JPS63142007A - Production of polymer - Google Patents

Abstract

PURPOSE:To obtain a polymer outstanding in color tone and transparency, highly resistant to yellowing when heated to elevated temperatures, by adding a specific polymerization terminator to a solution made by polymerization between a coujugated diene and vinyl aromatic compound fallowed by addition of an stabilizer and then expelling the solvent. CONSTITUTION:A polymer solution made by polymerization, in a hydrocarbon solvent, of a coujugated diene and/or vinyl aromatic hydrocarbon (e.g., 1,3- butadiene,styrene) using an organolithium compound (e.g., ethyllithium, isoprenyldilithium) as the initiator is incorporated with, as the polymerization terminator (A) 0.05-5 equivalents, based on said lithium compound, of an organic acid (e.g., octanoic acid, lactic acid) (B) 0.005-5pts. by wt. per 100pts. by wt. of the final polymer, of a phenolic compound [e.g., 2,2'-methylenebis (4-methyl-6-t-butylphenol)] followed by addition of an stabilizer to the resultant polymer solution and then expelling the solvent, thus obtaining the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a polymer that has excellent color tone and transparency that does not whiten when immersed in hot water, and is said to prevent yellowing when heated at high temperatures.

(Prior art) A block copolymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon is transparent and can be vulcanized without vulcanization when the vinyl aromatic hydrocarbon content is relatively low. It has the same elasticity as natural rubber or synthetic rubber at room temperature, and the same malleability as thermoplastic resin at high temperatures, so it is widely used in the fields of footwear, Plus Deck modification, asphalt, and adhesives. In addition, when the vinyl aromatic hydrocarbon content is relatively high, thermal ii, which is transparent and has excellent impact resistance, is used.
Because J-plastic resin can be obtained, its usage has increased in recent years, mainly in the field of food packaging containers, and its uses are becoming more diverse.

However, such block copolymers have poor color tone;
The disadvantage is that the molded product has a yellowish tinge and is of W size. Therefore, several attempts have been made to improve this drawback. For example, Japanese Patent Publication No. 54-2679 discloses that after adding water/carbon dioxide/phenolic antioxidant to a hydrocarbon solvent of an active block copolymer, 1. '+0・"200℃)q+
ull noi=m-(processp(!Ll-(i'f,i
a! ' - A method of direct solvent removal is described, and in Japanese Patent Publication No. 7459/1983, a hydrocarbon solution of a block copolymer is mixed with 1111 heat or heated water, and an organic acid is added before stripping the solvent. A method is described that avoids contact with aqueous solutions of the compound. Also, JP-A-58-168
No. 612 describes a method in which boric acid is added to a polymer and then a stabilizer is added to recover the polymer.

(Problems to be Solved by the Invention) However, although the color tone is improved by these methods, the whitening resistance is poor, and the polymers obtained by the above methods are not allowed to stand in a humid atmosphere for a long period of time or are immersed in water. As a result, it becomes cloudy and loses its transparency. Furthermore, extrusion has the problem that the yellowish tinge of the molded product increases due to the thermal history of the injection molding machine.

Under such current circumstances, the present invention has a color tone, warm water immersion 1
As a result of studying a method for producing 1q of polymers with excellent whitening resistance and yellowing resistance when heated at high temperatures, we found that 1. It was discovered that the first objective could be achieved by using a specific amount of , and the present invention was completed.

[Means for solving problems]

That is, the present invention involves polymerizing a conjugated diene and/or a vinyl aromatic hydrocarbon in a hydrocarbon medium using an organic libram compound as an initiator. ! Polymerization is terminated in the substantial absence of water in the polymer solution obtained [For organic lithium compounds in which (i) one or more of the following acids are used as a polymer initiator: (11) Add 0.005 to 5 parts by weight of one or more phenolic compounds to 100 parts by weight of the polymer, and then add a stabilizer to the polymer solution. This is a method for producing a polymer, which is characterized by removing the solvent.

Hereinafter, the present invention will be explained in detail.

