TWI300069B - - Google Patents

Description

1300069 V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) [Technical Field] The present invention relates to a kind of mound-polymer, in particular, to a light-diluted/vinyl aromatic block, and a low temperature resistant /, has a low softening point (Vicat S0ften) Lng film or sheet extrusion into a penetrating strength rigidity and other physical balance, suitable for [previous technology] 9 block copolymer.

A total of a rare/B 4 A thermoplastic polymerized earth-based 9-member I-segment copolymer is widely used, so it is often used for its transparency and impact strength, 1 or 'for food, K: Two: T, play, and other articles forming the method of making such a copolymer or /, his product packaging or container material.

4,584,346, US 5 Many patents mention, for example, US Patent No. 6,420,48 6 and the like. 419, US 5'2 9 0'875, US in the package of the material or Rong ^ crying block copolymer often in the thin $ on the 'light light rare / vinyl aromatic field, there may be a low slab Extrusion molding. Apply impact strength here. In addition, the 'dish: the case of sputum' is therefore required to have a low temperature rigidity. In addition to the above-mentioned low, and the application of the sheet, it is necessary to have sufficient film or sheet extrusion::: the balance of physical strength and rigidity is reduced, and the amount is reduced. Conjugated diene/, usually requires a gel (ge:l) content to be a conjugated diene block, which is produced by a polycogel in an amidine-based aromatic block copolymer, and thus is long, k The reason for the difference is that it is easy to reduce the temperature during the processing to avoid the amount of gelation of the condensed product. Generally, it will be tied and lower the temperature of the extrusion: soil. However, in the field of high softening point copolymer, the copolymer is subjected to a large shear force, but instead

Page 5 1300069 V. INSTRUCTIONS (2) Gelation occurs, and the expected effect of reducing the gel content cannot be achieved. Therefore, there is a need in the industry to produce a conjugated diene-based/vinyl aromatic block copolymer having a low softening point and a good balance of physical properties such as good clarity, low-temperature impact strength and rigidity. Generally, a conjugated diene/vinyl aromatic block copolymer having a large content of a polyvinyl aromatic block generally has a high rigidity, but also has a high softening point, and is various according to various The polymerization formula of some block copolymers also has poor low-temperature impact strength. On the other hand, the introduction of the tapered block into the common dibasic/vinyl aromatic block copolymer can lower the softening point, but the relative rigidity is also greatly reduced. Therefore, how to make the conjugated diene/vinyl aromatic block copolymer have a low softening point and good transparency, and a good balance of physical properties such as rigidity and low-temperature impact strength can be said to be a conjugated diene. The development of a system/vinyl aromatic block copolymer is in urgent need of improvement. SUMMARY OF THE INVENTION The main object of the present invention is to provide a common vehicle bismuth system/B with a ratio of the content of the vinyl aromatic polymerized unit to the content of the total hexadiene polymer unit of 65 to 95% by weight/35 to 5% by weight. Dilute-based aromatics: segment copolymers, especially one type of block copolymers which have a low softening point and good low-temperature impact strength and rigidity, and are suitable for extrusion molding of film or sheet. The conjugated diene/vinyl aromatic block copolymer of the present invention is obtained by coupling a coupling agent mainly comprising the following three kinds of living block polymers:

Si 4 - S2 -S3 -B2 -S4 - Y ’

I

Page 6 1300069 V. INSTRUCTIONS (3) s2 ~s3 -b2 -S4 - Y ? s3 - b2 - s4 - Y ; where -Y is an anionically active end, representing -B3 or 咄3-35, Si ~S5 represents a polyvinyl aromatic block, Bi~B3 represents a polyconjugated diene block, and a polyconjugated diene block block constitutes a whole vinyl aromatic polymer unit and a conjugated second of the block copolymer 1% by weight to 5% by weight based on the total amount of the olefinic polymerization unit. [Embodiment] The ratio of the content of the vinyl aromatic polymerized unit of the present invention to the content of the conjugated diene-based polymer unit is 65 to 95% by weight/35 to 5% by weight of the conjugated diene/vinyl aromatic block copolymer. The product is obtained by coupling a coupling agent mainly comprising the following three kinds of living block polymers: S "BrWBfSrY, - s3 - B2 - S4 - Y, s3 - - s4 - Y; wherein -Y is An anionically active terminal, representing -B3 or -B3 - S5, Si~S5 represents a polyvinyl aromatic block, Bi~B3 represents a polyconjugated diene block, and a polyconjugated diene block It accounts for 1% by weight to 5% by weight of the total of the vinyl aromatic polymerized unit and the conjugated diene polymerized unit of the block copolymer. The above anionic activity means that it has an anionic polymerization activity when -Y is -B3 When the poly-conjugated diene block B3 has an anionic polymerization activity, when -Y is -b3 -s5, s5 has an anionic polymerization activity. In the present invention, the content of the vinyl aromatic polymerized unit and the conjugated diene system

