TW552269B - Process of making conjugated dienic polymers - Google Patents

Abstract

This invention provides a process for making conjugated dienic polymers, particularly to a process that enhances high temperature stability, color phase stability and processing stability of the polymers via post-treatment steps carried out in a particular order and by utilizing a small amount of particular antioxidants. The process includes the steps of post-treating a living polymer formed by polymerizing conjugated dienic monomer and/or styrenic monomer: (1) adding 0.01-1 part by weight of an organic acid to 100 parts by weight of the living polymer; (2) adding at least 1 part by weight of water to 100 parts by weight of the living polymer; (3) adding a phenol-based antioxidant and a thiophenol-based antioxidant in a specific proportion; and (4) volatilizing and recovering the polymer resulting from the above post-treatment steps to obtain the conjugated dienic polymer according to the invention.

Description

Five 'hairpin description f refers to ::!: It refers to a method for manufacturing a co-light diene polymer. In particular, it is known to carry out post-treatment steps in a specific order, and to cooperate with a particular gasification agent and specific mediators. The manufacturing method of AA > t's multi-resistance resistance = oxidant, to improve coplanar dual-homing polymerization M ", son-in-law, hue and processing stability. Press 'Conjugated diene polymer is a catalyst under organic solvent' to promote the polymerization of co-diluted monomers and / or styrene-based monomers: Under the temperature, it has the thermal Tecogan-Mountain Of * Γ 玍 body, which has the same processing characteristics as the thermoplastic resin when processed at high temperature, such as: high temperature hot branch and color, so it can be used for Modification of plastic resin, asphalt, adhesives, food packaging containers or rubber for industrial use, etc., is a polymer with a wide range of applications. However, due to the poor high-temperature thermal stability of the co-light diene polymer, it will cause disadvantages such as poor hue of the polymer and yellowing of the molded product during use, and the polymer will also have poor processing stability. In the center of Fenglu Department «.ping '^', only _1. Cooperating with Fen ^ Printing In order to improve the shortcomings of diene-based polymers, many improvements are provided in known techniques, such as Yue Bente Japanese Patent Publication No. 55-7459 mentions that an organic lithium compound is used as a catalyst in an organic solvent to polymerize a conjugated diene monomer and a styrene monomer to obtain a styrene-butadiene block. Polymer solution, and then stop the polymerization reaction with methanol, before the devolatilization step, add an aqueous solution of an organic acid compound to the polymer solution to contact and mix, and then recover the polymer by devolatilization after the oil-water phase separation step, A conjugated diene polymer having a good hue can be obtained. In Japanese Patent Application Laid-Open No. 60-231717, it is mentioned that the organic lithium metal compound is used as a catalyst to polymerize a conjugated diene-based monomer and / or acetophenone-based monomer into a living polymer. ), And then add the appropriate paper size] Chinese National Standard (CNS) A4 specification (210X297 mm) ^ 3 1_ 552269 A7 ----------------- B7_ V. Description of the invention (≫) Stabilizers or stabilizers and stoppers are added, and after removing the solvent, fatty acids with more than 10 carbon atoms are added to obtain a polymer with improved hue. In Japanese Patent Application Laid-Open No. 62-232402, it is mentioned that after the above-mentioned active polymer is substantially free of water, after adding an organic acid and a stabilizer, the solvent is devolatilized, and the hue can also be improved. Polymer. In addition, Japanese Patent Application Laid-Open No. 4-252243 mentions that the use of conjugated diene rubber with two specific stabilizers, such as phenol-based and thiophenol-based stabilizers, can prevent the generation of gels, but Because the added amount of phenol-based stabilizers in this patent application is still too high, it still has some adverse effects on the hue of rubber, and conjugated diene rubbers with high phenol-based antioxidant content are used in rubber modified styrene-based During the graft polymerization of the resin, it also adversely affects the conversion of the monomers and the grafting rate of the monomers grafted to the rubber, which in turn results in poor physical properties of the modified styrene resin. Although the above-mentioned various known technologies can improve the lack of the hue of the conjugated diene polymer, etc., the improvement effect is limited, especially in terms of high-temperature thermal stability, it is impossible to achieve good hue and polymer Good processing stability and other effects, and in the aforementioned various known technologies, in order to achieve the hue or thermal stability required in the market, it is still necessary to add a higher content of phenolic antioxidants, which will affect the initial hue of the rubber and the The polymerization reaction of the rubber-modified styrene-based resin has an adverse effect; the present invention aims to improve the aforementioned defects, and carefully researches a solution. That is, the object of the present invention is to provide a method for producing a conjugated diene polymer having excellent performance in high-temperature stability, processing stability, and hue.