In the method of the present invention, a conjugated diene and σ/or vinyl aromatic hydrocarbon are polymerized in a hydrocarbon solvent using an organic libram compound as an initiator to produce a polymer solution. Polymers of conjugated dienes or vinyl aromatic hydrocarbons can be produced by any known method, including anionic polymerization of conjugated dienes or vinyl aromatic hydrocarbons with an organolithium compound in an inert hydrocarbon solvent. It can be manufactured by

Co(Ωdiene and vinyl aromatic fpi, when hydrocarbons are referred to as 7-mers, the composition ratio of conjugated diene and vinyl aromatic hydrocarbon in the polymer 17 is not particularly limited, but is generally 99.9:0. The polymer consisting of a conjugated diene and a vinyl aromatic hydrocarbon is a random copolymer. It may also be a polymer, which can be produced by anionic polymerization with an organolithium compound in an inert Pl hydrocarbon solvent in any known manner.

For example, U.S. Patent No. 3,094,514 shows that one combination of random
As described in No. 19 Kawaguchi (), a mixture of conjugated diene and vinyl aromatic hydrocarbon can be arranged in a small reactor by feeding it at a rate slower than the normal polymerization rate.

Furthermore, as described in U.S. Pat.
They can be combined to produce a random copolymer.

On the other hand, Bu [! As a method for producing ivy copolymer, for example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-179
Publication No. 79, Special Publication No. 46-32415, Special Publication No. 4
Publication No. 9-36957, Japanese Patent Publication No. 48-2423,
Special Publication No. 48-4106, Special Publication No. 56-28925
Examples include the method described in Japanese Patent Publication No. 51-49567. These 1j methods include J, S, B [1] The general formula is (A-B> A-(B-A).

, B-(-A-8),.

[1' (In the above formula, A is a polymer block mainly composed of vinyl aromatic/A hydrocarbon, and B is a polymer block mainly composed of conjugated divinyl. The boundary between A block and 8 block does not necessarily need to be clearly distinguished. Also, "1 is an integer greater than or equal to 1." Or the general formula, [(B-A)←-X, [(A-B). m
+1 [(B-A)-B←-X, [(A-B+-6AsuXn
m + 1 (In the above formula, A and B are the same as above, and X represents a residue of an initiator such as a polyfunctional organolithium compound. m and "1 is an integer of 1 or more" -) Obtained as a block copolymer.

In the above formula, the polymer block mainly composed of vinyl aromatic hydrocarbons refers to a copolymer block of vinyl aromatic hydrocarbons and co-19 diene containing 50Φ% or more of vinyl aromatic hydrocarbons, and/or It refers to a vinyl aromatic hydrocarbon homopolymer block, and a polymer block mainly composed of conjugated diene refers to a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon containing a conjugated diene in an amount exceeding 50% by weight. / or indicates a conjugated diene homopolymer block.

The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered. In addition, the copolymer portion coexists with a plurality of portions in which the vinyl aromatic hydrocarbon is uniformly divided and/or in a plurality of portions in which the vinyl aromatic hydrocarbon is divided in a 7-part shape.

i5 like this? The resulting block copolymer has a vinyl aromatic hydrocarbon content of 60% or more, preferably 5% or more.
If the content of vinyl aromatic hydrocarbon is less than 5% by weight, it exhibits properties as a thermoplastic elastic body, and if the content of vinyl aromatic hydrocarbon exceeds 60% by weight, preferably 65% by weight or more, it exhibits properties as a thermoplastic resin. .

Vinyl aromatic hydrocarbons used in the method of the present invention include styrene, 0-methylstyrene, p-methylstyrene, p-methylstyrene,
Examples include -tert-bublesubrene, 1,3-dimethylsubrene, α-methylstyrene, vinylpphthalene, vinylan-1-rahin, and a particularly common one is styrene.

These may be used not only alone, but also as a mixture of two or more.

The conjugated diene used in the present invention is a diolefin having a pair of divalent single bonds, such as 1,3-butadiene,
2-Methyl-1,3-butadiene (isoprene), 2.
Examples include 3-dimethyl-1,3-1tadiene, 1,3-pentadiene, 1,3-hexylidiene, and particularly common ones include 1,3-butadiene and isoprene.

