TWI273106B - Method of manufacturing polydiene-based rubber - Google Patents

Abstract

The present invention relates to a polymerization method of high-cis polydiene-based rubber. A lanthanide-based metal carboxylate catalyst system is used in diene-based monomer polymerization, and proper amount of phenolic-based compound is added into the polymerization solution contained in a reactor so that gel polydiene-based rubber would not be formed after the polymerization is finished. The polydiene of the present invention can be used in manufacturing impact resistance polystyrene-based resin, and in thin-film or board-pressing forming, the surface of polystyrene-based resin will not generate fish eyes.

Description

1273106 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) Field of the Invention The present invention relates to a process for producing a polydiene rubber, and more particularly to a process for polymerizing a high cis polydiene rubber. The lanthanide metal carboxylate catalyst system is used in the polymerization of the diene monomer. After the polymerization reaction is completed, an appropriate amount of the phenolic compound is added to the polymerization solution in the reaction vessel to obtain no gel (ge 1). Polydiene rubber. The polydiene rubber of the present invention can be used for producing an impact-resistant polystyrene-based resin which has an advantage that it does not cause an eye when it is formed into a film or a sheet. SUMMARY OF THE INVENTION Generally, a high molecular weight, impact-resistant polyethylene resin, modified polyphenylene strikeability. Conventional, the use of a single amount of stabilizer is low, or the intermediate tank of the reaction is added, in general, the olefinic rubber with styrene in the physical properties of the rubber is destroyed by the rubber. In the above-mentioned words, it is a catalyst-modified resin which is excellent in the catalyst. In order to change the polymerization, the phenolic styrene is a high cis-polymerized polymer of the cis-type polymerization. It can be applied to a variety of applications, especially in the case of a large number of excellent film or sheet forming, the polydiene system will be added between 5wt〇/〇~2wt%, resulting in the conversion rate in the reaction tank. Move from the reaction tank to the fixative. The high-diene rubber which is polymerized by the catalyst is used for its tires, adhesives, and impact resistance. For example, when rubber is used, it can improve the heat stability of the rubber. Or the reaction rate is reduced in the pipeline, and the intermediate tank is in the thin rubber 1273106

V. INSTRUCTION DESCRIPTION OF THE INVENTION (2) The above-mentioned phenolic compound (〇·5 wt% to 2 wt%) is added to the gum, and the polydiphenyl rubber is still prone to gelation (ge 1). Therefore, when a high-cis poly-diuretic rubber polymerized with a ruthenium-based catalyst is used for an impact-resistant polystyrene-based resin, the resin generates many fish eyes when it is subjected to film or sheet forming (fi Sh The shortcomings of eye), which is a small particle on the surface, affect the appearance and value of the molded article. Therefore, the modified olefinic monomer which is polymerized by a rare rubber is polymerized and reacted. The molar ratio of the reaction to be polymerized is 〇·[ If the raw material of the high-resin resin produced by the present invention is obtained, the raw material will be reduced, and in order to improve the lack of raw materials, the method is completed after the completion of the use, · 〇 (based on the complete mixing of the devolatilizer, does not produce a condensed polydiene.) The resin may have good properties and provides a high cis polydiene rubber. The present invention is based on a secondary metal. The carboxylate catalyst system is used to carry out the polymerization reaction solution in the polymerization reaction solution. The polymerization solution is added to the total amount of the mo 1 e number of the mo 1 _ series metal. The polymerization solution is then subjected to devolatilization or stripping and drying. Polydiene rubber.利 糸 糸 做 做 做 做 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 i Detailed description of the invention Generally, in the production of high-cis s ^ ^ 0 series, titanium (1 ^) system, in the industrial process, cobalt-based and lanthanide-based metal compounds are used to form a ruthenium-based rubber. The metal compound d and the nickel-based metal compound such as the Co) system and the lanthanum (La) system are relatively large. Since the 1990s, there have been a large number of production regulations.