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552269 A7 B7 V. Description of the invention (9 In addition, the manufacturing method of the conjugated diene polymer of the present invention consists of: a conjugated diene monomer and / or a styrene monomer as the main component, and the use of organic lithium It is a living polymer produced by catalytic polymerization. The living polymer is post-treated in the following order: (1) 0.01 to 1 part by weight of organic is added to 100 parts by weight of the foregoing active polymer. Acid; (2) adding at least 1 part by weight of water to 100 parts by weight of active polymer; (3) adding 0.02 to 0.5 parts by weight of antioxidant to 100 parts by weight of active polymer Contains: (a) a phenolic antioxidant; and (b) an antioxidant having the following structural formula (I); OH Ri R4 ~ "-Rule 2 -...... ... Structural formula (I) In the structural formula (I), R! And R3 are -CH2-S-R5, R5 is an alkyl group having a carbon number of 20 or less, R2 and R4 are a hydrogen group or a carbon atom having a number of Alkyl groups below 15; (4) High temperature thermal stability can be obtained by subjecting the polymer solution through the aforementioned (1), (2), (3) post-treatment steps to a devolatilization and recovery process. A conjugated diene polymer having excellent performance in color, hue, and processing stability. The living polymer of the present invention uses an organic catalyst as a catalyst, and conjugates diene in the presence of an organic solvent. Monomers and / or styrenic monomers are polymerized into polymers. If individual conjugated diene monomers are polymerized, they are polyconjugated diene polymers. There are two types: star and linear. Organolithium is a page (¾Please read the precautions on the back before filling this page) The size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 552269 A7 B7 V. Description of the invention (4) (Xu first read the back Please pay attention to this page, please fill in this page) When the catalyst is used, the conjugated diene polymer of the polymer is low-cis, and its structure has a typical weight composition of cis / vinyl. The range is from 30% to 40% / 5 to 40%, and the viscosity of the 5% acetophenone solution is between 5 and 400 cps; the above-mentioned manufacturing method is a well-known technology, and the detailed method is described in US No. 2,975,160, No. 3,094,514, No. 3,135,716, No. 3,244,664, No. 3,3 18,862 and other patent cases, as well as Japanese Patent Publication No. 48-875, Japanese Patent Publication No. 48-46691, Japanese Patent Publication No. 49-36957, Japanese Patent Publication No. 55-40734, Japanese Patent Publication No. 57-40513 Etc. In addition, the present invention can also be obtained by copolymerizing a conjugated diene monomer and a styrene monomer. The method for producing the above-mentioned living polymer is also a well-known technology, and the detailed method is described. In: U.S. Patent No. 3,094,514, U.S. Patent No. 3,451,988, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 46-32415, Japanese Patent Publication No. 49-36957 Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-4106, Japanese Patent Publication No. 56-28925, Japanese Patent Publication No. 51-49567, etc .; In order to manufacture the living polymer, the conjugated double The use amount of the olefinic monomer and the styrene-based monomer is not particularly limited, and is generally 99.9: 0.1 to 0.1.99: 9, and the preferred range is 98: 2 ~ 2: 98, It can be a random copolymer, a star type copolymer, a bloc k) Copolymer or taper copolymer; when the living polymer is a drum copolymer, in order to show the characteristics of a thermoplastic elastomer, the content of the styrene monomer in the polymer is 60% by weight Hereinafter, the content is preferably 55% by weight or less, and in order to express the characteristics of the thermoplastic resin, the content of the styrene-based monomer in the polymer is 65% by weight or more. The conjugated diene-based single system used in the present invention has a pair of conjugates._Page 6_ This paper is a Chinese standard (CNS) A4 size (210 × 297 mm) 552269 A7 B7 V. Description of the invention (5) (诩 Please read the notes on the