These may be used not only alone, but also as a mixture of two or more.

Hydrocarbon solvents include butane, pentane,
Aliphatic hydrocarbons such as isopentane, heptane, octane, and isooctane, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexylline, methylcyclopentane, and ethylcyclohexylline, or benzene, toluene, nibblepenpine, xylene, etc. yJ aromatic hydrocarbons and the like can be used. These may be used not only alone, but also as a mixture of two or more. Organolithium compounds are organic heptanolybium compounds in which one or more lithium atoms are bonded in the molecule, such as ethyllithium, ``)-probillibram, isopropylcuticum, ``)-butyllithium, 5ec-butyl. Examples include lithium, ter't-bugullithium, hexyrimethylene dilithium, butadinyl dilithium, isoprenyl dilibuum, etc. These may be used not only alone, but also as a mixture of two or more.

In the present invention, adjustment of polymerization rate, Miku L-IM8 (cis, trans, vinyl ratio) of the polymerized conjugated diene part
, the reaction of conjugated dienes with vinyl aromatic hydrocarbons [(
In order to adjust the ratio, polar compounds or randomizing agents can be used. (As a compound or a randomizing agent, -C is di[-pures, amines, thia-delta-1, phosphor)imide, al-4-rubenpine sulfonate, potassium salt or notrium alkoxide. Examples of suitable nephers are dimethyl ether, diethylene ether, sulfonyl ether and tetrahydrofuran, diethylene glycol dimebole ether, di(blen glycol) dibutyl ether, amine. Examples of phosphines and phosphoramides include tertiary amines such as trimethylamine, triniblamine, dimethyldiamine, and cyclic tertiary amines.Phosphine and phosphoramide include triphenylphosphine and Randomizing agents include potassium alkylbenvinsulfonate or thorium, potassium or notrium butoxide.

In the process of the present invention, the polymerization humidity during the production of the polymer is generally -40°C to 150°C, preferably 40°C.
C to 120'C. The time required for polymerization depends on the regulations, but it is usually within 48FF,
Particularly preferably, it is between 0 and 10 ff.%. Further, it is desirable to replace the atmosphere of the polymerization system with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited, as long as it is within a range of E which is sufficient to maintain the polymer and the solvent in a liquid phase within the above polymerization temperature range. In general, care must be taken to prevent impurities such as water, oxygen, carbon dioxide gas, etc. that would deactivate the catalyst and the σ-living polymer from entering the polymerization system.

The lff1 average molecular weight of the polymer thus obtained (q) is generally 5,000 to 5.000.000, preferably 10.000 to 1,000,000. The ω of hydrogen is generally 50 parts by weight to 2000 parts by weight per 100 parts by weight of the polymer.It should be noted that due to the nature of the polymer, the polymer is insoluble in hydrocarbon solvents!'
J. There are cases where the solution is obtained in a cloudy state =b, but in the present invention, these will also be referred to as polymer solutions.

The present invention involves adding (i) one or more organic acids (hereinafter referred to as component m), (ii) a phenolic compound to the polymer solution obtained above in the substantial absence of water. One or more types (hereinafter referred to as component (ii)) are used as heavy terminators.

The organic acid of component (i) here refers to an organic compound having acidity in a broad sense, and includes, for example, a compound having a functional group such as carboxylic acid, sulfonic acid, phenol sulfinate, enol, imide, or oxime, but is preferred. is an organic compound containing a carboxyl group, and the following are preferred.

(1) Fatty acid having 8 or more carbon atoms (2) Rosin acid (3) Oxycarboxylic acid (4) Aromatic carboxylic acid Specific examples of fatty acids preferably used in the present invention include A-cutylic acid, capric acid, lauric acid, Examples include myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolic acid, ricinoleic acid, belinic acid, tallow fatty acid, or mixtures thereof. Rosin acid may also be a hydrogenated product thereof.

