TWI293961B - Process for reducing water take up of vinyl aromatic-conjugated diene polymer - Google Patents

Description

1293961 V. INSTRUCTION DESCRIPTION (1) Field of the Invention The present invention relates to a method for producing a haze-free block copolymer, and in particular, the copolymer of the desired segment is composed of at least one hydrocarbon, such as dibutyl Ruthenium, prepared with at least one monovinylarene such as styrene via anionic polymerization using an alkali metal as a starter. [Background of the Invention] For the decolorized polymer of the acetamidine aromatic-co-diene block copolymer type, mineral acid, monobasic or polybasic carboxylic acid is used to avoid the formation of dark yellow during polymerization and processing. It is a technology of the prior art. This treatment produces a clear, yellowish polymer which, for the appearance of the polymer, renders such a yellowish color disappearing' to obtain a completely transparent, haze-free, colorless copolymer, especially such polymerizations. The application of food on food. There are many conventional methods for treating such copolymer solutions using a decolorizing agent to obtain a clear, haze-free, colorless copolymer. The use of an alkali metal initiator to prepare an ethylene-co-diene die-segment copolymer such as a styrene-butadiene-benzene (SBS) copolymer by anionic polymerization is a known technique. In this process, an alkali metal derivative, mainly an alkali metal alkoxide, needs to be neutralized and neutralized before the polymer is recovered, and these derivatives can be converted into the corresponding acid neutral and inert: ^ metal salt . A typical alkali metal is lithium, and its typical reaction equation is R-OLi + R' -COOH - R - 〇 - H + R, - C00Li where R is a polymer, representative of which is SBS block copolymer , butadiene rubber, butadiene rubber or polybutadiene, and R, a saturated fat

1293961 V. Description of invention (2) Family group. If this acidification step is not possible, an alkali metal species may be formed, and in addition to the subsequent unfavorable reaction, a higher opposite property may be produced in the block copolymer product. • In the presence of an antioxidant system, the block copolymer can be protected from thermal oxidation attack, which can result in the formation of colored by-products. The reaction of the alkali metal moiety thus reduces or controls the resistance of the transparent colorless ester copolymer to thermal oxidative attack; • reacts with certain antioxidant ether (R-0-C0R,) groups, resulting in chain cleavage and Produces volatile residues; < • Reducing the efficiency of the functional groups of fillers, pigments, pigments and UV-resistant additives. ~ [Description of the prior art] EP-A-0084795 and its corresponding US-A-4,403,〇74 disclose clear, haze-free, colorless, impact-resistant resin copolymers, especially SBS block copolymerization, , wherein the basic lithium derivative comprises a coupling polymer - the presence of lithium / the ping = water is selected from the group consisting of c2 'q and . Acidic linear saturated aliphatic two-rebel acid tt,. The linear saturation of the manufacture of haze-free polymers is also disclosed in the literature: Widely used acid, its previous specification reveals that when the polymer is prepared in a wet misty environment, it will significantly reduce the transparency and significantly increase the polymer for US^A-4,877,863 to reveal the vinyl aromatic "conjugated two The rod copolymer of the olefin copolymer is treated with a thiocarboxylic acid which may be a monobasic acid or a dibasic acid to carry out coloring. The patent also discloses that in high humidity environments, the use of sulfuric acid will lead

1293961

Degradation of the transparency and haze of the polymer. It is also known to use carbon dioxide or propionic acid as a decolorizing agent to neutralize the basic lithium residue system. When the polymer is required to be in a high humidity environment, the use of carbon dioxide or propionic acid also leads to the transparency and haze-free nature of the polymer. One purpose is to provide a transparent, haze-free, colorless block. In the preparation method, when the polymer is placed in a high-humidity environment, the resistance of the copolymerization of the crucible can be improved, especially the optical properties of the transparency and the haze-free property. Accordingly, the present invention also provides a neutralization and reaction in an alkali metal derivative of a vinyl aromatic-co-diene polymer. To the use of cie, a rebel acid to reduce the absorption of water by the polymer in a humid environment. [Object of the invention]

The present invention further provides a method for preparing a vinyl aromatic-conjugated diene block copolymer, which comprises at least one ethylene aromatic hydrocarbon and a co-polymerized liquid/liquid polymerization, together in a base. In the presence of a metal catalyst, an alkyl-carboxyl group is used to produce a copolymer chain and to treat the copolymer chain in solution, thereby enhancing the resistance of the copolymer to transparency and haze degradation in a humidity environment. Tannin has only 9 to 6 carbon atoms. The dicarboxylic acid is preferably a C9 to (12 linear dicarboxylic acid, more preferably azelaic acid, sebacic acid or lauric acid).