back before filling this page) Double bond diene compounds, which are selected from: 1,3-butadiene, 2-methyl-1,3-butadiene, 2 -Methyl-1,3-isoprene, 2,3-bis-methyl-1,3-butadiene, 1,3-isoprene, 1,3-hexadiene, etc., the above compounds They can be used singly or in combination of two or more kinds. Among them, 1,3-butadiene or 1,3-isoprene is more preferred. The styrenic monomer used in the present invention may be selected from the group consisting of: styrene, o-fluorenylstyrene, p-methylstyrene, p-tetra-butylstyrene, 1,3-bismethylstyrene, One or two or more kinds of α-fluorenylstyrene and the like are mixed and used. The hydrocarbon solvent used in the present invention is selected from the group consisting of: butane, pentane, n-hexane, pentane, heptane, octane, isooctane Isohydrocarbons such as isooctane, cyclopentane, methyl-cyclopentane, cyclohexane, methyl cyclohexane, ethyl -Cyclic aliphatic hydrocarbons such as ethyl cyclohexane, and / or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, can be used during use Choose a single type or a mixture of two or more types. The organolithium compound catalyst used in the present invention is a compound containing more than one clock atom in the molecule, which may be selected from the group consisting of ethyl, n-pentyl, isopropyl lithium, n-butyl lithium, and secondary butyl. Lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, benzyl lithium, naphthyl lithium, tertiary-butyl lithium, trimethylene dilithium, tetramethylene di lithium, butadiene dilithium and isopropyl One or two or more of pentadiene dilithium and the like are mixed and used. Polymerization rate of the polymer of the present invention during polymerization and micro structure of the polymer [ratio of cis, trans, vinyl], and a conjugated diene monomer The reactivity ratio between the polymer and styrene monomer can be determined by the polar _ page 7 _ this paper is suitable Λ] Chinese National Standard (CNS) A4 size (210X 297 mm) 552269 A7 _ B7 V. Description of the invention u) Compounds or randomizing agents to adjust, the above polar compounds or randomizing agents are selected from the group consisting of ethers, amines, thioethers, phosphonium amines, alkylbenzenes, and sulfon acids Potassium or sodium salts of alkyl oxides; specific examples suitable for the present invention are: (a) ethers such as: dimethyl ether, diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, tetra Hydropyran, diethylglycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diphenyl mystery, etc. (b) Amines such as tertiary amines, tri-methylamines, triethylamines, tripropylamines, tributylamines, tetra-methylethinediamines, diethylaniline, pyridine, Cyclic tertiary amines and the like. (c) Phosphine or phosphonium amines such as tri-phenylphosphine, hexamethylphosphine amine and the like. (d) Potassium or sodium salt of alkyl oxide, such as potassium butoxide (potasstium butoxide) ο In the polymerization of the present invention, a polyfunctional coupling agent can be used. Examples of the coupling agent are: bis or polyvinyl aromatic Compounds, bis or polyepoxides, bis or polytris-isocyanates, bis or polyimines, bis or polyacids, bis or polyketones, bis or poly compounds (especially halogenated stones and _ Fossil evening fire), single, double or multi-field, single, double or polyester, two or more or a combination of compounds in combination can be selected during use. Specific examples of ethynyl aromatic coupling agents suitable for the present invention include: diethynylbenzene, 1,2,4-trivinylbenzene, ι, 3-divinylnaphthalene, ^^ triethynyl , 2,4-Ethylene Diene's base copy and its analogues. Among them, Diethyl Ethylene ~~~ ___ Page 8 and Record Standards National Standard (CNS) Α4 Specification (2 297 Mm_) —--- 阅读 Read the notes on the back before filling out this page) Order d 552269 A7 B7 V. Description of the invention (A) Aromatic hydrocarbons are preferred, especially selected from the divinylbenzene , In, or pair equivalent isomers. Commercially available divinylbenzene by mixing three isomers and other compounds has satisfactory results. The epoxy hydrocarbon polymer suitable for the present invention is, for example, an epoxidized polybutadiene solution, an epoxidized vegetable