Page 5 1273106

Since the polydiene rubber using a lanthanoid metal is high, it can be applied to the use of a wheel-based resin. The compound has the best linearity of the molecular chain in the catalyst system, the industrial product and the high cis content as the polymerization, and the molecular weight is more resistant to impact polystyrene = lanthanide metal carrier salt catalyst system, And: i=USP454471 8, USP452〇m, or usp Γ匕, ΐ: # 'and preferred lanthanide metal compounds can be made from lanthanide metals using citric acid and a large amount of water. The lanthanide metal oxide I =: emulsified divergence (Nd203), hexadecyl oxyhydrazine (ΡΠ1016), chyloindole (Ce2〇3), etc.; the organic carboxylic acid is neonic acid, twelve burning k, myristic acid, or naphthenic acid, and the like. The polymerization method of the high cis polydiene rubber of the present invention is as follows: a diene monomer and an appropriate amount of a solvent are added to the first reactor, and a pre-doped lanthanide metal carboxylate catalyst system is used for polymerization. . After the appropriate amount of antimony is added to the polymerization solution in the reaction dad:, = the amount of the desired compound is between m〇丨e ratio 〇·5~3 · 〇 (relative to the mother m ο 1 e Between the metal). After the polymerization solution and the phenolic compound in the reaction dad are mixed, the devolatilization step can be carried out, such as direct devolatilization or stripping (stri pp i ng) and drying, etc., to obtain high cis. Polyadiene rubber. The present invention uses a preferred catalyst system to polymerize a high-cis poly-diuretic rubber such as a ruthenium metal carboxylate in combination with an alkyl-based gasification compound and an organic compound, which may be r A 1 c 1 2, R3 A12 Cl 3 or R 2 A 1 Cl and other structural formulas, wherein R is a hydrocarbon of 8 to 12 carbon atoms, such as 1273106. 5, invention description (4) dioctyl chloride, or divalent Di-isobutyl Alumium ch 1 oride (DIBAC), which can be added to a solvent to form a solution and then added. Further, the organoaluminum compound is a structural formula having R' 2 A 1 Η, and R ' is an alkyl functional group of 2 to 6 carbon atoms, such as diethylaluminum hydride, dibutyl hydride, or diiso Di-isobutyl Alumium hydride (DIBA Η ), which can be added to a solvent to form a solution and then added. In order to achieve high conversion polydiene polymerization, the ratio of the above catalyst must be limited, and the molar ratio of the lanthanide metal carboxylate to the sum of the alkyl aluminum chloride compound and the organoaluminum compound is 1: 1. Between 5 and 1: 1 0 0, the best range is between 1: 1.5 and 1: 60. The molar ratio of the lanthanide metal carboxylate to the alkyl aluminum chloride compound is preferably between 1:0.5 and 1··1 0 . The diene monomer used in the present invention may be butadiene, isoprene, 2-phenylbutadiene, 2,3-dimethylbutadiene, 1,3-hexadiene, and 1 , 3-octadiene and the like. In addition, when the diene monomer of the present invention is polymerized, a suitable solvent may be further added as a polymerization medium as needed, and an inert hydrocarbon suitable for use as a polymerization medium includes aliphatic, cycloaliphatic, aromatic And a monoolefinic hydrocarbon or a mixture thereof; the hydrocarbon is selected from the group consisting of aliphatic hydrocarbons having 4 to 8 carbon atoms, cyclic aliphatic hydrogen barrier compounds having 5 to 10 carbon atoms, An aromatic hydrocarbon having 6 to 9 carbon atoms, a monoolefin having 4 to 8 carbon atoms, and a mixture thereof. Examples of the above hydrocarbons include, but are not limited to, n-butane, n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, benzene, toluene, xylene,