In the present case, based on the surprise of the inventors of the present invention, in order to obtain the decolorization of the vinyl aromatic-conjugated diene polymer, many acidification techniques have been uncovered, and applied to commercial, most of the permits or reveals transparent, fog-free. degree

89111391.ptd Page 6 1393961 V. INSTRUCTIONS (4) and colorless block copolymer products, where the polymer needs to be placed in a high-humidity ring, even if it is impregnated in cold or hot water, its initial transparency and The haze-free beak will quickly lose. The decline in these optical properties is generally a function of processing time. This decay phenomenon, which is not verified in Ep-a-0084975, US-A-4, 403, 074 or US-A-4, 877, 863, destroys the technical advantages of the block copolymer, especially with regard to SBS. The block copolymer has high transparency and low haze. The SBS block copolymer has at least some clarity and haze-free properties when the styrene content is from 15 to 95% by weight, and has a complete transparency when the present ethylene content is at least 70% by weight. This optical property is required when the polymer is applied in a clear plastic hood package that contacts food containers, toys, plates, cups, and the like. Without being bound by theory, the inventors believe that the increase in haze of the copolymer is due to the humidity environment of the ’. In the polymer substrate, an increase in opacity and a decrease in transparency are caused by water entering the material. In addition, the high adsorption and absorption of water by the polymer leads to defects in the surface and appearance of the extruded or molded product during the manufacture of the block copolymer. The copolymer requires high cost and time consuming during the processing of the product. Dry operating conditions. The prior art described above does not understand that the block copolymer causes a decrease in transparency and an increase in haze under a special environment, particularly in a humidity environment in the south. The present inventors have surprisingly found that the selection of the level of decolorizer particles not only allows the production of a clear, haze-free vinyl aromatic-conjugated diterpene block copolymer, but also maintains this property in a high humidity environment. The decolorizing agent comprises c9 to Cie' which is preferably a Cg to C12 ditetic acid. Below C9, the increase in water absorption and transparency is not significant, but above (^6, due to the long chain length of the bleaching agent)

89111391.ptd Page 7 1293961 V. Inventive Note (5) Degree, the decolorizing agent is invalid. For various applications of SBS copolymers, not only is its low haze and high transparency necessary at the beginning, but it also remains high when the SBS block copolymer product is cold or hot water or water vapor. Transparency and low fog. For example, when SBS block copolymers are used in medical applications, they are usually required to be sterilized in steam; or when used in food packaging, foods that are often placed in containers are often warm and humid. For food or beverage packaging, the SBS block copolymer may need to be sterilized by heat sterilization by immersion in a high temperature aqueous medium for a period of time, such as 85 ° C for 4 5 minutes. This SBS block copolymer may also be applied to a heat shrinkable film. The film is shrinked by steam treatment. This heat shrink film is used for protection such as labels and obvious alterations. According to the present invention, the vinyl aromatic-conjugated diene block copolymer may be via a pure polymer or blended with other polymers such as polystyrene, which is conventionally used as a general purpose polystyrene (GPPS, ie, Known by Gristai ps), to manufacture a variety of products, such as extrusion sheets in the forming process, especially in thermoforming, to produce transparent, shock-resistant products such as food packaging. DETAILED DESCRIPTION OF THE INVENTION The process of the present invention can be applied to a copolymer of a resin and an elastomer, which is polymerized in a solution of a vinyl aromatic and conjugated diene monomer in the presence of an alkali metal-containing initiator. Produced by reaction. The block copolymer is formed by the polymerization reaction, and the - or multiple branches of these block copolymers may be composed of an irregular copolymer. Such polymerization is generally carried out in solution in the presence of a metal-containing initiator and a solvent. In addition, in order to couple the polymer, it can be aggregated.

