JPS6322852A - Block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain a composition with markedly improved heat resistance outstanding in transparency and impact resistance, by blending a specific vinyl bond-contg. block copolymer and polysulfone polymer. CONSTITUTION:The objective composition can be obtained by blending (A) 100pts.wt. of a block copolymer made up of one or more polymer blocks consisting mainly or vinyl aromatic compound and one or more polymer blocks consisting mainly of conjugated diene compound with a content of the vinyl aromatic compound being 5-95wt% and a 1,2-vinyl bond content >15% and (B) 5-70pts.wt. of a polysulfone polymer. The component A should contain either 10-60wt% or 60-90wt% of the vinyl aromatic compound. The component B should be of formula (Ar is phenylene; B is O, S or aromatic diol).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a block copolymer composition with improved heat resistance, and more specifically, a block copolymer composition comprising a vinyl aromatic compound and a conjugated diene compound as a heptad. The present invention relates to a composition comprising a structured block copolymer and a polysulfone polymer.

(Prior Art and Problems) As is well known, a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound can be cured at room temperature without vulcanization if the content of the vinyl aromatic compound is relatively small. It exhibits good elasticity, and when the mold content of vinyl aromatic compounds is relatively high, it has excellent transparency and impact resistance, and both of these exhibit fluidity similar to that of thermoplastic resins at high temperatures. It can be easily molded using a general extruder or injection molding machine.
Widely used for footwear, food packaging containers, etc.

However, despite having such excellent properties, a major reason why the scope of use of such block copolymers is limited is due to their poor heat resistance.
It becomes practically unusable.

Many attempts have been made to remedy this drawback. For example, there is a method of crosslinking using a peroxide or sulfur-vulcanization accelerator system, especially in footwear applications, but although this improves heat resistance to some extent, it is difficult to recycle after molding. This method has the drawback of losing the reworkability of thermolabile block copolymers.Also, another method is to blend poly-α-methylstyrene into the heat-resistant block copolymer. Although there have been attempts to improve this, the current situation is that the objective has not been fully achieved.

(Means for solving the problem) The inventors of the present application have conducted intensive studies on a method for improving the heat resistance of block copolymers without deteriorating their properties, and have found that the purpose can be achieved by using polysulfone. They discovered this and arrived at the present invention.

That is, the present invention provides (1) a block copolymer containing 7 or more polymer blocks mainly composed of a vinyl aromatic compound and 7 or more polymer blocks mainly composed of a conjugated diene compound, , the content of vinyl aromatic compounds! ~95 parts by weight of a block copolymer having a co-vinyl bond content of -゛-゛゛/l exceeding 10 parts by weight, and 70 parts by weight of a +11 polysulfone Eastoglycan. .

The present invention will be explained in detail below.

A block copolymer (hereinafter simply referred to as "block copolymer") containing 7 or more polymer blocks mainly composed of a vinyl aromatic compound and 7 or more polymer blocks mainly composed of a conjugated diene compound. The weight ratio of the vinyl aromatic compound to the conjugated diene compound in .) is ! /the law of nature! ~9
j/! , preferably 10/90 to 0//θ, more preferably /! ／♂Evening～♂! // Evening composition range. If the weight ratio is less than 5795, the properties of the block copolymer as a thermoplastic elastic body are poor, and the weight ratio is 95/J-
Exceeding this is not preferable because the impact resistance will be poor.

In the composition of the present invention (in which the vinyl aromatic compound content of the block copolymer is in the range of 5 to 60% by weight), an elastomer composition with excellent heat resistance is obtained; When the aromatic compound content is in the range of more than 60% by weight and 11% by weight and not more than 9% by weight, a transparent impact-resistant resin composition with excellent heat resistance can be obtained.

Therefore, in the present invention, the content of the vinyl aromatic compound can be arbitrarily changed within the above range depending on the required properties.

The polymer block mainly composed of a vinyl aromatic compound of the block copolymer is a hard segment of the block copolymer, and its glass transition point is 90°C or higher, preferably 0°C or higher. In this block, the weight ratio of the vinyl aromatic compound and the conjugated diene compound is
~/θ010, preferably ♂0/20 to 10010, more preferably lOθ10. The distribution of the conjugated diene compound, which is a minor component, in this block is as follows:
It may be random, Chibird (in which the number of heptomer components increases or decreases along the molecular chain), partially block, or a combination thereof.

