting needle < Let the bottle stand in a fume hood at room temperature for the desired reaction time. In Example 4, the polymerization reaction time was 2.5 hours, and in Examples 8 and 9, the reaction time was 1.5 hours. The pipette needle was removed and the polymer yield was determined. In Examples 4-7, antioxidants were added as individual solutions. In Examples 8-9, the antioxidant was present when the pre-formed catalyst was composed. ^ The polymer obtained in each of these experiments was scaled according to the Zhongguanjia standard ((^ fS) VIII.4 (2⑴x297 ^ H). '一' — ----- (Read the precautions on the back before filling. Write this page)

V A7 B7 Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, V. Description of invention (37) The output of the product is shown in Table 1. Examples of carbon black antioxidant production 4 Refer to 8.48 g — 5 3.0 g — 7.07 g 6- BHT 1,0.10 8.60 g 7 3.0 g BHT ^ 0.10 7.52 g 8 Wingstay® 29 5.96 g 9 3.0 g Wingstay® 29 5.15 g 1-BHT stands for butylated vial toluene. This series of experiments shows that 1,3-butadiene monomer can be used in the presence of a hindered phenol antioxidant ^ diarylamine antioxidant, using the three-component nickel catalyst system requested in the scope of the patent application, and polymerized by gaseous polymerization. Cis_1 > 4 · Polymer dimer rubber. In the case where the polymerization reaction is carried out in the presence of an antioxidant, a good yield can be obtained. In fact, the BHT used in Examples 6 and 7 showed improved polymer yield. In the gas phase polymerization of the present invention, the main content of the diene monomer to be polymerized is typically gaseous. Even if an appropriate combination of temperature and pressure is used in the reaction zone to maintain a portion of the difluorene monomer in a gaseous state, it is further expected that a portion of the diene monomer may be simultaneously liquid. In other words, it is expected that a part of the reaction zone, 3_ butadiene monomer or isoprene monomer, may be in a liquid state. "However, most of the single amount present in the reaction zone must be present. Gas phase. After understanding the description provided herein, variations in the present invention are possible. Although some representative specific embodiments and details have been shown for the purpose of explaining the present invention, various changes obvious to those skilled in the art -------- ^ yi ----., R Γ {旖Read the notes on the back before filling out this page}-Order

V A7, _ B7___ 5. The description of the invention (38) and amendments can be implemented without departing from the scope of the invention. Therefore, it should be understood that changes may be made in the specific embodiments described, which are within the full intended scope of the present invention, as defined in the scope of the patent application attached below. (Please read the notes on the back before filling this page) k__I_ Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs _ This paper size is applicable to China National Standards (CNS) A4 (2 丨 0X297 mm)

Claims (1)

A8 B8 Patent Application No. 85110601 Chinese Patent Application Amendment (June 88) Kun VI. Application for Patent Scope Dou η tu Central Ministry of Economy Ministry of Economics and Social Work Cooperative Cooperative Printing-Species in the Delivery Process Method for gas-phase polymerization of isoprene to cis-1,4-polyisoprene characterized by the following steps: (1) adding the isoprene and a preformed catalyst system to the reaction zone; The catalyst system is made in the presence of at least one ether by reacting an organic compound with titanium tetraoxide; wherein the isoprene is maintained in the reaction zone by an appropriate combination of temperature and pressure. Gas phase; (2) polymerize the isoprene to cis-1,4-polyisoprene at a temperature in the range of 35 ° C to 70 ° C; and (3) take it out of the reaction zone The cis-1,4-polyisoprene, wherein the organoaluminum compound has the following structural formula 〆1 A, r2 and its center is selected from the group consisting of alkyl, aryl'alkaryl, aralkyl, and hydrogen; and Wherein Chi 2 and Han 3 may be the same or different, and are selected from the group consisting of alkyl, aryl, alkaryl, and aralkyl. The ether contains 4 to 20 carbon atoms, and the molar ratio of the ether to the organoaluminum compound is in the range of 0.4: 1 to 1.2: 1, and the organic compound has a molar ratio to titanium tetrachloride. The ratio is in the range of 07: 1 to 1.2: 1. 2. The method according to item 1 of the scope of patent application, wherein the catalyst system is suspended on an inert solid support. 