1293961 1, invention description (6) " ---- t reaction process is added to the coupling agent. The copolymer thus formed is almost linear or radial, but only the color is unacceptable in the optimum use of the copolymer. The type of polymer suitable for use in the process of the present invention is described in us-A-3, 639, 5 1 7 'US-A-4, 091,0 53 and EP-A-0084795. The polymerization process is briefly described below. Suitable for the polymerization of the present invention; for a more detailed description of the process, reference is made to (10) - A-3 639, 5 1 7, Μ-A-4, 091, 053 and EP-A-0 084 795, which have a complete disclosure. The polymerization is carried out at a temperature of from -100 ° C to + 150 ° C in a solution in the presence of a solvent sufficient to maintain the medium at a liquid pressure. This solvent may be alkane, naphthenic or aromatic. The most common user is a mixture of cyclohexane or hexane, cyclohexane. Initially, a block of a non-elastomeric polymer is formed by feeding a vinyl aromatic monomer having an appropriate amount of an organolithium starter to form a long chain of a reactive polymer having a lithium atom at the end of the chain. The chain or reactive polymer is then contacted with a conjugated diene to form a polymeric bond having elastic and non-elastic blocks. A copolymer having an A-B structure (A = ethylene aromatic, 6 = conjugated diene), in the case of a linear structure, is optionally contacted with a coupling agent to form a polymer of the A-B-C-B-A structure, wherein c is a part of the coupling agent. It can be understood that a copolymer having a radial or linear structure can be formed, and the block may form a pure homogeneous polymer or an irregular polymer. The type of copolymer depends on the polymerization process, and the process of the invention is suitable for the decolorization of the copolymer. Examples of suitable co-diene monomers include from 4 to 12 carbon atoms.

89111391.ptd Page 9 1393961 V. Description of invention (7) For example: 1,3-butadiene isoprene diquat, 3-butyl-l 3 - xin- 荔 荔 # methyl 1,3 butyl Alkene, a mouth, a lane 1, d, and its analogues. Examples of 々7 early body are: styrene, alpha-methyl-vinyl aryl, and its analogues. Therefore, the process # Μ , vinyl naphthalene or its it is applied to the resin copolymer or even the % ^ ^ ^, the weight ratio of the stomach common diene / ethyl aromatic has j = body circumference, especially from 1 /99 to 85 /15 〇尹,泛之摩巳 The non-essential coupling agent is selected from the group consisting of: ethyl aceto aromatic compound, polyisocyanic acid, polyamine, polyaldehyde, poly _, such as tetradentate m ϋ _ , polyanhydride, polyacetal vinegar, polyester, ... 2:: coupling agents may also be used. Examples of suitable polyethylene aromatic compounds are tert-butyl 4-trivinylbenzene, 1,3-divinylnaphthalene, triethylene naphthene, diene, and the like. , 4 - ethoxylated epoxides can be used in the same way, in general, epoxidized carbon hydrides, such as: epoxidized liquid polybutadiene or epoxidized vegetables such as epoxidized soybean oil and epoxidized linseed oil Oil systems are used, others such as: 丨, 2; g 6 · 9, 1 〇; - triepoxydecane epoxy compounds can also be used. ,,,, - Examples of suitable polyisocyanates are: benzene-H 4_triisocyanate, naphthalene-1, 2,5,7-tetraisocyanate and the like. An example of a suitable polyamine is a hydride or sulfur physicochemical of trimethyl propane phosphine, such as: tris(1-indolyl)phosphine oxide, tris(2-methyl-i-indolyl)phosphine oxide, (2- Ethyl-3-mercapto-1-indol propane) phosphine sulfide and the like. 1,4,7-naphthalenetrialdehyde, 1,7,9-selycanaldehyde, iota, iota-5-pentanetrialdehyde, and the like are suitable examples of polyketones.

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1293961 V. INSTRUCTIONS (8) — — 1,4, 9, 10 — Onion tetraketone, 2, 3-diacetone cyclohexanone, and the like Examples of suitable polyketones. • Pyromellitic dianhydride, styrene-maleic anhydride copolymer, and the like are suitable examples of polyacids. An example of a suitable polyorganic compound is a tetrahalide of ruthenium, such as SiC14.

SiBq and Si I4 , trihalodecane, such as trifluorodecane, trichlorodecane, trichloroethyl decane, dibromobenzyl decane, and the like; and halogen-substituted hydrocarbons such as · 1,3 , 5-tris(bromomethyl)benzene, 2, 5, 6, 9-tetrachloro-3, 7-anthracene, and the like. Examples of the compound having one functional group or more include: hydrazine, 3_di-2-acetone, 2,2-dibromo-3-indanone, 3,5, 5-trifluoro- 4-octanone, 2, Dibromo-3-pentanone, ms-diepoxy-3-pentanone, diepoxy, 3-hexyl-1,2diepoxy-8-pentadecanone, 1,3; 18, 19-one % Oxygen-17, 14-eicosanedione, and the like. It is also possible to use other metal halides such as tin, argon, and lanthanum, and polyalkoxides such as tetramethicone. 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Parts by weight (pph or phr). In the process of the present invention, the coupling copolymer is subjected to decolorization treatment by formation of impurities, and the impurities are formed by reacting the lithium compound with a dicarboxylic acid according to the present invention and other coupling agents. When recovering a copolymer which is directly solvent-removed, the present invention provides a very advantageous method of polymerizing the polymer before it undergoes the decolorization of the present invention.