On the other hand, a polymer block mainly composed of a conjugated diene compound is a soft segment of a block copolymer, and its glass transition point is from O'C to F, preferably from -20C to below. In this block, the weight ratio of the vinyl aromatic compound and the conjugated diene compound is 0/100 to 4tO/Otsu0,
Preferably, the composition range is θ/10θ to 30/7θ. The distribution of the vinyl aromatic compound, which is the raw material component, in this block may be random, Chivord, partially block-like, or a combination thereof. When containing two or more polymer blocks mainly composed of vinyl aromatic compounds or polymer blocks mainly composed of conjugated diene compounds, each block may have the same structure or different structures.

In the above block copolymer, the weight ratio of the polymer block mainly composed of a vinyl aromatic compound and the polymer block mainly composed of a conjugated diene compound is j/9 j -93
7! , preferably in the range of 10/90 to θ/10.

The vinyl aromatic compounds constituting the block copolymer include styrene, θ-methylstyrene, p-methylstyrene, p-1crt butylstyrene, /, 3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene, etc. A particularly common example is styrene. These may be used not only as a mixture of seven types but also as a mixture of two or more types. Conjugated dienes include diolefins having a pair of conjugated double bonds with different carbon numbers, such as /, 3-butadiene, 2-methyl to 3-butadiene (isoprene), λ, 3-diolefin, ) +le/, 3 f9 i;'ene, /, 3-pentagene, 7
．． Examples include 3-hequinadiene, and particularly common examples include 7,3-butadiene and isoprene. These may be used not only as a mixture of seven types but also as a mixture of two or more types.

The average molecular weight of the block copolymer is 10. θθ0~/, 0
00,000 preferably Ha20,000~j″00,0
00, more preferably 30,000~! The range is θθ, 00θ.

Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

As an example, the following structural formula can be given.

(A-B)n%A+B-A)n, B-(-A-B
)n((A-B)n+FFrT-T-c((B
- 人hB 鈷四TC (in the formula, 人 is a polymer block mainly composed of a vinyl aromatic compound, B is a polymer block mainly composed of a conjugated diene compound, and C is a coupling agent residue or a polyfunctional organolithium compound) (m and n are integers of 7 or more.) The block copolymer used in the present invention usually contains benzene,
Anionic polymerization of a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as hexane or cyclohexane using an organic lyticum compound such as butyllithium as a polymerization catalyst A branched or radial block copolymer can be obtained by bonding a block copolymer having a lyticum active end with a polyfunctional coupling agent such as silicon tetrachloride.Vinyl aromatic compounds obtained by any other manufacturing method Even a compound-conjugated diene compound block copolymer can be used as long as it falls within the range of the above limitations.

The above-mentioned block copolymers are not limited to seven types, but it is also possible to combine two or more types of block copolymers with different polymer structures, such as the number of styrene contents, the number of molecules, and the number of blocks.

The block copolymer used in the present invention has 7.
A composition having a content of 2-vinyl bonds exceeding /1 fTo is necessary to obtain a composition with excellent heat resistance.

The content of /, 2-vinyl bonds in the copolymer (1) is A
r+alytical Chemistry Volume 2/Volume 9
It can be measured using an infrared spectrophotometer according to the method described on page 23 (79 years) E.

The polysulfone polymer has the general formula ÷Ar -B-R -802+ or +Ar-802
It is a thermoplastic polysulfone having a structural unit of ÷ (in the above formula, Ar represents a phenylene group, and B represents oxygen, sulfur, or an aromatic diol residue).

Preferred examples include poly(ether sulfone) and poly(¥, II-bisphenol ether sulfone).

The modified block copolymer composition of the present invention comprises component (1) 1
Ingredients (1) per 00 parts by weight! ~ 20 Jyusha Miyako.