Page 7 1300069 V. DESCRIPTION OF THE INVENTION (4) The ratio of the content of the polymerization unit is 65 to 65 to 90% by weight/35 to b. b is reset to P35 to 5% by weight, preferably .% by weight. The above vinyl aroma is preferably 70 to 80% by weight/3 Å. The element means that the copolymer has been obtained from the octagonal, / σ early enthalpy and conjugated diene polymerizable monomer. When the rigidity of the ethylene-based octadecyl aromatic monomer and the common diene-based copolymer is poor, and the content of (7) two early 70 is less than 65% by weight, if the embedding is more than 95% by weight, the block is Φ intensity difference, transparency is also not good. The block mound of the present invention and Ba Yong have poor low-temperature impact strength. The molecule, the pair of blocks == is a branch structure. +Ice, Shi and ', the water of the valley, the strength of the valley, the appearance of a good one group of Qiuqiu II said the block copolymer of the invention, preferably does not contain vinyl aryl, '..., 6, For tapered blocks, this has a good effect on the balance of physical properties such as low-strength impact resistance and rigidity. Specific examples of vinyl aromatic monomers include stupid ethylene and o-methyl stupid. O-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 1,3 -dibutyl styrene (1, 3-di-butyl styrene), α-methylstyrene-methyl styrene, ethyl methacrylate, 2,4-dimercaptophenylene, α-methyl-p-methylstyrene, desert - phenethyl hydrazine, in which styrene is preferred. Specific examples of co-dodiene monomers are: 1,3 -butane, 2-methyl-1,3-butadiene, 2,3-bis-indenyl-1,3 -butadiene And 1, 3-pentadiene, 1,3-hexadiene, etc., wherein -butylene or 2-methyl-1,3-butadiene is preferred.

Page 8 1300069 V. INSTRUCTIONS (5) -- The above vinyl aromatic monomer and the common dibasic monomer may be used singly or in combination. In the block copolymer of the present invention, the polyconjugated diene block h is preferably 1% by weight to 5% by weight based on the total amount of the total of the vinyl aromatic polymer unit and the conjugated diene polymer unit. 5重量%〜4. 5重量%, more preferably 2% by weight to 4% by weight. When the content of the polypyroxene block h is less than 1% by weight, the softening point of the copolymer is too high; and when the content of the polyconjugated diene block & is more than 5% by weight, the low-temperature impact of the copolymer Poor strength. In other words, in the block copolymer of the present invention, when the content of the polyconjugated diene-based block ruthenium is within the above-mentioned range, the invention can achieve high transparency and good low-temperature impact resistance of the block copolymer. Strength and rigidity (stretching strength, bending strength) physical balance, and low softening point. In the block copolymer of the present invention, the maximum amount of the polyvinyl aromatic block is preferably from 3 to 65% by weight, more preferably from 33 to 60, based on the total of the vinyl aromatic polymerized units in the block copolymer. The weight % is preferably 35 to 55 wt%. When the content of the maximum polyvinyl-based aromatic block is within the above range, the block copolymer can have a low softening point, and the low-temperature impact strength and the rigidity (stretching strength, bending strength) can be balanced. In the block copolymer of the present invention, the largest polyvinyl aromatic block of |丨 is preferably a vinyl aromatic block S!. In the polymerization of the present invention, a raw material such as a vinyl aromatic monomer, a conjugated diene monomer, a starter, and a solvent is sequentially added to the reaction vessel for reaction. After the monomer reaction is completed at each stage, the next stage of the reaction is carried out. Whether the reaction is complete or not can be judged according to the reaction temperature, and when the reaction temperature stops rising, the reaction is completed. Single system of the invention in the initiator