1293961 V. INSTRUCTIONS (9) One part of the reaction solvent may be removed. 9 to] C〗 6 竣 之 之 / / / / 1 1 1 « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « « "People", Λ · 5pph. The acid may be added alone or directly into the polymer:, :) polymer solution. The acid or acid mixture can be used in the P 〆 &&; Λ 〆 〆 〆 或In one of the solvents of cyclohexane, the combination of ', and more to Ci6 dicarboxylic acid can obtain excellent transparent poly-low such as yard, to obtain some antioxidant activity of the polymer, but can be reduced to -%. Similar to the amount of additives such as antioxidants. It has the use of c9 to (:16 aliphatic dicarboxylic acid, such as: azelaic acid, according to the smoke of the day, you ± ± six months, only the soil secret mountain 2 second It is to improve the transparency and the haze resistance of the mouth when the ethylene aromatic-conjugated two, = λ is used in a humidity environment. Especially the use of the dicarboxylic acid, the block copolymerization, t has high transparency and high barrier water properties. The use of this dicarboxylic acid also has process advantages, such as the addition of excess acid in the solution, which is in the block After the termination of the reaction, it is only necessary to add an adduct of a dicarboxylic acid to the reactor, and the terminator used in the termination reaction is, for example, propylene oxide, and a low volatile carboxylic acid of C9 to Cu. The invention further provides a process for producing a vinyl aromatic-conjugated diene block copolymer, the process comprising the solution polymerization of at least one ethylene aromatic hydrocarbon and a conjugated dilute in the presence of a metal test catalyst to prepare a base a copolymer chain of a metal end group, and a linear alkyl dicarboxylic acid having 9 to 6 carbon atoms and a slurry form having a granular form and an average particle size of less than 50 μm, which is treated in a solution Polymer chain. When the content of styrene is 丨5 to 95% by weight, the polymer may have a certain degree of transparency.

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89111391.ptd Page 12 1393961 V. Description of the Invention (ίο) The vinyl aromatic-co-diene block copolymer is transparent, haze-free, colorless, and comprises benzene having a styrene content of at least 70% by weight. Ethylene-butadiene-styrene block copolymer. In a still further aspect of the invention, the dicarboxylic acid decolorizer is added to the post-copolymer as a slurry in solution. Preferably, the slurry comprises finely divided particles of diweiric acid, preferably having an average particle size of from 5 to 50 microns, in an organic liquid such as a paraffin such as hexane. A particularly preferred organic liquid comprises a mixture of calcined <RTI ID=0.0>0> In this hexane mixture, sebacic acid, citric acid and lauric acid were measured at room temperature, respectively, at concentrations of 0 · 3 4 , less than 0·002 and 0.015 wt%. In the case of the present invention, it has been found that the application of the finely ground dicarboxylic acid slurry in an organic liquid can significantly accelerate the neutralization of the alkaline bell derivative. US-A-4' 403, 074 and EP-A-0084795 disclose that an aliphatic dicarboxylic acid can be added to the aqueous solution or dispersion in the neutralization step, or when a polymer binder or a wave-reducing polymer binder is added. Medium, with a dry solvent: preferably blended with each other. Then the inventor of the present case was surprised to find out; a rational, economical method to mix the dibasic acid, 2 2 f 2: the finely ground particles in an organic liquid two slurry = shape '% this a, so Significantly reduce the neutralization time and the desired, optical and mechanical properties. If the average grain is not in the environment, the health and safety issues must be considered, especially the risk of inhalation. Preferably, the H acid is ground into a powder, for example, by a known method, 1293961, and the invention (11) is micronized to obtain an average particle size of less than 50 μm, preferably 25 μm. It is less than! 〇 micron. The use of sebacic acid is less than micron particles, for example, with a flatness of 23 microns, as the accepted industrial azelaic acid particle size is reduced to 8 to 1 〇 Micrometers, wherein the time and time can be reduced to about [minutes.] The following examples are used to illustrate the invention more clearly, but without limiting the embodiments 1 to 3 in these examples, an SBS block copolymer ( An amount of about 12 kg is prepared by using a n-butyl quinone as a catalyst, and the basic lithium is neutralized with a q or a dicarboxylic acid, which uses 5 mol of a 1% based on n-butyllithium catalyst in accordance with the present invention. The monoacid is injected into the tetrazole (THF) in a solution. The dibasic acid of Example 1 includes a concentration of 8% and an amount of 0.11 7 phr (ie, every 1 part). The dicarboxylic acid of the copolymer. The dibasic acid of Example 2 comprises 98% by weight and 0.16 phr of sebacic acid. The dicarboxylic acid of Example 3 comprises azelaic acid in an amount of 126126 phr. The resulting rubbery copolymer is recovered to remove the solvent, and then a 2-leg thick compression molded plaque is formed therefrom. The optical properties of the plaques in Examples 1 to 3, especially the measurement results of haze, transmission, and yellowness index. It can be seen from Table 1 that the use of C9 + dinonanoic acid according to the present invention gives a haze of 2% or less. The permeability is higher than about 90%. The measurement of haze and transparency is based on the procedure of ASTM D 1 0 03-97, while the measurement of the yellow index is based on ASTM D1 925-7 0 (re-approved in 1 977) The steps.