Examples of A21 dicarboxylic acids include compounds having at least one human 1'xy group and at least one carboxyl group in the molecule, such as glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, A21 dicarboxylic acid, Examples of aromatic carboxylic acids include 2-hydroxystearic acid, lilithylic acid, o-''A2#cinnamic acid, and mixtures thereof.Aromatic carboxylic acids include benzoic acid, chlorobenzoic acid, aminobenzoic acid, and cinnamic acid. , phenyl[M, or a mixture thereof.2 The heptano-nor compound of component (ii) is a compound having at least one phenol f hydroxyl group in the molecule, such as butylated hydroxy l-/LzI. Bubbled anisole, 4-hydroxymethyl-2゜6-di-t-butylphenol, rl-octadecyl-β-(4'-
Hydroxy-31,5'-di-t-butylphenyl)propione-1~, triethylene glycol bis3
(2-1-Butyldidroxy-5-methylphenyl)propionate, 2-n-71cutylucci, t-4,
6-di (4''-human scolding-3' p 5'-di-t-
butylphenoxy)-1,3,5-triazine, 2+
4+ 5-trihydroxybubrophenone, 2-
(2'-Human[Ni1C-5'-methyl)1-nyl)benzotriazole, Propyl gallate, A-cubulgarate, Dodecyl gallate, 2-(2'-Human [
1x-3'-1-Abreu5'-Mebruch J.

Nyl)-5-chlorobenzotriazole, 2-(2'
-human[-1xy-3-5'-di[-butylphenyl)-5-chloro[1benzotriazole,tetrakis[methylene-3-(3'-5'-di-t-butyl-4'-hydroxy phenyl)p[1bionate]methane, 1~
loferol, 1,3゜5-tris(4-1-ablu 3-human axy-2,6-sisothylbenzyl)isocyanuric acid, methyl-P-hydro:V dibenzoate,
2,2'-methylenebis(4-methyl6-1-butylphenol), 2,2'-methylenebis(4-ethyl6
-1-bubulphenol), 2,2'-divide [1:
Vcy3,3'-dicyclohexyl-5゜5'-dimethyldifurylmethane, dosu(3゜3'-bis(4')
-Human[1x-3'-1-butylphenyl)butylphenyl]gly]-Luesdel, 4,4'-bubridenbis-(6-t-butyl-m-cresol), Tris(2-methyl-4- hydroxy-5j-butylph1-nylbutane), 1,3,5-trimethyl-2,4,6-
1 helis (3,5-di-t-butyl-4-hydroxybenpine, to p-t-butylphenylpurisiso-1,
2.4-di-t-butyl phenyl-3-butyl-4-hydro: t-dibenzoate, 2-butyl-6-(3-t-butyl-5-methyl-2-hydro[ dibenzyl)-4-methylphenyl acrylate-1,
2,4. -bis-(``]ocbulbusif)-6-(4-
Human [1x-3,5-di-butylanilino)-1
, 3,5-triazine, etc., but phenolic stabilizers having two or more hindered phenols in the molecule are preferred in terms of low volatility and prevention of yellowing during high temperature heating.

A specific example is 2,2'-methylenebis(4-tablue6)
-t-bubluf 1-nor), 2,2-methylenebis(4-nibble-6-1-butylphenol), 4.4
'-Bubridenbis (6-1-butyl m-cresol), 4.4'-buobis (6-L-ablu m-cresol), 1.1.3-1 helis (2-methyl-4-
Human [1:1C5j-butylphenyl)butane,
1,3゜5-trimethyl-2,4,6-tris(3,
Examples include 5-di-t-ablu (4-hydroxybenzyl)benpine, 2,2'-dihydroxy-3,3'-dicyclohelicyl-5,5'-dimethyl-diphenylmethane, and the like.

The amount of component (i) added is -(0,05 to 5 equivalents, preferably 0.
．． 2-2 g equivalent, more preferably 0.3-01 g equivalent FJ! are blended substantially in the absence of water.

If the blend of organic acids exceeds a certain level, the effect of improving various color tones, which is the objective of the present invention, will be insignificant, and conversely, if the blend is more than necessary, the whitening property of 6.1 in hot water immersion 11) will worsen. This is not preferable because it lowers the thermal stability of the polymer and may also cause a bad odor during addition.