Page 9 Ϊ300069

V. INSTRUCTIONS (6) Aggregation in the presence of the condition, the sacred sacred area ^ on the hair - smuggling A R can be: Ci~c20 alkyl, 璟桉2: soil 'preferably alkyl' and M Represents alkali metal, such as hydrazine, sodium, etc., Γ::: ΐ 起始 起始 之 依 依 依 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 Among the organic metal compounds, organic crystallization. n-propyl lithium, n-butyl lithium, _ town-but I / Λ 一 Step 1 J storm, Le Dibutyl, Zheng / 3⁄4 soil, Li, n-hexyl Lithium, alum-based lithium (ben llthlu (10) yHlthl (10)), trimethylene di-periphery, tetramethylene methyl 1 di-, di-di-bi- and di-isoprene double-chain, etc. In addition, the above-mentioned initiators may be used singly or in combination of plural kinds. Specific examples of the solvent used in the present invention are: pentane, hexane, cyclohexane, etc., wherein cyclohexane is preferred. The above solvent may be used in a plurality of kinds, such as hydrazine, seed or mixture. 1 - the polymerization rate of the block copolymer of the present invention during polymerization, 1, 2 - ethyl yttrium containing 'polarization The polar compound may be selected from the group consisting of guanidine, am i ne, sulfur, phosphine (ph〇sph i ne ) or phosphinium depleted amine, potassium or sodium of the alkyl oxide Salts. Specific examples suitable for the present invention are: (a) ethers: dimethyl ether, diethyl ether, dibutyl ether, dihydrofuran, tetrahydrofuran, tetrahydrofuran Diethyleneglycol dimethyl ester, B-'θ-dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl, a scale, and the like.

Page 10 1300069 V. INSTRUCTIONS (7) (b) Amines: amines, mercaptoamines, ethylamine propylamine butylamine, tetramethyl-ethylenediamine, diethylaniline, D-pyridine , a tertiary amine, and the like. (C) Phosphine or phosphoniumamines: tris-phenylphosphine, hexamethylphosphoniumamine, and the like. (d) Potassium or sodium salt of a base oxide: potassium butoxide 〇 The amount of the above polar compound added is relative to 100 parts by weight of the total I erdiene and vinyl aromatic monomer The amount is usually about 0. 0 0 5 to 1 part by weight, preferably 0.03 to 1 part by weight, more preferably 0.06 to 0.6 part by weight. Further, the polar compounds may be used singly or in combination of plural kinds, and among them, tetrahydrofuran is preferred. In the method for producing a block copolymer of the present invention, the polymerization temperature is usually from -40 ° C to 150 ° C, preferably from 40 to 120 ° C, and the polymerization time and polymerization pressure vary depending on the polymerization conditions, wherein the polymerization time is usually It is within 20 hours, preferably 0. 1~1 0 small time, the best is 0. 5~5 hours 'In the polymerization, it is necessary to prevent the incorporation of impurities, such as water, acid, carbon dioxide and the like. In the present invention, when the polymerization reaction is completed to form a living block polymer, a coupling agent is added to the reaction tank. Here, the living block polymer means that the living block polymer has an anionic polymerization activity. 0 〜5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1重量份。 More preferably 0. 0 6~0. 6 parts by weight. The coupling agent used in the present invention contains two or more functional groups, for example, a vinyl aromatic compound containing two vinyl groups or a plurality of vinyl groups, and having two epoxy groups or a plurality of epoxy groups.

Page 11 1300069 Containing two isocyanides, containing two subunits or a plurality of acid compounds, or a plurality of vinegar tin, dioxygenated soybean oil can be adjusted as needed. In other words, the number is not solid z3-x