89111391.ptd Page 14 1293961 V. INSTRUCTION DESCRIPTION (12) SBS block copolymers prepared according to Example 1 and Example 3, which are formed into a thickened compression molded plaque, and these plaques are 3 immersed in water at a temperature of 〇 °c for 8 days. Figure 1 shows the water uptake (measured in ppm) of the plaque as a function of impregnation time. It can be seen that after the 7-day impregnation time of Example 1, the water absorption is very low, about 1 250 ΡΡΠ1, and the water absorption of Example 3 is even lower, after 8 days of immersion, about 50〇ppm. Fig. 2 is a view showing the relationship between the haze and the impregnation time of the decorative sheets of Example 1 and Example 3. As can be seen from Figures 1 and 2, the haze generally increases with time and is generally consistent with the water absorption of the rubber trim. The fascia of Example 1 had a haze of about 20% after a dipping time of 7 days, while the fascia of Example 3 had a haze of about 5% after an 8 day dipping time. Comparative Examples 1 to 5

In Comparative Examples 1 to 5, the steps of Examples 1 to 3 were repeated except that propionic acid (a monobasic acid) and (: 4 to G dicarboxylic acid were used, and therefore, in Comparative Examples 1 to 5, A monobasic acid or a dicarboxylic acid, which is propionic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid, respectively, is used, and the amounts thereof are shown in Table 1. In Comparative Example 1, propionic acid was used as a solution. The method was added to hexane, and in a comparative example 2 to 5, a monobasic acid was added as a solution to τ η F as in Examples 1 to 3. Once again, the preparation of the SBS block copolymer was measured. The optical properties of the plaques are shown in Table 1. As can be seen from Table 1, the use of certain dicarboxylic acids smaller than C:9, such as glutaric acid, adipic acid and octanoic acid, The optical properties of the SBS back-end copolymers obtained in Examples 1 to 3 are similar. However, these optical properties are initial optical properties, and according to the present invention, the inventors found that:

1293961 V. INSTRUCTIONS (13) Comparative Examples When preparing SBS block copolymers under high humidity, for example, in impregnated cold water, the copolymers of these comparative examples exhibited significant water absorption & The haze of the object increased significantly. The elastomers prepared according to Comparative Examples 丨 to 5 were also subjected to a water immersion test, which can be referred to the above Examples 1 to 3 for the comparison of the water absorption and haze increase of the rubber of Examples 1 to 5'. It is a function of the measured impregnation time and the results are shown in Figures 1 and 2. It can be seen from Fig. 1 and Fig. 2 that in the application of the CQ + dicarboxylic acid as a neutralizing agent and a decolorizing agent according to the present invention, when the copolymer rubber is applied to a high temperature environment, the absorption of water unexpectedly drops significantly. And there is a considerable drop in haze as it falls. This phenomenon cannot be predicted by prior art. Therefore, when the sample of the polymer is neutralized using a dicarboxylic acid in a high-humidity environment, such as water impregnated in 3 Torr, the chain length of the carboxylic acid is determined by the time as a function of water absorption, thus determining Increased rubber haze. From the best results of these comparative examples, namely glutaric acid, it can be seen that after a period of 8 days, the haze is greater than 30%, which is significantly higher than in Examples 1 and 3. In this comparative example, a commercial SBS block copolymer 1 was used to cut the compression molded plaque, sold by Phillips Petroleum of Bartlesfield, Oklahoma, USA. The trade name is KR04, which is tested by the impregnation water method as in Comparative Examples} to 5, and Figures 2 and 2 are the results. It can be seen that the increase in haze of the rubber in Comparative Example 6 with time is slightly higher than that of Example 1. Table 1 lists the initial optical properties of the rubber of Comparative Example 6 in terms of haze, transmittance, and yellowness index. The copolymer is neutralized with carbon dioxide.