oil, an epoxide, and the like, wherein the epoxidized vegetable oil is, for example, an epoxidized soybean oil ), Epoxidized linseed oil (epoxidized linseed oil) 〇 polyisocyanates suitable for the present invention are, for example: benzene-1, 2,4-triisocyanate (1,2,4-triisocyanate), 1 , 2,5,7-tetraisocyanate naphthalene (xanthine 1 ^ 1 ^ 16116-1, 2,5,7-tetraisocyanate), and the like; and polyimine is a known polyaziridine Compounds, which can use compounds containing 3 or more aziridine rings per molecule, for example ... have triaziridinylphosphine oxygen or triaziridinylphosphine sulfur, specific examples are: three (1-aziridinyl) phosphine oxide, tris (2-methyl small aziridinyl) phosphine oxide, tris (2-ethyl-3-decyl-1-aziridinyl) phosphine sulfur , And its analogs. The representative polyaldehydes of the present invention are, for example: 1,4,7-naphthalene-tricarboxaldehyde, 1,7,9-onion-tricarboxaldehyde, 1,1,5-pentane-tricarboxaldehyde, aliphatic Polyaldehydes and aromatic polyaldehydes; and typical examples of polyketones are: 1,4,9,10-anthracene ketone (1,4,9,10-anthracenetetrone), 2,3-dipropyl gu 1 -Cyclobutanone and its analogs; and examples of multi-needle are pyromellitic dianhydride, styrene-maleic anhydride, and the like; examples of polyesters are: Ethyl-diethyladipate, triethylcitrate, 1,3,5-triethylcarbethoxybenzene, and the like. And the halide can be selected from: silicon tetrachloride, silicon tetrabromide, silicon tetraiodide _ page 9 _ This paper size is suitable for Sichuan National Standards (〇 奶) 8 4 specifications (210 > < 297)厘) 阅读 Read the precautions on the back before filling in this page) Order 552269 A7 B7 V. Description of the invention (s) i Fossil evening, such as silicon trifluoride, silicon trichloride, trichloroethyl silicon, tribromobenzene Trihalide sulfide and its analogs; and, for example, halogenated silanes; and, for example, 3,3,3-tris (,; methylol), 2,5,6,9-tetrachloro-3,7- Decacyclene and its analogs are substituted by multiple halides; among them, halogen is added with a carbon atom of type ^ to form an active atom group such as an ether chain, a carbofluorenyl group, a carbon atom bonded by a double bond ; A substituent which is inert to the lithium atom in the terminally reactive polymer may also be present in the active i-containing compound, and in addition, other suitable reactive groups other than the above-mentioned halogen may also be present. In the production method of the polymer of the present invention, the polymerization temperature is generally between 40 ° C and 150 ° C, and the optimal temperature is between 40 ° C and 120 ° C. The polymerization time and polymerization pressure vary depending on the polymerization conditions. Among them, the polymerization time is usually within 48 hours', especially in 0.5 to 10 hours. During the polymerization, it is necessary to prevent impurities such as: water, §underlying, carbon monoxide and other impurities from entering; the weight average molecular weight of the above polymer Generally in the range of 5,000 to 5,000,000, and most preferably 10,000 to 1,000,000. The active polymer of the present invention polymerized by the above-mentioned polymerization components and conditions must be post-processed in accordance with the order of the following four steps: ir, the middle part of the meaning; j U _τ elimination fr combined ^ 1 卬 1. "(1) Adding 0.01 to 1 part by weight of organic acid to 100 parts by weight of the aforementioned active polymer; (2) Relative to 1 〇〇Replacement part of the active polymer is added with at least 1 part by weight or more of water; (3) Relative to 100 parts by weight of the active polymer, 0.02 ~ 0.5 parts by weight of an antioxidant is added, the above antioxidants include: 0) phenolic antioxidants; and

552269 A7 B7 V. Description of the invention (1) (b) Antioxidants having the following structural formula (I);