X, Z9-X or a plurality of imine groups of imine groups, an imine group-like compound, a halogenated compound containing two ketone halogens or a plurality of imines, and specific examples are tetraoxin linseed oil, Epoxy soybeans 5. Description of the invention (8) Epoxy compounds, cyanate ester compound compounds, ketones containing two acids or a plurality of ketone groups, an ester group containing gasified hydrazine, four gasified oils, etc. Among them, the above-mentioned coupling agent active block polymer > the active block polymer may be a Z-acid acetamide group or a base aldehyde containing two ester tins and rings. The entire addition amount is used to couple all or part of each, and the coupler molecules can be coupled to each other, that is, the mixture obtained after coupling, wherein z represents a mixture of n-functional groups. The coupler residue, η represents an integer of 2 or more, and Ζ represents the active block polymer before coupling, which contains at least the following three linear block polymers: 51 - Β! -S2 -S3 - B2 -S4 - Υ ' 52 - S3 - B2 - S4 - Y, 53 - b2 - S4 - Y ; . wherein -Y is an anionically active terminal, representing -B3 or -B3 - S5, and Si~S5 is a polyvinyl aromatic Block, Bi~B3 represents a polyconjugated diene block, and the polyconjugated diene block 匕 accounts for the total amount of the vinyl aromatic polymer unit and the conjugated diene polymer unit in the block copolymer. 1% by weight to 5% by weight. The order of feeding of the initiator, monomer, coupling agent and the like in the polymerization of the present invention is exemplified below.

Page 12 1300069 V. INSTRUCTIONS EXAMPLES 1 Step 1 Step 2 Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 Example 2 Step 1 (9) Starter Agent Add aromatic to the reaction monomer. When the reaction and the ethylene vinyl group are reacted and the ethylene ethylene group is reacted as a monomer. When the reactive monomer is a reactive monomer. When the reaction and ethylene, the end of the monomer, the end, the end of the aromatic aromatic end, the base aromatic aromatic knot, the base aromatic into the vinyl aromatic mouth, and then the mouth temperature is no longer in the body simultaneously Feed, or start the fragrance monomer, or vinyl into the initiator. When liter is added, when the bismuth is added, the initiator is added at the same time as the initiator, and then the liter is added. At the same time, the initiator is added first, and then the temperature is no longer the monomer. , or monomer. The temperature is no longer a monomer, or a monomer. When the temperature is no longer rising, the addition of the total of the Ershi series ends. When the temperature is no longer rising, the addition of the vinyl aromatic end is completed, and when the temperature is no longer rising, the addition of the divalent diene system is completed, and when the temperature is no longer rising, the coupling agent is added. Step 2 •• The initiator and the vinyl aromatic single agent are added first, then the vinyl aromatic aromatic monomer is added first, and then: when the reaction is finished, the temperature is no longer in the upper body at the same time, or the starting fragrance Monomer, or vinyl, into the initiator. When it is rising, it is added to the common diene system.

Page 13 1300069 V. INSTRUCTIONS (10) Monomer Step 3 Step 4 Step 5 Step 6 Step 7 Step 8 Step 9 When the reaction is over and the temperature is no longer rising, the initiator and vinyl aromatic monomer are added at the same time. Or the initiator is added first, followed by the addition of a vinyl aromatic monomer. When the reaction is complete and the temperature is no longer rising, the initiator and the vinyl aromatic monomer are added simultaneously, or the initiator is added first, followed by the addition of the vinyl aromatic monomer. When the reaction is over, the temperature is no longer rising when the monomer. When the reaction ends, the family monomer. When the reaction is over, the monomer. When the reaction ends, the family monomer. When the temperature at the end of the reaction is no longer rising, the temperature is no longer rising. A total of diterpenoids is added. Ethyl aryl is added. The conjugated diene is added. When the temperature is no longer rising, a vinyl aromatic is added to the coupling agent. When the coupling coupling degree is no longer increased, the block copolymer of the present invention may be further added with a terminating agent for terminating the activity of the polymer chain after the completion of the polymerization reaction. The amount of the terminating agent is usually determined according to the amount of the starting agent, generally relative The amount of the starting agent is 3 0 to 2 0 0% by mole. The terminating agent is, for example, a compound such as water, an alcohol, an S-class compound, an organic acid or an inorganic acid, wherein the organic acid refers to an organic compound having a generalized acidity, for example, carb ο X y 1 icacid, feldspar. Compounds such as sulfonic acid, sulfinic acid, and phenol are preferably organic compounds containing carboxylic acid.

Page 14 1300069 V. Description of Invention (11) Compounds, specific examples of which are: formic acid, acetic acid, valeric acid, octanoic acid (cty 1 ic acid), capric acid, lauroylic acid, meat Myristinic acid, pa 1 mitinic acid, stearic acid, oleic acid, linoleic acid , ricinoleic acid, rosin acid, behenic acid, neodecenoic acid or versatic acid, among which neodecanoic acid is preferred.