3. The method according to item 1 of the scope of patent application, wherein the reaction zone is based on the Chinese National Standards (CNS) from the paper (21〇 > < 297) I m In HI I i In HI ^ HI nn 1. ^ 1 i ^ i 1— m 1 .ϋ .f. Fv. T a * ^ r, t Please read the note on the back ^^ before filling out this page) A8 B8 Patent Application No. 85110601 Amended version of Chinese patent application patent (June 88). Kun VI. Patent application scope tutu Central government ministry of economy Ministry of Economics and Social Cooperative Consumer Cooperative Printing-Kind of isoprene gas phase polymerization during the process The method of -1,4-polyisoprene is characterized by the following steps: (1) adding the isoprene and a preformed catalyst system to the reaction zone; the catalyst system is based on at least one ether In the presence, it is made by reacting an organic compound with titanium tetraoxide; wherein the isoprene is maintained in the gas phase in the reaction zone by an appropriate combination of temperature and pressure; (2) at 35 Polymerize the isoprene to cis-1,4-polyisoprene at a temperature in the range of ° C to 70 ° C; and (3) remove the cis-1 from the reaction zone , 4-polyisoprene, wherein the organoaluminum compound has the following structural formula 〆1 A, r2 and its center is selected from the group consisting of an alkyl group, an aryl'alkaryl group, an aralkyl group, and hydrogen; Han 3 may be the same or different, and is selected from the group consisting of alkyl, aryl, alkaryl, and aralkyl, wherein the ether contains 4 to 20 carbon atoms, and the molar ratio of ether to organoaluminum compounds, It is in the range of 0.4: 1 to 1.2: 1, and the molar ratio of the organic compound to titanium tetrachloride is in the range of 07: 1 to 1.2: 1. 2. The method according to item 1 of the scope of patent application, wherein the catalyst system is suspended on an inert solid support. 3. The method according to item 1 of the scope of patent application, wherein the reaction zone is based on the Chinese National Standards (CNS) from the paper (21〇 > < 297) I m In HI I i In HI ^ HI nn 1. ^ 1 i ^ i 1— m 1 .ϋ .f. Fv. T a * ^ r, t Please read the note on the back ^^ before filling out this page) Ministry of Economic Affairs Central Central Bureau Printed by the Consumer Cooperative A8 B8 C8 D8 VI. Patent application Fanyuan fluidized bed reactor. 4. According to the patent application Fan Yuandi! The method of claim, wherein the organoaluminum compound is a trialkylaluminum compound. 5. The method according to item 4 of the scope of the patent application, wherein the polymerization reaction is performed in the presence of p-phenylethylfluorinated diphenylamine. 6. The method according to item 4 of the patent application range, wherein the temperature is in the range of 40 scoop to 60 ° C. 7. The method according to item 5 of the scope of the patent application, wherein the molar ratio of p-styrylated diphenylamine to titanium tetraoxide is in the range of 0.05 to 5 to 1 The method according to item 5 of the scope of patent application, wherein the molar ratio of the organoaluminum compound to titanium tetragas is in the range of 0.7: 1 to 1.2: 1. 9. The method according to item 8 of the scope of patent application, wherein the high-cis' 4-polyisoprene has left the reaction zone, and the devolatilization β thereof is caused. 10. The method according to item 9 of the scope of patent application, The reaction zone is maintained at a temperature ranging from 35t: to 85 ° C. 11. A method according to item 1 of the scope of patent application, wherein the polymerization is performed in the presence of at least one diarylamine. 12. The method according to item 2 of the scope of patent application, wherein the polymerization is performed in the presence of a diarylamine. 13. The method according to item 12 of the patent application range, wherein the diarylamine system is carried on an inert solid support together with the catalyst system "14. The method according to item 13 of the scope of patent application, wherein the catalyst system The molar ratio of the diarylamine to titanium ranges from 0.05: 1 to 5: 丨. The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) II— I- Ik---I. N 111-—-I, 1τ. ....... I ι ( *. {Please read the note ^^ on the back before filling this page) A8 B8 C8 ^^ — —_ D8__ 'Application for patent scope 15 · According to the method of patent application scope No. 14 in which the diarylamine It is a p-vinyl diphenylamine 'and the molar ratio of p-styrylated diphenylamine