In the structural formula (I), Ri and R3 are -CH2-S-R5, R5 is an alkyl group having a carbon number of 20 or less, R2 and P4 are a hydrogen group or an alkyl group having a carbon number of 15 or less (4) The conjugated diene polymer of the present invention can be obtained by subjecting the polymer solution after the above-mentioned steps (1), (2), and (3) to a process of devolatilization and recovery. Wherein, the organic acid in step (1) refers to an organic compound having acidity in a broad sense, which is selected from the group consisting of carboxylic acid, sulfonic acid, sulfinic acid, and hope ( Compounds such as phenol are preferably organic compounds containing carboxyl. Specific examples include: formic acid, acetic acid, valeric acid, octylic acid, capric acid, lauroylic acid, Myristinic acid, palmitic acid, stericlic acid, oleic acid, linoleic acid, linolenic acid, ramie Ricinoleic acid, behenic acid, neodecenoic acid or versatic acid, among others, neodecanoic acid is more preferred. There is no specific limitation on the amount of organic acid used in the present invention, and the method of addition is also not particularly limited. Based on consideration of the convenience of operation, it is preferable to dissolve the organic acid in a solvent and then add the polymer solution. On the other hand, based on the quality stability of the polymer, the oxygen content of the organic acid solution added is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. ___ page 11 _ This paper size applies to China National Standard (CNS) A4 (210X297 mm) 1¾ Read the precautions on the back before filling in this page)

、 1T 4 552269 A7 B7 V. Description of the invention (\ c The aforementioned organic acid is added in an amount of 0.01 to 1 part by weight, preferably 0.03 to 0.5 part by weight relative to 100 parts by weight of the active polymer. When the added amount is less than 0.01 parts by weight, the hue of the polymer cannot be improved, and when the added amount is more than 1 part by weight, it will affect the physical properties of the conjugated diene polymer or its application in subsequent processing. If more than 1 part by weight of an organic acid is added to a batch-type conjugated diene polymerization reaction tank, the organic acid will remain in the polymer and affect the next batch polymerization reaction; the aforementioned organic acid can be used as living polymerization It can be achieved only when the amount of addition is accurately controlled during the addition. Improper use will cause the polymer's thermal stability to decrease, hue difference, and then affect the quality of the polymer. The step (1) of the active polymer in the present invention ) After the organic acid is added, the operation of adding water in step (2) has the advantage that a large amount of water can completely stop a small amount of residual active end groups, and the catalyst reaction generated during the reaction process, such as: hydrogenated clock The chlorinated material insoluble substances are dissolved in water towels to facilitate the removal of these substances; reducing the aforementioned impurities has an adverse effect on the hue, thermal stability, and transparency of conjugated diene polymers. Steps of the invention ( 2) The amount of reclaimed water is 1 part by weight or more relative to 100 parts by weight of the active polymer, preferably 2 to 50 parts by weight, and most preferably 3 to 20 parts by weight. The point can be added in the polymerization reaction tank, or in the pipeline at the exit of the reaction tank, or in the intermediate storage tank. For convenience and quality stability, it is better to add in the reaction tank outlet and the & line, and The water to be added is not limited in particular. Quality and safety _ choose Beiwen 疋 11 g, pure water is a better choice. Read the notes on the back before filling out this page.) Order the anti-oxidants used in the process of the present invention. Oxidation is divided into the following two 552269