Specific examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, boric acid, and streptoic acid. Specific examples of the alcohol compound include a lower alcohol such as decyl alcohol, ethanol or propanol, a higher alcohol of Ce~C1S, and a polyvalent alcohol such as ethylene glycol, propylene glycol or glycerin. Specific examples of the phenolic compound include phenol, 2,6-di-t-butyl-4-indenyl hydrazine, biguanide A and the like. • As described above, the reaction of the block copolymer of the present invention is carried out by reacting a monomer in a solvent, and after the reaction, the block copolymer is dissolved in a solvent to form a polymer cement. The slurry usually contains 10 to 35 wt% of solid matter, 1 is preconcentrated to 50 to 99% by weight of solid matter by means of reduced pressure and/or heating, and then vacuum oven, devolverizing extruder, or Import hot water to remove the remaining solvent. After the block copolymer is recovered, it can be formed into a desired shape by grinding, extrusion, or the like. Suitable additives such as antioxidants, slip agents, antistatic agents, weathering agents and the like may be added after the reaction to the recovery. Among them, antioxidants, thioether-based antioxidants, and dish-based antioxidants can be used as the antioxidant. The amount of antioxidant added is 0 · 0 0 5~

Page 15 1300069 V. Description of the invention (12) 2. 0 parts by weight (relative to 100 parts by weight of the block copolymer) is preferred, representative: octadecyl 3-(3,5 - two -T-butyl-4-hydroxyphenyl)propionic acid • S|(octadecyl-3-(3,5-di-t-butyl-4-hydroxy-phenyl) propionate), triethylene glycol bis[3- (3-tert-butyl-4-hydroxy-5-fluorenyl) propionate (D1^61:1171€116817 (3〇11318[3-(3-七61'1:-butyl-4) -hydroxy-5-methylphenyl )propionate]), pentaerythritol tetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid vinegar] (pentaerythritol tetrakis (3-(3, 5-di-tert-butyl-4-hydroxypheny1 ) propionate)), 2 - tert-butyl-6 - (3 - tert-butyl-2 -hydroxy-5-methylbenzoinyl)-4-methyl Phenyl phenyl acrylate, 2,2'-methylene bis(4-methyl-6-tert-butyl), 2,2'-thiobis(4-mercapto-6-t-butyl Phenol), 2,6-di-tert-butyl-4-methylphenol, 2,2,-thiodiethylene bis[3-(3,5-bis-tert-butyl-4-hydroxybenzene) Propionate], 2-[1-(2-propionyl-3,5-di-tripentylphenyl)ethyl]-4,6-di-third-pentyl A acrylate or the like. The thioether-based antioxidant is preferably added in an amount of from 0. 0.05 to 2 parts by weight (relative to 100 parts by weight of the block copolymer), and representative ones are: two-eighteen burns. 3,3'-thiodipropionic acid S (Distearyl 3,3'-丨thiodipropionate), di-dodecyl 3,3,-thiodipropionate (

Dilauryl 3,3'-thiodipropi〇nate), pentaerythritol tetrakis(3-dodecylthiopropionate) [?611七&611:111^71161^&1^3(3-dodecy 1 thiopropionate)], dioctadecyl sulfide, 2,4-bis(2,3'-di-hydroxypropylthiomethyl)-3,6-dimethylphenol [2,4-bis ( 2,,3,-di-hydroxy propyl thio methyl)-3,6-di-methyl phenol]

Page 16 1300069 V. Description of the invention (13), 2,4-bis(2'-acetoxyethylthiomethyl)-3,6-di-methylphenol [2,4-bis (2, -acetyloxy ethyl thio methyl)-3,6-di-methyl • phenol ], 4, 6-bis(octylthiomethyl)-o-cresol [4, 6-bis ( octylthio methyl)-. — cresol, thiol-)-o-曱S, etc., of which 4,6-bis(octylthioindenyl)-o-nonylphenol, 4,6-bis(dodecylthiomethyl) - o-cresol is preferred. The phosphorus-based antioxidant is mainly a phosphite-based antioxidant, and the amount thereof is preferably 0. 015 to 2 parts by weight (relative to 1 part by weight of the block copolymer), and representative ones are: Trimethyl phosphite, Trilauryl phosphite, Distearyl pentaerythritol diphosphite, three (2, 4-di-t-butylphenyl) sulphuric acid vinegar (d): 13 (2,4-(11-161'1:-butylphenyl)phosphite), tetrakis (2,4-di-tributyl) Phenyl)[1,1'biphenyl]-4,4'-substituted bisphosphonite (Tetrakis(2,4-di-tert-butylphenyl)[l,1'-biphenyl]-4,4 ' - (^丫11^3011〇3?11〇11116), 2,2' methylene bis(4,6-di-t-butylphenyl) octyl yanoate (2,2' - Methylenebis (4,6-di-tert-butylphenyl) octyl phosphite), etc. Specific examples of the slip agent are: metal soap such as calcium stearate, magnesium stearate, stearic acid clock, ethylene distearylamine , methylene distearylamine, palmitic acid amine, butyl stearate, palmitate stearate, polypropylene Alcohol tristearic acid vinegar, compound of '11-burning acid, stearic acid, etc., polyethylene sulphur, sulphuric acid wax, carnauba wax, petroleum wax, etc.; The amount is 1 part by weight relative to the block copolymer of 〇. 〇3~5 · 〇 by weight.