89111391.ptd Page 16 1293961 V. INSTRUCTION DESCRIPTION (14) Example 4 In this example, the SBS block copolymer was prepared on an industrial scale: 3.5 tons of sebacic acid was used. The sebacic acid added to the SBS block copolymer solution comprises a selenic acid particle having an average particle size of 8 to 10 μm and 20 wt% (6 alkanede, which is added as a slurry. The resulting SBS block copolymer is The granules were then granulated and then subjected to a 10 minute treatment at 130 ° C for 10 minutes to prepare a 2 mm thick compression molded plaque. The haze of the plaque is listed in Table 2, Transmittance, optical properties of yellow index. Comparative Example 7 In this example, the treatment procedure of Example 4 was repeated, except that the propionic acid solution was used to replace the liquid azelaic acid in the C6 paraffin. Table 2 lists the corresponding optical properties of the 2 mm thick compression molded plaque. Adipic acid instead of propionic acid as a decolorizing agent can be seen to have better optical properties, ie, reduced haze, increased transmittance, and Lower yellow index. Comparative Example 8 In this example, a commercial SBS block copolymer sold by Phillips Petroleum, Bartlesfield, Okla., under the trade name KR04 , made into 2 leg thick compression molding plaques, and measured the optical properties of these plaques, the results column In Table 2. It is generally believed that the copolymer is neutralized with carbon dioxide. Compared with the commercial SBS block copolymer of Comparative Example 8, it can be seen that the SBS block copolymer prepared according to Example 4 has The lower haze, transmittance and yellow index were slightly improved. The SBS copolymer of Example 4 and Comparative Examples 7 and 8 was made into a 1 mm thick extrusion molded panel at 30 °. C, immerse it in deionized water for up to 7

89111391.ptd Page 17 1293961 V. Inventions (15) One " days. Figure 3 and Figure 4 show the relationship between the impregnation time and the water absorption and haze measurement results. As can be seen from a comparison of Comparative Example 7 using propionic acid, water absorption and haze were significantly decreased with time according to the SBS block copolymer prepared by using sebacic acid. Further, in Example 4, the polymer prepared using sebacic acid was lower than that of the commercial polymer of Comparative Example 8 as the amount of water absorption and haze decreased with time. It is used in the rigorous test of the polymer in 30 X: water for many days, and the use of 'eg + diterpenic acid increases. As the haze increases at a relatively low rate, the absorption of water has a very low tendency. Meets the rate at which transparency disappears. Embodiment 2 In these examples, an SBS block copolymer is neutralized with sebacic acid according to the present invention, and then blended with general-purpose polystyrene (ps) (refer to the above, in different weight ratios, Then, an extruded sheet having a thickness of 400 or 80 μm was formed, and the sheet was then immersed in water of 65 Torr, and the haze of the sheet was measured as a function of the time of the collapse. The results are shown in Fig. 5. 5 ^ The blend contains 40 wt% SBS / / 6 〇 wt% ps to form a thick 4 〇 () micron extruded sheet. Example 6 is comprised of 6 〇 wt% SBS / 4 〇 wt% ps blended 盥An extruded sheet having a thickness of 400 μm. Example 7 is an extruded sheet comprising 5 Å wt % SBs / & = wt / ePS 4 α to a thickness of 8 μm. It is impregnated with η, after which the sheet is composed of Removed in water, and entered for 40 minutes, desorbed into ^ ^ 』, after 10 minutes and 40 minutes of desorption, the measured P 匕 〉 〉 贝 贝 贝 , , , , , , , , , , , , , , , , , , , , , , Minutes), Figure 5 is the result. 71 can be seen in Figure 5, as the immersion time increases

1293961 DESCRIPTION OF THE INVENTION (16) The addition of haze is not particularly high, and has a final haze of less than 丨〇% after 5 minutes of immersion. This haze is reduced during the desorption period. Comparative Examples 9 to 1 In Comparative Examples 9 to 11, the SBS block copolymer and the general purpose styrene (ps) blending system were decolorized by using propionic acid instead of sebacic acid to decolorize the SBS block copolymer. Prepared by neutralization. The weight ratio of the comparative example 9 to the blend of bismuth and the thickness of the sheet correspond to Examples 5 to 7, respectively. Fig. 5 shows the results of the water immersion tests as in Examples 5 to 7 in comparison with Examples 9 to 11.