The ratio of component (11) to component 11) / 00 parts by weight is! If it is less than the electric lamp part, the effect of improving heat resistance is small;
If the amount exceeds 70 parts by weight, the elastic properties of the composition will be lost.

Additives can be added to the block copolymer composition of the present invention as needed. The type of additive is not particularly limited as long as it is commonly used in the formulation of plastics. For example, glass fibers, glass peas, inorganic reinforcing agents such as phosphorus, charcoal, and talc, organic reinforcing agents such as organic fibers, coumaron indene resins, crosslinking agents such as organic peroxinides and inorganic peroxides, titanium white, and carbon black. , pigments such as iron oxide, dyes, flame retardants, antioxidants, ultraviolet absorbers, antimagnetic agents, lubricants, plasticizers,
Other fillers or mixtures thereof may also be used.

The block copolymer composition of the present invention comprising component +11 and component 1) can be produced by any conventionally known blending method. For example, open roll, internal mixer, internal mixer, co-kneader,
A melt-kneading method using a general mixer such as a continuous kneader or an extruder equipped with a twin-screw rotor, a method in which each component is dissolved in a solvent or a dispersion mixer, and the solvent is removed by heating are used.

The block copolymer composition of the present invention obtained in this way can be processed by any conventionally known molding method, such as extrusion molding,
Injection molding, etc. (2) It can be easily molded into molded products of various shapes, and can be used for rubber hoses, belts, anti-vibration materials, footwear, wire covering materials, packing, foam products, toys, food packaging containers, etc.

(Examples and Effects) Some Examples are shown below, but these are intended to explain the present invention more specifically, and are not intended to limit the scope of the present invention.

Reference Examples / ~ 3 (and Comparative Reference Examples /) Production of block copolymer The inside of a dry polymerization vessel with an internal volume of 301 cm was sufficiently replaced with nitrogen gas, and purified and dehydrated cyclohexane of 1 kg was added to it. /, 3 and 9 styrene were charged, and then a hexane solution containing 2 and ♂ of n-butyllithium was added as a polymerization initiator, and then the internal temperature was raised to 20° C. to carry out polymerization. After the polymerization of styrene is substantially completed, the butadiene, /, j! (g of styrene and 7., r
A mixture of Kf cyclohexane was added and polymerized at 70°C. After the polymerization was substantially complete, a small amount of methanol was added to stop the polymerization. Next, 2Of, Otsu-
DiterL-butyl-4t-methylphenol and 20
After adding trisnonylphenyl phosphite (1), the solvent cyclohexane was distilled off under heating to obtain a block copolymer (sample/). The styrene content of this copolymer was 25% by weight, and approximately ♂j% of the styrene was present as block polystyrene.

A production sample of a block copolymer composition was mixed with polyphenylene sulfide fine powder or polysulfone in the blending ratio shown in Table 1. A solid mixture was obtained.Then, this mixture was made into pellets using a 30 m/m extruder.The obtained pellets were injection molded to prepare test specimens, and the tensile strength, Izotsu Yamaki strong absorption, and heat absorption were measured. The deformation temperature was measured.Also 0
A press sheet with a thickness of 2 m/m was produced, and the total light transmittance of the sheet was measured. These measurement results are shown in Table 1.

Example 1 (and Comparative Examples/, 2) The same polymerization vessel as used in Reference Examples 7 to 3 (charged with purified, dehydrated g, rKy cyclohexane and/or O's styrene, and then added rope as a polymerization initiator) After adding a chitin solution containing 2.2% of chilllithium, the internal temperature was raised to θ°C to carry out polymerization.

After the polymerization of styrene has substantially completed (2), add 0.♂ butadiene, 7 kg of styrene, ?,!; Kq of cyclohexitine and ♂2 of tetrahydrofuran U compound, and heat at 30°C. After the polymerization was substantially completed, a block copolymer was obtained by the same treatment as described above.
Sample, 2). The styrene content of this copolymer is ♂θ
The content of 2-vinyl bonds in weight percent was approximately 2j%.

The results of evaluating the sample according to Reference Example/~3 are shown in the first
Shown in the table.