The amount of component (jl) added is o, oo 5-5 parts by weight, light part or 0.01-3 (i2
The amount is preferably 0.03 to 1 part by weight.

0.005 x=part H1>', (7) Addition amount - C'
(,1?J!l The yellowing prevention effect of 11.1 is insufficient, and the improvement effect of 1. cannot be achieved even if the 5-fold hanging part is exceeded.

Component m and component (ii) above may be added directly to the polymer solution (b) or as a hydrocarbon solution;
In the present invention, component (i) and component (ii) are terminators, and they are added to the polymer solution in the absence of water.
needs to be done. When component (i) and component (ii) are added in the presence of water F, whitening resistance of 7HA water immersion [1,1
This is not preferable because it detracts from 1.

In the present invention, the addition to liquid (polymer) d in the absence of water means that component (i) and component (ii) are dissolved or dispersed in a large amount of water. Specifically, it means not to perform an operation of adding at least 10 equivalents, preferably 5 equivalents, to the active living end in the polymer solution.
This means that the amount of water is added in a state where the presence of water is less than an equivalent amount, more preferably less than 1 equivalent amount. In addition, component (i)
Alternatively, when component (ii) coexists with water in the form of water, etc., the state of addition of these components is substantially the absence of water.
It is assumed that the

As a stabilizer, any of the conventionally used public Xl+ stabilizers may be used, including phenol-based, phosphate-based, organic small-snort (1~-based, amine-based, and Various known oxidation inhibitors are used, such as the stabilizer, which is generally used in an amount of o, ooi to 1, based on 0 monomer parts of the polymer.
(Used within the range of IQ quantity.

Mixing and contacting of the R solution (polymer) with the component (i) and component (ii) stopper agent is carried out using a conventional stirring tank, line mill, or the like. Also, the temperature range is 0°C to 120"
C1 Preferably, warm melon is used at 50° C. to 100° C. 1, and 11.1 minutes is 11 minutes within several minutes to several 11.1 minutes. The next step in the present invention involves the ingredients (
This is a step of removing the solvent from the copolymer solution to which the terminator and stabilizer of i) and component (ii) have been added.

The solvent may be removed from the polymer solution by any known method, such as heating the solution to evaporate the solvent, dispersing the solution in water or hot water, and blowing steam to remove the solvent. Evaporation method (Steam I ~ Ripping d1
), a method in which a large amount of precipitant such as methanol is added to prevent the polymer from precipitating and the solvent is separated from the solvent by vacuum drying; after a part of the solvent is evaporated in a flash tower, etc. A method such as removing the solvent using a type extruder can be adopted.

Depending on the purpose, the additives described in Section 2 may be added to the polymer obtained by method d1 of the present invention.

For example, softeners, plasticizers, antistatic agents, h'
additives, ultraviolet absorbers, flame retardants, pigments, fillers, stones, carbon black and other reinforcing agents, other thermal plastics, etc. can be used as an additive.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.

Incidentally, the 1" 1 tsuku copolymer used in the examples was produced as follows. The suspension ratio of the polymer to the solvent of the obtained copolymer solution was 1:4-( .

[Block copolymer (8)]

1,33-Butacynin 1 in a nitrogen gas atmosphere
Add 0.11 part of [l-butyl lithium to the Kirin solution containing 5 parts by weight and 20 parts of styrene, and after combining 1F with 70'C-(-2tl='), c Rani 1, ', 3-1 Tajikun 45 single hanging part and styrene 20
[1-Hekirin solution containing 70' C-C
- We merged for 215 minutes. 1'', 7 was a block copolymer having a [3-A-B-A structure] with a styrene content of 40% by weight.

[Block copolymer (8)] In a nitrogen gas atmosphere, 0.1% of 1-butyllithium was added to a Schiff[1-hexylline solution containing 15 parts by weight of styrene.
After adding 1 part by weight and combining at 70°C for 1.1 months, 1.
A cyclohekirin solution containing 70 parts B of 3-butadiene was added and polymerized for 2115 times at 7()°C. Thereafter, Kirin solution was added to Schiff [21 containing styrene 15 (i22) and -C70"C-(m"] and polymerized for 1 hour. -A block copolymer.