1273106 I. Description of the invention (5) Butene and decene. The method of the present invention is carried out in a polymerization medium of aromatized hydrocarbon, and the second & electrification is carried out in a aryl-free group. The C4-C8 aliphatic hydrocarbon, C5 is a mixture of hydrocarbons selected from the following: The catalyst system has a preferred activity in this - polyci~C8 monoolefin. It is used to be a person A. In the medium, the display is selected from the group consisting of n-hexane and cyclohexane. ～ Λ ” ; ; 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性 惰性The temperature of the solution and the catalyst system configuration is melted by the solvent: t compound solution. It needs to be controlled in the range of 〇12〇. It can be added separately, preferably the organic catalyst is added first, the acid salt compound is added. 'After adding the burning base gasification Minghe: and, the base metal rebel can be used in the polymerization reaction, first the organoaluminum compound:: need also | compound mixed together., bismuth metal carboxylate in the configuration of the invention In the case of the medium system solution, small denier|ene can be added to increase the activity of the catalyst, and the conjugate-induction time of the two-miles is shortened, and the conjugated diene is added to the contact enthalpy: t is the initial polymerization stage. The molar ratio of the metal carboxylate to the conjugated diene is based on 丨·· wind, 1 0 0 0, wherein 1 ···· 5 to 1 ··· 5 〇〇 is preferred, ^ · · 1 ·· 1 0 0. The conjugated diene can be di-M, 彳1 ·· 2 to wait. " When the monomer is polymerized with pentylene, butyl or 1,3-pentene, it is said that the sputum olefinic precursor can be added before the catalyst or 1273106. DESCRIPTION OF THE INVENTION (6) After being added, it is pumped into the reaction tank or added between the time when one catalyst and the other catalyst are added, and the reaction may be added in one time or in several portions. The reaction tank used in the present invention is It is preferred to have a stirring device, and one or more reaction tanks connected in series may be used, preferably in the form of a batch feeder. When the polymerization reaches a certain conversion rate, the polymer solution in the reactor is added. The molar ratio is 0·5~3 (based on the lanthanide metal per mol e) of the desired compound, wherein the mo 1 e is preferably in the range of 0·7~2. 8. The best is 0. 8~2.

The phenolic compound described above is not particularly limited, but the effect of the hindered phenol compound is preferred. Specific examples thereof are: tetrakis[methylene-3-(3',5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-tri-methyl-2 , 4,6-tris(3,5-di-t-butyl-4-phenyl)-phenyl

Benzene, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butyl-butyl, 2,4-bis-n-thiooctyl-6 - (4-hydroxy-3,5-di-t-butyl-phenylamino)-1,3,5-triazine, octadecyl-3-(3,5-di-t-butyl 4-hydroxyphenyl)propionate, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,3, 5- Tris-(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)isocyanate, 2,2'-indenylene-bis-(4-methyl-6-tributyl) Phenyl), 3,9-bis[2-{3-t-butyl-4-hydroxy-(5-methylphenyl)propoxyphene, 1,didecylethyl] -2,4 , 8.10-tetra-ethylenedidecyl (5, 5) undecane, 4-hydroxymethyl-2,6-di-t-butylbenzene, 2,6-di-t-butyl-4- Ethylbenzene, butylated-trans-benzyl-benzoquinone, 2,2 '-di-based-3,3 '-dicyclohexyl-5,5-diindenyl-diphenyl anthracene, 1, 1,3 -tris(2-methyl-4-carbosyl-5-t-butylphenyl)butane, [4,4'-butylene-bis(6-t-butyl-m-cresol)