to titanium in the catalyst system is in the range of 0 25: 1 to 2: 丨. 16- The method according to item M of the patent application park, wherein the molar ratio of p-benzylated vinylated diphenylamine in the catalyst system to the catalyst system is in the range of 0.05 · 1 to 1.5: 1 . The method according to item Π of the patent application, wherein the inert solid support system is carbon black. The method according to item 6 of the patent application range, wherein the molar ratio of the ether to the organoaluminum compound is in the range of 0.5: 1 to 1: 1, and the molar ratio of the organic compound to the tetrakisduranium , In the range of 0: 1 to 1: 1. Ϊ9. The method according to item 18 of the scope of patent application, wherein the molar ratio of the organoaluminum compound to titanium tetraoxide is in the range of 0.85: 1 to 0.95: 1. 20. The method according to item 1 of the patent application scope, wherein the reaction zone is tied in a stirred bed reactor. Printed by the Central Government Bureau of the Ministry of Economic Affairs and Consumer Cooperatives' Please read the precautions on the back before filling out this page) λ 21. —Plant polymerization of 1,3-butadiene into cis-ΐ, 4 in the process A method for polybutadiene, characterized by the following steps: (1) adding the 1,3-butadiene and a catalyst system to the reaction zone, the catalyst system comprising (a) an organoaluminum compound, (B) a nickel-containing compound and (c) a gas-containing compound selected from the group consisting of hydrogen fluoride or a hydrogen fluoride complex; wherein the 1,3-butadiene is a suitable combination of temperature and pressure in the anti-3 _ This paper is scaled to the national standard (CNS) A4 size (210X297 mm). The scope of patent application is A8 B8 C8 D8. The gas phase is maintained in the printing zone of the Bencon Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs; (2) in Polymerize the 13-butadiene into cis · 1,4-polybutadiene at a temperature ranging from 10 ° C to 130eC; and (3) take out the high-cis'4 · polybutadiene from the reaction zone Ene, wherein the organoaluminum compound has the following structural formula A ^ R2 and its center # 'is selected from the group consisting of alkyl, aryl, and aryl' And hydrogen and fluorine; and R2 and & may be the same or different and are selected from the group consisting of alkyl 'aryl' alkylaryl and aralkyl groups, wherein the soluble organic nickel compound is selected from the group consisting of nickel salts and Nickel-containing organic acid containing 1 to 20 carbon atoms, and the molar ratio of the organoaluminum compound to the soluble nickel-containing compound is in the range of 0.3: 1 to 300: 1; among them, the fluorine-containing compound The molar ratio to the soluble nickel-containing compound is in the range of 5: 1 to 20.1 (and the molar ratio of the fluorine-containing compound to the organoaluminum compound is in the range of 0.4: 1 to 10: 1 22. The method according to item 21 of the claimed patent, wherein the catalyst system is suspended on an inert solid support. 23. The method according to item 21 of the patent application, wherein the reaction zone is at In a fluidized bed reactor "24_ The method according to item 21 of the scope of patent application, wherein the compound containing the compound is a gasified nitrogen complex. 25_ The method according to item 24 of the scope of patent application, there is a molecular weight regulator (Please read the notes on the back of the poem before filling in this page) ————— 1 ----- Λ.Λ.,: ------ Order ----—— m I- II -4-Α8 Β8 C8 D8 Ministry of Economic Affairs, Central Prospective Bureau, Industrial and Consumer Cooperatives印 *. 六 、 The scope of patent application exists. 26. The method according to item 25 of the scope of patent application, wherein the molecular weight regulator is E. jin. 27. The method according to item 24 of the scope of patent application, wherein the temperature is between 2 〇 «c to 100 ° C. 28. The method according to item 25 of the scope of patent application, wherein the molecular weight regulator is ethylene or an alkane containing 3 to 10 carbon atoms. 29. The method according to item 28 of the application, wherein the α-fluorene is present in the reaction zone at a concentration of 0.1 phm to 15 phm. 30. The method according to item 23 of the application, wherein the organoaluminum compound is trialkylaluminum, and the soluble nickel-containing compound is selected from the group consisting of nickel salts and nickel-containing organic acids. The organic acid contains 1 to 20 carbons. Atom, and wherein the fluorine-containing compound is a hydrogen fluoride complex. 