As can be seen from Fig. 5, the SBS copolymer/polystyrene blend is prepared by neutralizing the SBS copolymer with sebacic acid under the severe humidity test state of being immersed in water at 65 °C. Extruding the flakes is a neutralizer with propionic acid, and the haze increase has a very low tendency. What is more, in the subsequent water immersion f process, the use of propionic acid causes a π-desorption period due to the high concentration of adsorbed water. In other words, propionic acid was used as a neutralizing agent according to the comparative example. In the example of the cost case, the haze was still very high at the end of the desorption period. Da Aijfe example 1 2

In this comparative example, Phillips Oil Company, from Phillips, Oklahoma, USA, under the trade name KK38, has a 3:2: $ degree, 90.6% transmittance, 3 A commercially available SBS block copolymer of 4 yellow index and a general purpose styrene to form a blend of 50 wt% SBS block copolymer / t〇w^t% PS. It is generally believed that the commercial block copolymer is neutralized with carbon dioxide. This blend was extruded into a sheet having a thickness of 8 μm. The second = sheet was treated with the same impregnation test as in Examples 5 to 7 and Comparative Example 9 to ,, and the results are shown in Fig. 5. In accordance with the method according to the invention

1293961 V. Inventive Note (17) As compared with the SBS block copolymer blend, it can be seen that the blend of Comparative Example 12 using a commercial SBS block copolymer has a period of impregnation and subsequent desorption. Higher haze. Examples 8 to 12 In some of the examples, the effect of particle size on neutralization time was investigated for C9 + ditoponic acid, especially sebacic acid. In these examples, the properties of the bismuth = particles are listed in Table 3, and the azelaic acid is contained in a solvent containing cyclohexane/15 wt% hexanone, in a concentration of 2% by weight, 〇: An amount of 132 phr is added to the reaction vessel containing the copolymer solution, followed by depolymerization by the copolymerization reaction. The residual time is measured, and the pH of the liquid: the liquid is measured, and then an antioxidant system is added to the polymer solution. The pH value of the test is based on the Merck general indicator 9175. The results show two: Then the 'pH 6 polymer solution for neutralization reaction, the visual detection and results of the color and appearance of the polymer solution In Table 3. It can be seen from Table 3 that the addition of sebacic acid particles can be obtained from industrial azelaic acid. Also, the particles have an average particle size of 1 38 μm, and are added in a slurry in a & solvent. 6 hours to reach a pH of 6, which is the index of the neutralization reaction (the value is less than 7 or equal to 7.) If only after 1,5 hours, the polymer is recovered, after the solvent is removed, the yellow turbidity The polymer solution is produced, due to the aggregation after 15 hours The pH of the solution is about 9, so the solution is not neutralized, and a polymer having a strong color and a low processability is produced. If the neutralization lasts for 6 hours, a colorless and transparent polymer solution is recovered. At this point the neutralization has brought the pH to 6 'but the neutralization reaction time is obviously too long.

1293961

In Examples 9 to 12, it can be seen that the azelaic acid particle size decreased to 23 μm, 8.3 μm, and 10 μm, respectively, with a shorter neutralization time.

This is quite attractive to the industry. B Example 1 3 to 15 In these examples, Example 13 uses octanoic acid in suberic acid, and lauric acid in Examples 14 and 5 to neutralize the test derivative of the SBS oxime copolymer, the sheet of which is The preparations are described with reference to Examples 1 to 3, which is a variation of water absorption (ppm water) versus time (days) at a total time of 7 days. It can be seen from the figure that using the suberic acid as in Example 13 and using the lauric acid neutralizing block copolymer as in Examples 14 and 15 has a low water absorption during the 7-day period, as in the example; As for 丨5, the water uptake after 7 days was 304, 247, 285 ppm water, respectively. The measurement of the increase in haze of the sheets in each of these examples and the results are shown in Fig. 7. After 13 days, Example 13 had a haze maximum of about 25%. Comparative Example 1 3 to 15 In these comparative examples, Comparative Examples 13 and 14 were prepared using propionic acid, and corresponding to Examples 13 and 14 while the SBS block of Comparative Example 15 was used. The copolymer used was a commercial SBS block copolymer from Phillips Petroleum, Inc. of Bartlesfield, Okla., under the trade name XK40. The SBS block copolymers of these comparative examples were tested by the same water immersion test as in Examples 13 to 15. The relationship between the water absorption amount and the haze is shown in Figs. 6 and 7, and it is understood from the use of the drawings. The comparative example of propionic acid as a neutralizing agent has a larger increase in haze and water absorption during the immersion time than the use of suberic acid or lauric acid. For commercial SBS block copolymer XK40, this is more