1300069 V. INSTRUCTION DESCRIPTION (14) Further, other polymers such as styrene homopolymer-, styrene-based may be further formulated without significantly impairing the transparency of the block copolymer of the present invention. Acrylonitrile copolymer, styrene-acrylate-type, acrylonitrile-based copolymer, styrene-mercapto acrylate-acrylonitrile-based copolymer, stupid vinyl-acrylate copolymer, stupid vinyl - mercapto acrylate copolymer, styrene-acrylate-acrylonitrile-maleimide copolymer, stupid vinyl-methacrylate-acrylonitrile-maleimide Copolymer, stupid vinyl-acrylate-maleimide copolymer, styrene-mercaptoacrylate-maleimide copolymer I, acrylate-maleimide The copolymer, the methacrylate-maleimide-based copolymer, or the copolymer modified with a diene rubber, wherein a styrene-based homopolymer is preferably added. The addition or mixing of the aforementioned other components or polymers can be carried out by mixing with a general mixing and kneading machine such as a Brabender plastometer, a Banbury mixer, a kneading-mixer, a roller press, a one-axis or a two-axis extruder. After mixing and mixing, the finished product can be further cooled and granulated. The above kneading is generally carried out at 140 to 250 ° C, and further preferably 1 7 〇 to 2 2 ° ° C. Further, the mixing and kneading of the above-mentioned respective components is not particularly limited in order. [Physical property test] 1. Softening point: It is tested according to ASTM D- 1 52 5 method. Specimen size: 1 / 4 inch thickness in °C. 2. Low-temperature impact strength: measured by the drop hammer impact strength tester manufactured by T0Y0SEIKI, the maximum height (mm) of the test piece without breaking under 2 kg load 〇

Page 18 Ϊ300069 V. INSTRUCTIONS (15) Specimen specifications: Injection molded discs with a thickness of 1/8 inch and a diameter of 55 mm. The test pieces were placed at -20 °C for 4 hours before the test. The unit is m m. 3 Bending strength · According to the ASTM D-790 method test. Specimen size: 1 / 4 thickness in k gf / c m2. ^ Tensile strength and elongation · According to the A S T M D - 6 3 8 method. Test piece Specifications · · Thickness 1 / 8 吋, the unit is kgf / cm2. 5. Transparency (Haze): According to the ASTM D-100 standard test. Test piece specifications: 3mm thick test piece, the unit is %. The higher the Haze value, the less > the worse the transparency. [Examples 1 to 4 and Comparative Examples 1 to 8] Herein, the examples of the preparation of the block copolymer and the physical properties thereof are described by way of Examples 1 to 4 and Comparative Examples 1 to 8, in which the vinyl aromatic monomer is benzene. Ethylene, the decadiene monomer is 1,3-butadiene, and the initiator is 8% by weight of n-butyllithium (in the cyclohexane). The polar compound is tetrahydrofuran, and the coupling agent is The epoxy is large and the oil' reaction is carried out in a solvent of cyclohexane. The stupid ethylene/butadiene block copolymer is polymerized in a batch reactor in the presence of a gas, and has a reaction starting pressure of 1 Kg/cm2G and a reaction starting temperature of 60 Qc. The reactor volume was 160 liters, and the feed sequence was as shown in Table 1. The monomer in each stage of the table was filled in > after the material was fully reacted in the reactor before the next stage of the feed. One of the tables indicates that the embodiment or the comparative example does not have this step, so that the next step can be directly performed after the completion of the previous step. The active block polymer structures before coupling of the respective examples and comparative examples are listed in Table 2. After the reaction is completed, the cement contains about 18% by weight of solid content, and the weight of each 〇