31. The method according to claim 21, wherein the organoaluminum compound is selected from the group consisting of triethylaluminum, tri-n-propylaluminum, triisobutylaluminum, dihexylaluminum, and diisobutylaluminum hydride. And diethylaluminum fluoride. 32. The method according to item 31 of the application, wherein the soluble nickel-containing compound is nickel octoate. 3. The method according to item 32 of the scope of patent application, wherein the molar ratio of the organic compound to the soluble nickel-containing compound is in the range of 2: 1 to 80 ·· 1; among which the fluorine-containing compound is to the soluble nickel-containing compound The molar ratio is in the range of 50: 1 to 150: i; and the molar ratio of the fluorine-containing compound to the organic compound is in the range of 07: 1 to 7: 1. Method according to item 33 of the scope of patent application 'wherein it is in the high cis--5- A4 rule 4 (210X297 mm) (4F read the precautions on the back before filling this page) y 44 n ^ i —mmet m _11 ai ^ i mmei Order In Printed by the Central Sample Rates Bureau of the Ministry of Economic Affairs, Consumer Cooperatives, Printing 387903 bI 08 ——-08____ VI. The scope of patent application 1,4-polybutadiene has left the reaction zone and it will be devolatilized Serving. 35. The method according to item 34 of the patent application park, wherein the reaction zone is maintained at a temperature in the range of 35 ° C to 85 ° C. 36. The method according to item 22 of the scope of patent application, wherein the organoaluminum compound has the following structural formulas A1-R., Z R3 and its center is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, and alkoxy Group, hydrogen, and fluorine, and R_2 and R_3 may be the same or different, and are selected from the group consisting of alkyl, aryl, alkylaryl, and aralkyl; wherein the soluble organic nickel compound is selected from the group consisting of nickel salts and containing An organic acid containing 1 to 20 carbon atoms, and wherein the fluorine-containing compound contains hydrogen fluoride or a hydrogen fluoride complex. 37. The method according to item 36 of the patent application, wherein the molar ratio of the organoaluminum compound to the soluble nickel-containing compound is in the range of 0 .. 1 to 300: 1; wherein the fluorine-containing compound is The molar ratio of nickel compounds is in the range of 0.5: 1 to 200: 1; and the molar ratio of organic compounds in fluorine-containing compounds is in the range of 04: 1 to 10: 1. Wherein, #Hio temperature is maintained in the range of 20 ° C to 10 ° C. 38_ The method according to item 37 of the scope of patent application, wherein the molar ratio of the organoaluminum compound to the soluble nickel-containing compound is 2 ·· 1 Within the range of 80: 丨; the molar ratio of the fluorine-containing compound to the soluble nickel-containing compound is in the range of 3: 1 to 100: 1; and the fluorine-containing compound in the organic -------- ΗΛ /, ------ Order ---- fd read the notes on the back ^^^ before filling out this page) 6- A8 B8 C8 D8 387903 K, the molar ratio of the compound in the patent application range is in the range of 0.7: 1 to 7: 1; wherein the organoaluminum compound is selected from the group consisting of triethylaluminum, tri-n-propylaluminum, diiso Butyl aluminum, trihexyl aluminum, diisobutyl aluminum hydride, and diethyl aluminum fluoride; and the soluble nickel-containing compound is selected from the group consisting of nickel naphthenate, nickel octoate, and nickel neodecanoate. 39. The method according to item 21 of the application, wherein the polymerization is performed in the presence of a hindered phenol antioxidant. 40. The method according to item 39 of the application, wherein the hindered phenol antioxidant has the following structural formula: OK | R2 R3 wherein R1 and R2 represent alkyl groups containing 1 to 10 carbon atoms, and wherein A fluorenyl group containing 1 to 10 carbon atoms. 41- The method according to item 40 of the scope of patent application, wherein ... and ^ represent tertiary alkyl groups containing 4 to 10 carbon atoms, and let R3 represent a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms. The 13th method is based on the method of item 4G of the patent application, wherein the hindered anti-oxidant is carried on the distribution agent. 