A7 B7 V. Description of the invention (Π) (a) Antioxidants are phenolic antioxidants, which are selected from the commonly used phenolic antioxidants. Specific examples are ... , 5, Di-Third-butyl-4-hydroxyphenyl) propionate] Pentane, ι, 3,5-Tri-fluorenyl-2,4,6-tri (3,5-Di · Third Butylhydroxyphenyl) benzene, 2,6-di-third-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-third-butylphenol, 2,4-bis-n Thiooctyl-6- (4-hydroxy 5-—-second butyl-benzylamino) -1,3,5 -triuyahridyl, octadecyl-3- (3,5-di- Third butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-third butyl-5-methyl-4-hydroxyphenyl) propionate, ι, 3 , 5-tri- (4-third-butyl-3-hydroxy-2,6-dimethylphenyl) isocyanate, 2,2, -methylene-bis- (4-methyl-6 · Third butyl phenol), 3,9-bis [2_ {3 · third butyl_4_hydroxy · 5_fluorenylphenyl) propanyloxyb 1,1-dimethylethyl] 〇_ Tetra-ethylenedifluorenyl [5,5] undecane, 4-hydroxyfluorenyl_2,6 · di-third-butylphenol, 2,6-di-third-butyl-4-ethylphenol, Butylated_hydroxy_anisole, 2,2, dihydroxy_ 3,3'-Dicyclohexyl_5,5-dimethyl-diphenylphosphonium, ι, ι, 3-tris (2-fluorenyl-4-hydroxy-5-tert-butylphenyl) butane Alkane, [4,4, _butylene · bis (6-third-butyl-m-cresol)], bis (3-cyclohexyl-2-hydroxy-5-fluorenylphenyl) methane, 2,2 -Methylene-bis (4-ethyl-6-third-butylphenol) and ι, ΐ-bis (2, -methyl-4, _hydroxy-5'_third-butylphenol), etc., among which Octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate is preferred. The fluorene-based phenol-based antioxidant of the present invention does not include the (b) type antioxidant having the following structural formula (I). (b) Antioxidants are thiophenol-based antioxidants, which have the following structural formula (work): • Structural formula (I) Page 13 This paper reads the towels Guan Jia (210X 297 mm) Please fill in this page again)-\ 口 552269 A7 B7 V. Description of the invention (α) Structural formula (I) where I and R3 are -CH2-S-R5, and R5 is an alkyl group with a carbon number of less than 20, R2 and R4 are a hydrogen group or an alkyl group having a carbon number of 15 or less; specific examples thereof include 2,4-bis (n-octylthiofluorenyl) -6-fluorenylphenol [2,4-bis (n-octyl thio methyl) -6-methyl phenol], 2,4-bis (2 ', 3'-bis-propylpropylthiomethyl) 3,6-dimethylpan [2,4-bis ( 2 ', 3'-di-hydroxy propyl thio methyl) 3,6-di_methyl phenol], 2,4-bis (2, -ethoxyethylethylthiomethyl) -3,6-dimethylmethyl [ 2,4-bis (2'-acetyloxy ethyl thio methyl) -3,6-dimethyl phenol], 4,6-bis (octylthiomethyl) -o-pyrophenol [4,6-bis (octyl thio methyl ) -o_cresol], among which 4,6-bis (octylthiomethyl) -o-cresol is preferred. Other antioxidants that can be used in the present invention, such as phosphorus-based antioxidants, thioether-based antioxidants, and hindered amine-based antioxidants, are used in an amount between 0.01 and 0.5 parts by weight. g is an antioxidant or a phosphate ester antioxidant, and its representative are: tris (nonylphenylphosphite), undecylidenesulfonic acid, S, cyclic neopentyl tetrahydronaphthylbis (18 Alkylene phosphite), 4,4'-butylene bis (3-fluorenyl-6-third butylphenyl-bistridecyl phosphite), tris (2,4-third butyl Phenyl) phosphite, tetrakis (2,4-second butylphenyl) -4,4-biphenylene acid, g, 9,10-dihydro-9-oxy-10-phenanthrene phosphate · 10-oxon and so on. Representative examples of thioether antioxidants are: distearylsulfonyl dipropionate, thiodipalmitinyl dipropionate, pentaerythritol_tetra_ (dot-dodecylmethyl-thiopropyl Acid esters), dodecyl sulfide, ditridecyl sulfide, ditetradecyl sulfide, dioctadecyl sulfide, and the like. The total amount of the antioxidants (a) and (b) used in the present invention is relative to 100 ________ Page 14 Paper Size (CNS) (210x297 ^^) " 'Read the precautions on the back before fraud Fill this page

、 1T-· The central iT of the seal envy department.-quasi-XJB_T. Eliminates the combination of bamboo and it 552269 A7 --------_________ B7 5. Description of the invention (丨 3) 1 ^ parts of active polymer 〇2 ～ 0.5 parts by weight, preferably 0.02 ～ 0.3 parts by weight, and more preferably 〇2 ～ 2. 2ΐ parts by weight, in which the amount of the antioxidant used is 〇1 ～ 〇 · 18 parts by weight, preferably 0.001 to 009 parts by weight, and the amount of the (b) antioxidant used is 0.001 to 0.32 parts by weight, preferably 0.001 to 0.21 parts by weight, More preferably, it is 0.001 to 12 parts by weight. When the total amount of (a) antioxidants and (b) antioxidants exceeds 0.5 parts by weight, or the amount of (b) antioxidants exceeds ο · % By weight, it will have an adverse effect on the initial hue of the polymer, and when the total amount of ⑷-type antioxidants and (b) -type antioxidants is less than 002 parts by weight, or (b) When the amount is less than 0.01 parts by weight, the hue, thermal stability, and processing stability of the conjugated diene polymer