Comparative Example 7 was produced in the same manner as Sample 2 except that tetrahydrofuran was not used during polymerization.
．． This is a composition prepared using a block copolymer (sample λ') having a 2-vinyl bond content of 77%.

(Note/) Heat deformation temperature approx. 2oz ℃ (Load/♂, Otsu Kf)
polyether sulfone was used.

(Note 2) Based on JISK-Otsu♂2/. Incidentally, the isot surface impact strength is a measured value with a notch.

(Note 3) Based on A3TM D Otsu 4t♂ (Load/L!'',
t(-y) (note) Based on JISK-67/da.

Reference Examples y to B (and Comparative Reference Example 2) Manufacture of block copolymers The same polymerization vessel used in Reference Examples 7 to 3 (2 Kt of hexane and θ, / 9 of styrene and 0.6~ of butadiene were added, and then a hexane solution containing n-butyrrhizicum as a polymerization initiator was added, and the internal temperature was raised to 20°C to carry out polymerization. Target (After finishing the second, go to 71 to 9,
θ,! A mixture of styrene and/or butadiene was added and polymerized at 20°C. After the polymerization was substantially completed, a block copolymer (Sample 3) was obtained by the same treatment as in Examples 7 to 3 (Sample 3).The styrene content of this copolymer was About ♂0 of styrene
was present as block polystyrene.

Manufacture sample 3 of block copolymer composition and polysulfone were dissolved in chloroform according to the blending ratio shown in Table 2, and after thorough mixing, chloroform was distilled off by heating to obtain a solid mixture. The mixture was sufficiently kneaded in a plastic bender and compression molded to prepare a test piece, and the tensile properties and heat distortion temperature were measured.The measurement results are shown in Table 2.

As a comparative reference example, a composition was prepared in which 100 parts by weight of polysulfone was added to Sample 3 (xoo = a part), and the tensile properties were determined.
It is clear that elastic properties are lost below % (
It was two.

Example 2 (and Comparative Example 3) Radial block Koa combination 5-tt/y (manufactured by Phillips Petroleum) (Namburg, Steam λ-
The vinyl bond content (FJ/7%) was evaluated according to Examples q to B (= f + lfi). The results are shown in Table 2 (-). (Table 2 is as follows) (Note J-) J I 8 K-630B: Compliant.

(Note 6) A compression molded sheet with a thickness of 2 m in the form of a strip (=, based on the cross-sectional area of the original sample) is applied with a load of OKv'cd at room temperature, and then the temperature around the sample is lowered to about 2. C15
) and the temperature at which the sample was elongated by 104 of its original length was defined as the heating deformation temperature.

Comparative Example In the production of the block copolymers shown in Reference Examples D to 6, a mixture of hexane, styrene and butadiene was
A block copolymer (sample sample) was obtained in the same manner as the block copolymer except that it was continuously fed into a polymerization vessel (-) at a speed of - and polymerized.

The styrene content of this copolymer was 0 m tit %, about 23 wt % of the styrene was present as block polystyrene, and the content of 2-vinyl bonds was //.

sample! were evaluated according to Reference Examples y-6 (==), but no improvement effect on dj4 thermal properties was observed as much as that shown in Reference Example 4t-6.

Claims (1)

[Claims] 1(1) A block copolymer containing one or more polymer blocks mainly composed of a vinyl aromatic compound and one or more polymer blocks mainly composed of a conjugated diene compound. 100 parts by weight of a block copolymer having a vinyl aromatic compound content of 5 to 95% by weight and a 1,2-vinyl bond content of more than 15%; (ii) 5 to 90% of a polysulfone-based polymer; Block copolymer composition 2 consisting of 70 parts by weight Component (i) is a block copolymer having a vinyl aromatic compound content of 10% by weight or more and less than 60% by weight, according to claim 1. Composition 3 Component (i) has a vinyl aromatic compound content of 60 to
Composition 4 according to claim 1, which is a block copolymer having a content of 90% by weight. The polysulfone polymer of component (ii) has the general formula -
[Ar-B-Ar-SO_2]-or-[Ar-SO
_2]-(In the above formula, Ar represents a phenylene group, and B represents oxygen, sulfur, or an aromatic diol residue.) Composition