(Block copolymer (C)) In nitrogen gas atmosphere F, styrene 30 city ω part and jl
To a cyclobequinone solution containing 0.3 parts by weight of hedihydrofuran, 0.08 parts by weight of 1-butyllithium was added,
After combining the vehicles at 70'C for 1 hour, a schiff containing 20 parts by weight of 1,3-butadiene and 50 parts by weight of styrene was added
4 phosphorus) solution a was added and polymerized at 70°C for 20.1 hours.

1j′l polymer G; soot content 80%
A-[3-A 4M-built bu[-1] car combination (there was one).

[Polymer (D)] In a nitrogen atmosphere, 1,3-butadiene 1
() Adding 07 parts of 1-butyl lithium to a rl-4 phosphorus solution containing 20 parts of heavy Lv and 20 parts of styrene,
After polymerization at 70°C for 211 minutes, a solution of 1,3-butadiene containing 15,000 parts by weight and 50 parts by weight of styrene and 0.02 parts by weight of ``]-butylithium were added. 2 fl, 'j f2 former E were combined at 70°C. The obtained polymer contained styrene-containing ff47Q car♀% [3-
It is a mixture consisting of the A = B-A structure Bu[] ivy coconjugate and the B-A structure Bu[1 (F) co-association, and only: (:
)2. r: -76FL (1 The combined solution was in the form of a suspension.

[Block copolymer ([)]

In a nitrogen gas atmosphere, 1,3-butane I [80
Add 0.08 parts by weight of 1-butyllithium to a solution containing 20 parts by weight of styrene and 20 parts by weight of styrene.
Polymerization was carried out at 0°C for 20.1 hours. 1) The polymer containing soubrene contains >200 6% 13-A i+'+1
There was a J['lltsuku co-fusion of construction.

Examples 1 to 4 and Comparative Examples 1 to 5 Component (i) and component (1) were added to the polymer solution of the block comonomer (C) produced above according to the blending method shown in Table 1.
1) was added. Then as a stabilizer 4-tablue2.
After adding 0.5 weight part of each of 6-di-tart-butylphenol and 1-helisnonyl phenyl phosphite to 0 weight part of polymer 1(), the solvent was removed by heating.

The obtained pellets of each polymer were press-molded at 180°C to create sheets 1 to 2 mm thick, 3 cm long and 4 cm wide.
cm Test 7-t color tone, 1li=l whitening ↑1 when immersed in hot water, and color stability of press 11t, 'l. The results are shown in Table 1.

Margin Umbrella 1 Indicates the blending amount for 100 ♀ parts of double coalescing 1゜*
2: To1 mains (!!, lT, N0-V6 manufactured by Co., Ltd.
BulA match? I measured the b (iQ) of the J7 sense measuring device and checked the color tone.

b value is less than 5 ◎ b (direction is 5 to 100 b value or more than 10) The haze of each test piece was measured in accordance with Asnt D-1003, and the difference between the test pieces of each polymer was measured by adding only the stabilizer and removing the solvent, and then immersed in hot water. The whitening resistance of 1
(1 or bad.

Difference in rotation is +5 (less than +5) 1 to ◎ Difference is +5 to -15 0 Difference exceeds -115 × Book 4: 30 m1mφ extrusion
~ was extruded and the color tone change of the pellet was measured.The color tone after the change was measured. The values are expressed in the same ratio as *2-.

Comparative Example 6 In Example 1, benzoic acid and 2,2'-methylenebis(
4-methyl-61-butylphenol) was added to 0.0% water.
2 and 1.0 parts by weight (8.9 and 44.4 parts for Li)
equivalent amount). All test pieces subjected to 45f had extremely poor whitening properties (evaluation rank: X).

Examples 5 to 12 Each test piece was prepared in the same manner as in Example 1, except that the polymer solution and compounding method shown in Table 2 were followed. The color tone, warm water immersion mouth, whitening resistance of 1, and color tone stability during extrusion of the obtained test piece were measured.

The results are shown in Table 2.