89111391.ptd Page 21 1393961 V. INSTRUCTIONS (19) The example has a greater water uptake than Example 1 3 to 15 but at the end of the 7-day impregnation period, the haze is approximately 22%, Example 13 is somewhat lower, but is higher than the value of about 11% of Example 14 and about 9% of Example 15. Example 1 6 In this example, lauric acid was used as a neutralizing agent, and the immersion test was carried out by preparing a SBS block copolymer as in Examples 1 to 3 and performing haze and water absorption with time. . The results are shown in Fig. 8 and Fig. 9, and it is known that the increase in water absorption amount and haze during the 7-day impregnation period is low. tComparative Example 1 6 In this comparative example, the same SBS block copolymer as in Example 中6 was neutralized with propionic acid, and then the SBS block copolymer was formed into a sheet, which was the same as in Example 1 6 The same 7 days in the water impregnation test, the relationship between the amount of water absorbed and the degree of enthalpy is shown in Figures 8 and 9. As can be seen from Figures 8 and 9, when embedded, the copolymer is subsequently treated under wet environment, using laurel The acid-substituted propionic acid into the sigma agent has a significant decrease in water absorption and an increase in haze.

1293961

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黄谢® ^ π ί 1—( l〇rH 'Through ship ' % $ 1 1 2 inch cn oo 冕 冕 1 i I liHil 89111391.ptd Page 24 1293961 V. Invention description (22) Total septic rot Transparent transparent transparent ¢1 魃^ ¢1 ¢1 Shoes and shoes are recommended to indicate the time of pH値/JN0寺〇\ mv〇v〇v〇ν〇〇ν〇ν〇ν〇r- Ό ν〇Η 〇〇 ν〇ν〇ν〇rH 〇\ "Q mixed 醎(°C) <〇> ιη ^τ) <〇> V〇V〇V〇V〇m 癸2 chick size 50% <113μ , 90% < 293 μ (average · 138 μ) 50% < 14 μ, 90% < 52 μ (mean: 23 μ) 50% < 7 μ, 90% < 13 · 5 μ (mean: 8 · 3 μ) 50% <9μ, 90%<17μ (Average: ΙΟμ) 50% <7μ, 90%<13·5μ (Average: 8.3μ) Example 8 Example 9 Embodiment 10 Example 11 Example 12 !! 89111391.ptd 1293961 The following is a brief description of the steps of the present invention, which are briefly described by way of examples, and are schematically illustrated as Fig. 1 which is an SBS block copolymer sheet prepared according to an embodiment of the present invention and a comparative example, which is absorbed. Water and dipping time Department of Fig. Fig. 2 is a graph showing the relationship between the haze and the immersion time of the sheets of the examples and comparative examples. Fig. 3 is a graph showing the relationship between water absorption and impregnation time of an SBS copolymer sheet obtained in accordance with another embodiment of the present invention and another comparative example. Fig. 4 is a graph showing the relationship between haze and impregnation time for the sheets of the comparative examples and the examples. Figure 5 is a graph showing the relationship between haze and impregnation time for SBS copolymer sheets prepared in accordance with further embodiments of the present invention and further comparative examples during subsequent desorption periods. Figure 6 is a graph showing the relationship between absorbed water and impregnation time of an SBS copolymer prepared in accordance with an embodiment of the present invention. Fig. 7 is a graph showing the relationship between haze and impregnation time of the sheets of the examples and comparative examples. Figure 8 is a graph showing the relationship between absorbed water and impregnation time for a sheet of SBS copolymer prepared in accordance with an embodiment of the present invention and a comparative example. Fig. 9 is a graph showing the relationship between haze and impregnation time of a sheet of another embodiment and a comparative example.

89111391.ptd Page 26

Claims (1)

1293961 Case No. 89111391 々年修(ψ正本修正2006 1 4 SEP Replacement) s. Patent application scope, 1. A method for reducing the water absorption of a vinyl aromatic-conjugated diene polymer, selected from the group consisting of 壬Treating the alkali metal derivative of the polymer with an alkyl dicarboxylic acid of a diacid or azelaic acid to neutralize the period μ 'the method can reduce the water absorption of the polymer under the degree of fishing = where the vinyl aromatic _ conjugated diene polymer system 1 contains a styrene-butadiene-phenethyl hydrazine block copolymer, and the alkyl bismuth W has an average particle size of less than 5 〇 micro# of acid particles + t liquid added to the organic liquid中〇2 ·If the method of claim 1 is burned. 3. The method of applying the scope of the patent is 〇·11 to 〇·13 phr. 4. If the method of claim 1 is The organic liquid includes a styrene unit in which the styrene-butadiene-benzene block copolymer is transparent and includes at least 7Q% by weight of styrene unit 0 5 ΐ : :: " a method wherein the ethylenic-conjugation comprises from 15 to arbitrarily as the ethyl aromatic component In the humidity, the nature of the haze also decreased together. C:\Total file\89\89111391\89111391 (replace)-3.ptc Page 27