are not good. In order to achieve the invention, a small amount of antioxidant is added to the conjugated diene polymer [that is, the total usage of (a) type antioxidant and (13) type antioxidant is less than one serious injury] 'can still make the copolymer have Sufficient thermal stability and good hue and processability, whether it is the order of steps (1), (2), (3), (4), or the addition of organic acid in step ⑴, or i parts by weight in step ⑺ The addition of water and other guarding conditions will have a significant impact on achieving good hue and color stability. The method of adding step (2) and ⑺ in the present invention can be directly added to the tank or the s-line, and then mixed by mixing, or can also be mixed by static mixing. The processing temperature is 0 ~ 120 ° C, preferably 50 ~ HHTC, processing time from minutes to hours. In order to devolatilize the solvent in the polymer solution, the present invention adopts a well-known method such as heating and evaporating the polymer solution to remove the original paper size of the solvent. · Home Standard (CNS) a ^^ _ 21〇x297 公 菱 ^ (诮 Please read the notes on the back before filling this page)

552269 A7 B7 V. Description of the invention (β) (诘 Please read the notes on the back before filling this page) method; or the method of adding the polymer solution to water or warm water to disperse, and then evaporating the solvent with steam, ie steam Devolatilization method; or separation method in which polymer is precipitated after adding a large amount of methanol and other sink agents to the polymer solution; or vacuum drying method for polymer solution; or using an extruder with a deaeration port Direct solvent devolatilization. [Test method] 1. Hue and thermal stability test of polymer: The polymer is pressed into a test piece with a size of 4inX4inX l / 8in (length X width X thickness), and its yellow index is measured by color difference. That is the YI value. After the test piece was placed in an oven at 200 ° C for 30 minutes, the change of hue was observed, that is, the test of thermal stability. In Table 1, ◎ indicates that the hue is slightly yellow, ○ indicates that the hue is light yellow, △ indicates that the hue is dark yellow, and X indicates that the hue is brown. 2. Processing stability test of polymer: 60 grams of polymer was placed in a Brabander tester, and the curve of torque and time was recorded at 150 ° CX 60rpm to obtain the induction time of the colloid. ), The longer the induction time, the better the processing stability of the polymer. [Preparation Example] Preparation of f Living Polymer A 1 Wash a 200 liter reactor with nitrogen, and then add 13 kg of butadiene and 6 g of tetrahydrofuran to 100 kg of a n-hexane solvent. After mixing, add 5.5 grams of n-butyllithium, and then react at 55 ° C for 1 hour, then add 1.5 grams of silicon tetrachloride (SiCl4) to obtain a star-shaped active polymer A. _ 第 16_ The paper size is in accordance with China State Standard (CNS) A4 (210X 297mm) 552269 A7 _ ___B7 V. Description of the invention (β) Preparation of active polymer B] Same as [active polymer A] ] Method, but the n-butyl lithium was changed to 7.5 grams, and without using silicon tetrachloride, linear active polymer B can be obtained. f Preparation of living polymer C] The reactor with 200 liters of nitrogen was also washed. After that, 3.2 kg of styrene monomer, 9.4 kg of butadiene and 110 kg of n-hexane solvent were mixed, and then added. 11.4 grams of tetragas and 6.4 grams of potassium butoxide, then preheated at 70 ° C, and then added 9.7 grams of n-butyllithium to react for 1 hour. A linear living polymer C (butadiene_styrene polymer) was obtained. [Example] The active polymers A, B, and C prepared in the preparation example are post-processed according to the order of addition in Table 1. That is, step (1): In the active polymer solution, add an organic acid stopper, And mix well. Step (2): Add water to completely stop the activity of the active polymer. Step (3): Add antioxidants and mix. The above-mentioned four compounds are subjected to a step of solvent devolatilization through a steam stripping process, and then dried to obtain a conjugated diene polymer. According to the foregoing embodiment, if the Adding an organic acid stopper and a water stopper, and then adding an appropriate amount of antioxidant, and adding in the order of steps (1), (2), (3), you can get good hue, good thermal stability And processing stable polymers. However, if the steps (丨) and (2) are not distinguished, page 17 This paper size applies to Chinese national standards (----- ~-(ii read the precautions on the back before writing this page)