43. The method according to item 42 of the patent application, wherein the distribution agent is a dream stone ° 44. The method according to item 42 of the patent application, wherein the distribution agent is carbon-7-^ paper from tBBJlT fresh ( CNS) (210X297 mm) ------ ί ----- Λ < ------- Order — — I- ^ Please read the note on the back before filling out this page) Central Ministry of Economic Affairs 橾Printed A8 B8 387903 g by the Zhuhai Bureau Shellfish Cooperative Co., Ltd. 夂. The scope of patent application 45. According to the method of 39 patent applications, the amount of the blocked antioxidant is in the range of 0.25 phm to 3 phm. 46. The method according to item 40 of the patent application, wherein the amount of the hindered anti-oxidant is in the range of 0.5 phm to 2 phm. 47. The method according to item 42 of the scope of patent application, wherein the amount of the hindered age · antioxidant is in the range of 1 phm to 1.5 phm. 48. The method according to item 21 of the application, wherein in the reaction zone, a part of the 1,3-butadiene monosystem is liquid. 49_ A method for gas-phase polymerization of isoprene into cis_14-polyisoprene during the manufacturing process, which is characterized by the following steps: (1) adding the isoprene and the preformed contact to the reaction zone Media system 'This catalyst system is made by reacting organic compounds with osmium tetrachloride; wherein the isoprene system maintains gas in the reaction zone by an appropriate combination of temperature and pressure. Phase; (2) polymerize the isoprene to cis-1,4-polyisoprene at a temperature in the range of 0 ° C to 100 ° C; and (3) remove the isoprene from the reaction zone Cis-1,4 · polyisoprene, wherein the organoaluminum compound has the following formula Ά1-R,, ^ 3 Printed by Zhengong Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs (read the note on the back ^ 'before filling out this page) Its central system is selected from the group consisting of Tongji, Aromatic, and Shuangfang And aryl, and hydrogen; and R2 and & may be the same or different, and are selected from the group consisting of alkynyl, aryl, alkaryl, and aralkyl, and their organoaluminum compounds. This paper size is applicable to China National Standard (CNS) A4 specification (210X297) A8 B8 C8 D8 387903 VI. Patent application scope The molar ratio of titanium gasification is between 0 · 7: 1 to 2.1: 1 50. The method according to item 49 of the scope of patent application, in which a part of the isoprene monosystem in the reaction zone is in a liquid state. 51. —Isoprene is polymerized into cis by the solution polymerization process. The method of polyisoprene is characterized by the following steps: (1) Adding an inert organic solvent to the reaction zone, the isoprene and (c) the preformed catalyst system, this The catalyst system is made by reacting an organoaluminum compound with titanium tetrachloride; (2) at a temperature in the range of 0 ° C to 100 ° C, The isoprene polymerized into cis-1,4-polyisoprene; and (3) taking out the cis-1,4-polyisoprene from the reaction zone, wherein the organoaluminum compound has the following structure The formula / Rl A1-R, \ · its center is selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, and hydrogen; and 112 and 113 may be the same or different, and is selected from the group including alkyl, The molar ratios of aryl, alkaryl and aralkyl, and the organoaluminum compounds to titanium tetrachloride are between 0.7: 1 and 2.1: 1. 52. According to the scope of patent application No. 51 The method of item 5, wherein the pre-formed catalyst system is made by reacting an organoaluminum compound with titanium tetrachloride in the presence of at least one ether. 53_ The method according to item 52 of the scope of patent application, wherein the cis _14_ Polyisoprene is taken out of the reaction zone in the form of polymer sludge. Its -9- This paper is from Post® ® Green JfM CMS > A4iWM 21DX297 mm) L --- --- ΛΑ: Please read the note # ^ on the back before filling out this page), 1T Printed Bags of Shellfish Consumer Cooperatives, Central Liangzhun Bureau, Ministry of Economic Affairs · A8 iy · 387SO 3 a D8 6. Scope of patent application It includes cis-1,4-polyisoprene and inert organic solvent. 54. The method according to item 53 of the scope of patent application, wherein in step (2), the isoprene is polymerized into cis-1,4-polyisocyanate at a temperature ranging from 35 ° C to 70 ° C.戍 二 晞. Please read the precautions on the back before filling out this page) n ^ — m 1 ^ 1 ml In — ^ n —i ^ mr * tT -C Printed by Shelley Consumer Cooperative, Central Bureau of Standards, Ministry of Economy-10- This paper size Applicable to Chinese family standard (CNS> A4 specification (210X297mm)