Page 19 1300069 V. Description of the invention (16), part of the German: paragraph of the copolymer is added about 0.2 parts by weight of octadecyl 3 - (3,5-di-t-butyl-4-hydroxyl Phenyl) propionate (abbreviated as IX-1 0 76), and • 0.6 parts by weight of trimethyl phenyl phosphite (TNPP for short). The block copolymer is obtained by passing the glue into hot water to remove the solvent, and the wet rubber particles are recovered and dried by depressing the machine. After granulation, the test piece is tested to evaluate the physical properties, and the evaluation results are shown in Table 3. The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and other equivalent changes without departing from the spirit of the present invention should be included in the scope of the present invention. Inside. 〇 [Description of Schedule] Table 1: The polymerization sequence of Examples 1 to 4 and Comparative Examples 1 to 8 of the present invention. Table 2: Structures of the living block polymers of Examples 1 to 4 and Comparative Examples 1 to 8 of the present invention. Table 3: Results of physical property evaluation of Examples 1 to 4 and Comparative Examples 1 to 8 of the present invention.

1300069 V. Invention description (17) * : 9/5 ' 7/00' 8/17, νϊΑ> 1,3-τ"$舛6 Mo Xizhong-铖一窗烊唞- by 2 windows牦屮铋舛6荽~>Wei#. \ 〇OC <1 〇to A feeding order dare big poly acetylene block / all vinyl aromatic bald polymer 箪 Η 1 ' Mo IL3-butadiene / stupid ethylene | 11.3-butadiene/stupid ethylene" | u-butadiene / stupid ethylene | 1 stupid ethylene 1 | 丨, 3-butadiene | 1 stupid ethylene 1 Η !' | stupid vinyl n-butyl lithium | u- Butadiene 1 stupid ethylene! | n-butyl lithium 1 1,3-butadiene 1 stupid ethylene i | n-butyl lithium tetrahydrogen.喃 I I cyclohexane wt% i wt% / wt% | ί parts by weight 1 1 part by weight 1 1 part by weight 1 1 part by weight 1 part by weight 1 1 part by weight 1 1 part by weight 1 1 part by weight 1 1 part by weight 1 1 part by weight, 1 part by weight, 重量 parts by weight, 1 part by weight, 1 part by weight, 1 part by weight, i, 1 part by weight, 1 part by weight, 1 part by weight, I, 47%, 76/24 I 〇丨丨' 2 OC Μ 1 0.021 丨〇〇1 0.024 K) OJ On 1 0.035 Ο 1 455.5 Example 1 58% ! 76/24 | 〇•丨丨丨(-/1 Μ 1 0.021 丨〇〇Γ 0.024 1 0.035 ο 1 455.5 Example 2 59% 76/24 | 〇丨1 丨丨丨1 0.021 j 〇1 0.024 j 5; 1 0.035 I ο 1 455.5 1 Example 3 ί 55% | 76/24 | ·〇丨丨1 丨· ' ν〇OJ 1 0.021 1 1 I 0.024 | UJ N) Γ 0.035 1 ο 1 455.5 j Example 4 33% 1 76/24 | 1 °·03 1 1 8/17* 1 1 7/8* 1 | 9/5* 1 丨'丨丨二1 0.016 1 1 〇1 0.036 ij NJ Ul 1 0.023 j •ο 1 455.5 1 Comparative Example 1 47% 76/24 1 〇丨丨丨2 1 0.021 1 〇〇1 0.024 00 〇1 0.035 ο Γ 455.5 Comparative example 2 47% [76/24 | 丨丨丨C: 〇〇1 15.5 to 1 0.021 1 〇〇1 0.024 〇UJ ON 1 0.035 ο 1 455.5 Comparative Example 3 47% | 76/24 | ρ 1 ,丨〇〇5; 1 0.021 丨〇〇1 0.024 ' OJ On 1 0.035 ί •ο [455.5 1 Comparative Example 4 58% 1 76/24 1 ·〇1 ' ' ' J ro Cloud 1 0.021 'Two 1 0.024 UJ Nian 1 0.035 ρ [455.5 Comparative Example 5 47% I 76/24 | | 0.09 1 1 1 丨' 1 1 o 1 0.021 丨1 0.022 On 1 0.038 ο 1 455.5 ! Comparative example 6 1 49% 1 1 76/24 ] | 0.40 1 1 1 丨•丨2 1 K) UJ 1 o.iio 5; 1 0.025 Ου 1 0.025 ο 1 455.5 Comparative Example 7 47% 1 76/24 1 _丨,, 1 丨〇〇1 0.021 1 丨〇〇1 0.024 1 r〇o 1 0.035 1 •ο LillU Comparative Example 8 Page 21