Page 9 ^ 273106 Description of the invention (7) J, bismethyl ~ bis 1 - hydroxy [3,5 ~ bismuth 2, 6 phenol system in the kettle, added to the reaction side, then as a film resistant or added The requirements for lowering the shortcomings. The liquid has not yet reached the above-mentioned per m ο 1 e and this film or extrusion (based on the rate of each, cloth. The above-mentioned base phenyl) A, 2,2-Asian and 1, Bu (2' - In the methyl group, octadecyl-3-propionic acid ester (abbreviated as IX-1076 or BHT for short) is preferred. The solution after the liquid is added to the polymerization is mixed after the reaction, if it is in the middle of other places. When the raw material is added to the storage tank, the resin is produced. If the feed solution is at a rate that causes the conversion rate to be extremely important, the diene rubber solution is added to the reaction vessel. / , m 0 1 e ratio is less than 0 · 5 Γ Long rubber is easy to produce gel phenomenon, and the polystyrene resin is thin; if the mole ratio is greater than 3 ', the next batch of polymerization is easy to obtain stable molecular culture 3-cyclohexyl-2 -trans group n (4~ethyl-6-tert-butylphenol)~5'-tert-butylphenol), etc., its second butyl-4-phenylphenyl)' 'Di-t-butyl- 4-methylphenol (the compound is soluble in the solvent to dissolve. For the purposes of the present invention, the polymer solution in the phenol-based label makes it as a reaction In the tank outlet line, or when the rubber impinging the polystyrene resin is molded, there will still be a compound of the fisheye, which will reduce the reverse. Therefore, when the phenolic compound is added, the front of the diene rubber is polymerized. The appropriate amount of phenolic compound is combined with the purpose of the invention. When the amount of the compound is used, if it is a metal, the polydiene rubber is used as a raw material to produce an eye-resistant phenomenon when impact-resistant molding, l〇le The lanthanide metal) will cause a decrease in the conversion rate, and the polydiene rubber which is not transmitted by the B can be used as an impact resistance poly 1273106. 5. Description of the invention (8) A rubber-modified raw material of an olefin resin. The polydiphenyl rubber is dissolved in a styrene monomer (may be added to a solvent if necessary), and is polymerized in a bulk or solution or a bulk solution in a suspension and is suitable for use in the benzene of the present invention. Ethyl sulphate, benzyl-methyl styrene, p-methyl styrene, m-methyl styrene, 2,4-di-methyl styrene, ethyl styrene Ethyl styrene), alkyl-substituted styrene such as p-tert-butyl styrene, and such as: α-methylstyrene methyl styrene, α-methyl-p-- An α-alkyl substituted styrene such as α-methyl p-methyl styrene, or bromine-styrene, dibromo-styrene, 2,4·6-tribromo-styrene or the like. The above styrene monomer may be used singly or in combination of several, and the above monomers are preferably styrene a • methyl stearic ethylene. The following examples are illustrative of the invention, and therefore the present invention should not It is limited to the scope specifically described in the examples. [Example 1] A 3-butadiene monomer 1 〇 Kg and n-hexane 8 〇 Kg were pumped into a 50 ° liter reaction with an interlayer. When the temperature was raised to 65 ° C, a catalyst was added to carry out a polymerization reaction. The catalyst is a mixture of 23 mmole neodymium ruthenate, 〇. 23 [11〇]^ DIBAE^ 〇· 〇7 mo 1 e D I BAC. After the polymerization reaction is completed, the polymerization in the reactor

1273106 V. INSTRUCTIONS (9) Add 2 1 · 8 5 mm ο 1 e 2 · 6 - di-t-butyl-4-methylphenol (BHT) to the solution (relative to each mole of titanium metal) Said, the amount of BHT is 0. 95 m ο 1 e, that is, m ο 1 e is 0. 9 5), then the polymer solution is pumped into the intermediate storage tank, and after the drying step is obtained by steam, the polybutyrin is obtained. The diene rubber was used to calculate the average conversion rate of the 50 batches of the reaction. Next, 84% by weight of styrene and 6% by weight of the above polymerization were carried out to obtain a polybutadiene rubber and 10% by weight of ethylbenzene, and a starter of 0. 0 2 weight ° / 〇 was added, and the reaction was carried out. After the reaction, the polymer solution is sent to a devolatilization tank to remove volatiles, and then an impact-resistant polystyrene resin is obtained. The resin is then extruded through a film, and the surface of the molded article is observed to have a fi sh eye. The phenomenon. [Example 2] A polybutadiene-based rubber was prepared as in Example 1, except that after the completion of the polymerization reaction, a polymer solution of 3 1.46 mm ο 1 e was added to the reaction solution of the dad. A compound (i.e., a ratio of m ο 1 e is 1 · 3 5). Further, the polybutadiene-based rubber obtained as described above was subjected to a method for producing a shock-resistant polystyrene-based resin of Example 1, i.e., an impact-resistant polystyrene-based resin was obtained, and the physical properties thereof were measured. [Example 3] Polybutadiene rubber was prepared as in Example 1, except that polymerization was carried out.