Below is the margin Example 13 In a nitrogen gas atmosphere, 1,3-butadiene 75 car parts, styrene 25 car parts, and
Added 0.0 part by weight of 1-butyl lithium and 0.4 part by weight of tetoshisothylbrendiamine, and heated at 50°C-C6[
Polymerization occurred for 1.1 minutes. Benzoic acid 0,
85 equivalents (relative to Li), 2,2'-methylenebis(
After adding 0.04 parts by weight of 4-methyl 6-t-bublphenol) and adding 1,000 R 1 part of 4-tabl 2,6-di-tert-bublphenol, the polymer solution was heated to about 120° C. and the solvent was removed. The polymer obtained in this way was (!2 tone, washing 1 water immersion 11, 1
It was a polymer with good white resistance.

Example 14 In a nitrogen gas atmosphere F, 0.05 parts by weight of ``)-butylurium was added to ``1-he4 phosphorus'' containing Jfi part in 1,3-butadiene 100, and polymerized for 70'C-(-4 hours. .

Add 0.85 equivalents of benzoic acid (L-i
), 2,2'-methylenebis(4-methyl6-
After adding 0.04 parts by weight of tert-butylphenol (tert-butylphenol) and then adding 1 part by weight of 4-methyl-2,6-tert-butylphenol, the solvent was removed by heating. As a result, polybutadiene with good color tone was obtained.

〔Effect of the invention〕

The polymer obtained by the method of the present invention is transparent and has excellent color tone, so it can be used for a wide variety of moldings such as sheets, films, injection molded products of various shapes, blow molded products, pressure molded products, vacuum molded products, etc. It can be used as a product. In particular, the polymer obtained by the method of the present invention has excellent whitening resistance when immersed in hot water of 0.1, so it can be used in a humid atmosphere or in fields where it comes into contact with water, such as food containers and food packaging materials. It can be effectively used for toys, Kuhara supplies, etc. Furthermore, the method of the present invention can be applied to block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, as well as conjugated diene polymers, vinyl aromatic hydrocarbon polymers, and random copolymers of conjugated dienes and vinyl aromatic hydrocarbons. It can also be used in polymers.

Patent Applicant: Asahi Kasei Industries Co., Ltd. Agent, Patent Attorney: Kusari Nozaki, Masaaki Nozaki) (Volunteer) Revised on March 13, 1985, Attorney Tadashi [U Akio 1, Indication of Case 1986 Patent Application No. 288722 2, name of the invention Process for producing a polymer 3, person making the amendment Relationship to the case: Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka (003) Representative of Asahi Kasei Industries, Ltd. Makoto Koshin 4, Agent Postal code 104 2-15-15 Tsukiji, Chuo-ku, Tokyo Room 6, 802, Rentral Higashi Ginza, Contents of amendment (1) "Buthirikand" on page 15, line 13 of the specification
Correct it with "Butiric Ashitoko".

(2) The amount of 2,2'-meblenbis(4-methyl 6-t-butylphenol) in Comparative Example 2 in Table 1, page 24, [0,005J] is corrected to [0,001J].

(3) The amount of 2,2'-methylenebis(4-methyl 6-t-butylphenol) in Comparative Example 5 in Table 1 on page 24 of the same page is corrected to 0.02J.

(4) The amount of 1.3゜5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benbin in Comparative Example 5 in Table 1 of Table 24 of the same [,03J
is corrected as ro, 03j.

(5) “Oshide” on page 25, line 19 of the same page [Oshide J
says NerliE.

(6) “-” between “6” and rtJ on page 26, line 4
Insert.

Claims (1)

[Claims] A polymer solution obtained by polymerizing a conjugated diene and/or a vinyl aromatic hydrocarbon using an organolithium compound as an initiator in a hydrocarbon solvent is subjected to polymerization termination in the substantial absence of water. (i) 0.05 to 5 equivalents based on the organolithium compound used as a polymer initiator with one or more organic acids; (ii) one or more phenolic compounds as a polymer initiator; A method for producing a polymer, which comprises adding 0.005 to 5 parts by weight per 100 parts by weight of the polymer, followed by adding a stabilizer to the polymer solution and removing the solvent.