^ 52269 A7 B7 Description of the invention (...) ~~ '^ ^ ---- Do not add organic acids and water, or use too much antioxidant, or do not follow the amount of antioxidant ⑷, ⑻ in step (3) Limited or not in the order of steps (^) '(2), (3), polymers with excellent hue, thermal stability, and processing stability cannot be obtained, so the present invention is indeed novel and advanced. Manufacturing method with industrial value. However, the above are only a few of the preferred embodiments of the present invention. For those skilled in the art, those modifications or changes made according to the spirit of the present invention should be included in the scope of the patent application.阅读 Read the precautions on the back before filling in this page. J Ding 麫 浐 Decision ^. ^-^ ”5Consumer bamboo buckle i / fl i One degree rule paper one CN | ί iί 一 国 一Country

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Claims (1)

552269 VI. Apply for a patent irnr No. 88-3721 Application for a patent application amendment (please read the precautions on the back before filling this page) 1. A conjugated diene polymer A manufacturing method, comprising: a living polymer produced by using a conjugated diene monomer and / or a styrene monomer as a main component and polymerizing an organic lithium as a catalyst. The post-treatment is performed in the following order: (1) 0.01 to 1 part by weight of an organic acid is added to 100 parts by weight of the aforementioned active polymer; (2) 1 part by weight or more is added to 100 parts by weight of the active polymer Water, and the water is added in the pipeline at the outlet of the reaction tank, or in the subsequent intermediate storage tank; (3) 0.02 to 0.5 parts by weight of antioxidant is added to 100 parts by weight of the active polymer, the above antioxidant Comprising: (a) a phenolic antioxidant; and (b) an antioxidant having the following structural formula (I); R2 ............... Structural formula (I) The structural formula (I) printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where Ri and R3 are -CH2 -S-R5 'R5 is an alkyl group having a carbon number of 20 or less, R2 and R4 are a hydrogen group or an alkyl group having a carbon number of 15 or less; (4) will pass through (1), (2), (3) The polymer solution after the step) is subjected to a devolatilization and recovery process to obtain a conjugated diene polymer. According to the method for manufacturing a conjugated diene polymer described in item 1 of the scope of the patent application, wherein (a) the phenolic antioxidant is 0.01 to 0.18 parts by weight, and the paper size is applicable to China National Standard (CNS) A4 specifications (210 $ 297! | 厘 7 552269 4 6 A8 B8 C8 D8 Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to apply for a patent scope (2) and the (b) antioxidant with the structural formula (1) is 〇_〇1 ~ 0.32 According to the method for producing a sulfonium compound described in item 1 of the scope of the patent application, wherein (a) the phenol-based antioxidant is 0.01 to 0.09 parts by weight, and (b) the antioxidant having the structural formula (1) It is 0.001 to 0.21 parts by weight. According to the method for manufacturing a total of diene polymers described in item 丄 of the patent application scope, wherein the water added in step (2) is 2 to 50 parts by weight. According to the application The method for producing a conjugated diene polymer described in item 丨 of the patent scope, wherein the organic acid in step (1) is neodecanoic acid. The conjugated difluorene polymer described in item 1 of the scope of patent application The manufacturing method, wherein the antioxidant of the structural formula (1) is 4, 6-bis (n-octylthiomethyl) -o-cresol. 箆 20 hundred paper size, using China National Standard (CNS) A4 specification (210 > < 297 mm)