Page 12 1273106 V. INSTRUCTIONS (ίο) After the reaction is completed, add 6 2 . 1 mm ο 1 e to the polymer solution of the reaction dad Η T test compound (ie m ο 1 e ratio is 2 · 7 ). Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the production method of the impact-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured. [Example 4] A polybutadiene-based rubber was prepared as in Example 1, except that after the completion of the polymerization, 3 1.46 mm ο 1 e of octadecyl group was added to the polymer solution of the reaction oxime. a compound of -3 - (3,5-di-t-butyl-4-hydroxyphenyl)propionate (i.e., m ο 1 e ratio is 1 · 3 5). Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the method for producing an impact-resistant polystyrene resin of Example 1, to obtain an impact-resistant polystyrene resin, and the physical properties thereof were measured. [Comparative Example 1] A polybutadiene-based rubber was prepared as in Example 1, except that a 2.00 mmole of a BHT phenolic compound was added to the feed solution for preparing polybutadiene (i.e., the mo 1 e ratio was 0. 4), the feed solution is pumped into the reaction dad for polymerization. Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the production method of the impact-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured.

Page 13 1273106 V. Description of the Invention (π) [Comparative Example 2] The polybutadiene-based rubber was prepared as in Example 1, except that after the polymerization was completed, the reaction was carried out in the reaction solution of the dad. Mm ο 1 e Β 盼 T expectant compound (ie m ο 1 e ratio is 0 · 1). Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the production method of the impact-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured. [Comparative Example 3] The polybutadiene-based rubber was prepared as in Example 1, except that after the completion of the polymerization reaction, a cationic compound of 2 7 6 mm ο 1 e was added to the reaction solution of the reaction dad (i. The mo 1 e ratio is 1 2). Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the method for producing a shock-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured. [Comparative Example 4] A polybutadiene-based rubber was prepared as in Example 1, except that after the polymerization reaction was completed, the polymerization solution was pumped into the intermediate storage tank, and then 276 mmol e of Β was added to the intermediate storage tank. The T-trying compound (i.e., the mo 1 e ratio is 1 2). Therefore, the amount of BHT added herein is 0 · 5 7 parts by weight (i.e., 0 · 5 7 phr) with respect to 100 parts by weight of polybutadiene. Further, the polybutadiene-based rubber obtained as described above can be obtained by the same method as the impact-resistant polystyrene resin of the first embodiment to obtain impact-resistant polyphenylene.

Page 14 1273106 V. INSTRUCTIONS (12) Ethylene resin and its physical properties were measured. [Comparative Example 5] A polybutadiene-based rubber was prepared as in Example 1, except that after the polymerization reaction was completed, the polymerization solution was pumped into an intermediate storage tank, and then 690 mmol of methanol was added to the intermediate storage tank. 4.6 mmole of T-trying compound (ie, methanol mo 1 e ratio of 30 and BHT mole ratio of 0.2).

Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the method for producing a shock-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured. [Comparative Example 6] A polybutadiene-based rubber was prepared as in Example 1, except that after the completion of the polymerization reaction, 31.46 mmol e of Η 2 0 was added to the reaction dad (the ratio of mo 1 e of Η 2 0 was 1). · 3 5). Further, the polybutadiene-based rubber obtained as described above was obtained in the same manner as in the production method of the impact-resistant polystyrene-based resin of Example 1, to obtain an impact-resistant polystyrene-based resin, and the physical properties thereof were measured.

The present invention uses the following three physical property test methods to observe the results of the examples and comparative examples of the present invention:

I. ΜI: Fluidity ASTM D-1238G II. Gel phenomenon of polybutadiene rubber:

Page 15 1273106 V. INSTRUCTIONS (13) 5 g of polybutadiene rubber is dissolved in 250 ml of Toluene and dyed red. It is filtered on 70 mm filter paper. After drying naturally, it is observed by the naked eye. The amount of ge 1. III. F i s h e y e phenomenon on the surface of the impact-resistant polystyrene resin: The impact-resistant polystyrene resin film was extruded to visually observe the fish eye phenomenon on the surface of the film. The physical property test results of the examples and comparative examples of the present invention are as follows: Table 1 and physical property test results of the examples [Examples] 1 2 3 4 Polybutadiene rubber phenolic compound (I) (I) (I) (Π Add to the feed (mole ratio) - _ - - Add to the reactor (mole ratio) 0.95 1.35 2.7 1.35 Prepare the reaction dad outlet (mole ratio) - - - - 50 batch average conversion rate (wt%) &gt ;95 >95 93 >95 Gel phenomenon is rare, very few, very little impact resistance, polystyrene tree, moon object MI 5.3 5.1 5.2 5.1 sex fish eye Very few very few very few Note: (1) means 2.6_ two third 4-methylphenol (BHT) (9) represents an eighteen-yard-3-(3,5·di-t-butyl-4-ylphenyl)propionate ※mole ratio: relative to each mole In the case of base metals

Page 16 1273106 V. INSTRUCTIONS (14) Table 2, physical property test results of comparative examples [Comparative Example] 1 2 3 4 5 6 Polybutadiene rubber phenolic compound (I) (I) (I) (I (1) + methanol water feed (mole ratio) 0.4 - - - - Add to the reactor (mole ratio) - 0.1 12 - - 1.35 Prepare the reactor outlet (mole ratio) - - - 12 0.2 ( 1) - 3 〇 (methanol) 50 batch average conversion rate (wt%) >65 >95 85 >95 >95 71 Gel phenomenon is severely serious, severely severe, and more than an inch of impact polystyrene resin MI 7.0 5.1 6.0 5.2 5.3 5.2 Sex fish eye Severely serious, very serious, serious and serious

Note: (I) indicates 2.6_di-t-butyl-4-methylphenol (BHT)

It is known from the above [Comparative Example 1] that the addition of the phenolic compound in the feed solution (before the reaction) lowers the average conversion rate, and the surface of the film of the impact resistant polystyrene resin is severely formed. Fish eye

Page 17 1273106 V. Description of Invention (15) Phenomenon; It is known from the above [Comparative Example 2] that the amount of the compound used is too small (less than 0 · 5 mo 1 e ), and the effect is not good; 3] It is known that when the phenolic compound is used in a large amount (mo 1 e ratio is 1 2 ), the average conversion rate is decreased a lot; from the above [Comparative Example 4], it is like a general method, and is stored at the outlet of the reactor (such as intermediate storage). When a phenolic compound is added to the tank (this is a process in which a phenolic compound stabilizer is conventionally added), it is found that the impact-resistant polystyrene resin causes a severe fi eye phenomenon; from the above [Comparative Example 5], A large amount of methanol is used in combination with a small amount of a BHT phenol-based compound, and the impact-resistant polystyrene resin has a serious fi eye phenomenon; when the phenol-based compound is replaced by H2 0 by the above [Comparative Example 6], the conversion rate is lowered and the resin There is still a phenomenon of fisheye. Therefore, the effect of the present invention can be attained by adding an appropriate amount of a phenolic compound to the reaction vessel after completion of the polymerization reaction. The above description of the present invention is intended to be illustrative of the present invention and not to limit the scope of the present invention, and those skilled in the art will be able to make certain changes and modifications as appropriate, without departing from the scope of the invention. Without departing from the spirit and scope of the invention.

Page 18 1273106 Schematic description

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Claims (1)

1273106 VI. Patent application scope 1. A polymerization method of a high-cis polydiene rubber, which is subjected to polymerization in the presence of a diene monomer and a lanthanide metal carboxylate catalyst system; the polymerization reaction is completed. 5摩尔之间。 The phenolic compound is added to the phenolic compound, wherein the amount of the phenolic compound is 0. 5~3. 2. The method for polymerizing a high-cis polydiene rubber according to claim 1, wherein the preferred range of the amount of the phenolic compound is 0 with respect to each m of the metal. 7 to 2. 8 m ο 1 e between. 3. The method for polymerizing a high-cis polydiene rubber according to claim 1, wherein the optimum range of the amount of the phenolic compound is 0.8 to 0.80 per m of the lanthanide metal. Between 2.0 mol e. 4. The method of polymerizing a high-cis polydiene rubber according to claim 1, wherein the conjugated compound is a sterically hindered compound. Page 20