1300069 V. INSTRUCTION DESCRIPTION (18) Table 2 Examples 1 to 4 and Comparative Examples 1 to 8 Active Block Polymer Structure Active Block Polymer Structure Example 1 S 丨-B 丨-SyS B3-S5 S2-S3- B2-S4-B3-S5 S-5-B2*S4~B3~^5 Example 2 S jB j-S2~S^-B2"S4"B3~S5 52- S3-B2-S4-B3-S5 53 - B2-S4-BrS5 Example 3 S |-B j-S2"S3-B2~S4-B3 S3-B2-S4-B3 Example 4 Si-B|-S2_S3~B2-S4-B3 S3-B2- S4-B3 Comparative Example 1 SrSrSs-Bi/S^BySrB;^ Ss-B Comparative Example 2 S jB jS?"S3_B2"S4-B3-S5 S3-B2-S4-B3-S5 Comparative Example 3 S jB j- S2~S3-B2_S4-B3-S5 . S2-S3-B2-S4-B3-S5 83-82-84-63-85 Comparative Example 4 S j-S2_S3-B j -84-62-85 S3-B J -S4-B2-S5 Comparative Example 5 S jB j-S2~S3-B2~S4 S3-B2-S4 Comparative Example 6 S jB j-S2*S3-B2 S2-S3-B2 SrB2 Comparative Example 7 S jB j- S2*"B2"S3-B3 S3-B3 Comparative Example 8 S pB 1-S2-S3-B2-S4-B3-S5 52- S3-B2-S4-B3-S5 53- B2-S4-B3-S5 Page 22 1300069 V. Inventive Note (19) 雾 Haze Bending Strength Elongation Tensile Strength Low Temperature Impact Strength Softening Point Kgf/cm2 Kg/cm2 mm o° Unit One. 268 > 180 00 〇〇 450 Embodiment 1 〇 273 > 180 〇〇 ο 500 Example 2 4^ 274 > 180 K) 500 Example 3 匚 270 > 180 〇〇 500 ON Example 4 > 180 1 450 1 〇 \ Comparative Example 1 2280 > 180 s to < 50 Comparative Example 2 322 > 180 230 1 450 〇〇〇 \ Comparative Example 3 384 ! > 180 262 -1 450 O to Comparative Example 41 - 316 > 180 260 <50 00 Comparative Example 5 350 〇\ U) 243 <50 oo Comparative Example 6 350 > 180 1 244 1 <50 Comparative Example 265 > 180 < 50 Comparative Example 8 洳卜衅箨窆1»Khan 3:1~8棼^^齑雒> Page 23 1300069

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Claims (1)

1300069, June coffee correction replacement page VI, patent application scope 1 · A vinyl aromatic and conjugated diene block copolymer, the content of vinyl aromatic polymerized units and the content of the second-generation polymer unit is yang ~ 95 cc / / 35 ~ 5 conjugated diterpene / vinyl aromatic segment copolymer 'by a mixture containing the following three active new polymers, coupled by a coupling agent: S "Bl -S2-S3-B2-S4-Y, 52-S3-B2-S4-Y, 53-B2-S4-Y; wherein -Y is an anionically active end, representing a tax or preparation &, & The mountain represents a polyethylene-based aromatic block, and also the private representative of the two-dimerized system. The poly-co-diene-based block β1 accounts for the entire vinyl aryl 5-unit of the block copolymer and the co-light diene polymerization. 1% by weight to 5% by weight of the total amount of the unit 〇2. The block copolymer according to the above item 1, wherein the content of the most fragrant block is the total amount of the compound in the block copolymer. 4 to 30% by weight of the unit. Page 25