JPS6255548B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polymer composition, more specifically a modified block copolymer obtained by modifying a vinyl aromatic compound-conjugated diene compound block copolymer with a dicarboxylic acid or a derivative thereof, and an oligomer containing a polar group. This invention relates to a novel polymer composition consisting of a combination of the following. BACKGROUND ART Vinyl aromatic compound-conjugated diene compound block copolymers, particularly styrene-butadiene block copolymers, which are representative thereof, are polymeric materials that have attracted attention in recent years. Among the above styrene-butadiene block copolymers, those containing two or more polystyrene blocks and one or more polybutadiene blocks and having a relatively low styrene content exhibit rubber elasticity even without vulcanization, and As a thermoplastic elastomer that can be molded in the same way as thermoplastic plastics,
It is used in various fields such as molding materials for shoe soles, modifying polystyrene resins, and adhesives. These thermoplastic elastomer styrene-butadiene block copolymers are known, for example, under the trade names "Tuffprene" (manufactured by Asahi Kasei Industries), "Solprene T" (manufactured by Nippon Elastomers), and "KRATON" (manufactured by Ciel Chemical). There is. In addition, styrene-butadiene block copolymer with a high styrene content is a transparent impact-resistant resin and is used in fields such as sheets and films.
"Resin" (manufactured by Philips Petroleum) is known. These vinyl aromatic compound-conjugated diene compound block copolymers have useful properties as described above, and are compatible with vinyl aromatic polymers, conjugated diene polymers, polyolefin polymers, etc. Because of its good solubility, it is also effective as a modifier for these various polymers. However, vinyl aromatic compound-conjugated diene compound block copolymers do not necessarily have good compatibility with polar substances, especially polar polymer compounds.
The reality is that it is difficult to obtain the expected results with polymer blends with polar polymers. Furthermore, the vinyl aromatic compound-conjugated diene compound block copolymer does not have good oil resistance due to its polymer structure. The present inventors have already published Japanese Patent Application No. 53-99102 (August 16, 1978) for the purpose of improving vinyl aromatic compound-conjugated diene compound block copolymers.
proposed a method to obtain a modified block copolymer by adding an unsaturated dicarboxylic acid represented by maleic anhydride or a derivative thereof to the above block copolymer without losing its fluidity. However, as a result of further intensive studies, it has been found that a new and useful polymer composition can be obtained by combining a block copolymer modified with the above-mentioned dicarboxylic acid or its derivative and a polar group-containing oligomer. They discovered this and arrived at the present invention. The gist of the present invention is that (a) component: content of vinyl aromatic compound is 5 to 95
A modified block formed by bonding 1 to 50 molecular units containing a dicarboxylic acid group or its derivative group per molecule of the block copolymer to a block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound in the same amount by weight. 100 parts by weight of a copolymer; (b) Component: 0.5 to 100 parts by weight of an oligomer having a number average molecular weight of 100 to 10,000 and containing a polar group selected from an amino group, a hydroxyl group, an epoxy group, and an isocyanate group; A polymer composition comprising: The composition of the present invention is a novel polymer composition that has not existed before, and its characteristics are as described below. The point is that it has various characteristics that are not found in other countries. The present invention will be described in detail below. The modified block copolymer used as component (a) in the present invention is a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound as a base, and a molecular unit containing a dicarboxylic acid group or a derivative thereof is bonded. It is something. The block copolymer consisting of the vinyl aromatic compound and the conjugated diene compound (hereinafter simply referred to as "block copolymer") serving as the base has one or more, preferably two, polymer blocks mainly composed of the vinyl aromatic compound. and one or more polymer blocks mainly composed of a conjugated diene compound. The content of the vinyl aromatic compound in this block copolymer is 5 to 95% by weight, preferably 10 to 90% by weight, and more preferably 15 to 85% by weight. When the content of vinyl aromatic compounds in the block copolymer is less than about 70% by weight, often less than about 60% by weight, the block copolymer is rubbery, and when this content exceeds about 70% by weight, The block copolymers are usually transparent impact resistant resins. Further, in the above block copolymer, the weight ratio of the polymer block mainly consisting of a vinyl aromatic compound to the polymer block mainly consisting of a conjugated diene compound is 5/95 to 95/5, preferably 10/90 to 10/90. 90／
The range is 10. The polymer block of the block copolymer, which is mainly composed of vinyl aromatic compounds, is the hard segment of the block copolymer, and its glass transition point is 40°C.
The temperature is preferably 60°C or higher. In this block, the weight ratio of the vinyl aromatic compound and the conjugated diene compound is 60/40 to 100/0, preferably
Composition range from 80/20 to 100/0, more preferably
100/0, and the distribution of the minor component of the conjugated diene compound in this block can be random, tapered (increasing or decreasing monomer component along the molecular chain), partially block-like, or any combination thereof. It may be. On the other hand, a polymer block mainly composed of a conjugated diene compound is a soft segment in a block copolymer, and its glass transition point is 20°C or lower, preferably -20°C or lower. In this block, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 40/60, preferably 0/100 to 40/60.
With a composition range of 30/70, the distribution of the minor vinyl aromatic compound in this block may be random, tapered, partially block-like, or any combination thereof. 2 polymer blocks mainly composed of vinyl aromatic compounds
or when it contains two or more polymer blocks mainly composed of conjugated diene compounds, each block may have the same structure or different structures. As the vinyl aromatic compound constituting the block copolymer, one or more types are selected from styrene, α-methylstyrene vinyltoluene, p-tert-butylstyrene, etc., and styrene is particularly preferred. On the other hand, as the conjugated diene compound, one or more types are selected from butadiene, isoprene, 1,3-pentadiene, etc. Among them, butadiene or a combination of conjugated diene compounds mainly composed of butadiene is preferable, and butadiene is particularly preferable. . In the block copolymer, the number average molecular weight of each polymer block is 1,000 to 300,000, preferably 3,000 to 300,000.
200,000, more preferably in the range of 5,000 to 100,000, and the number average molecular weight of the entire block copolymer is
The range is 5,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 20,000 to 300,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is
It ranges from 1.01 to 10, preferably from 1.01 to 5. Furthermore, the molecular structure of block copolymers is linear,
It may be branched, radial, or any combination thereof. Further, the above-mentioned block copolymer may be slightly modified with an organic compound or an inorganic compound as long as its properties are not lost. The various polymer structure limitations regarding the block copolymer described above are necessary for the modified block copolymer to maintain its mechanical properties as a thermoplastic polymer. The block copolymer used in the present invention is usually produced by anionically polymerizing a vinyl aromatic compound and a conjugated diene compound using an organic lithium compound such as butyllithium as a polymerization catalyst in an inert hydrocarbon solvent such as benzene, hexane, or cyclohexane. By combining the block copolymer having lithium active terminals obtained by the above method with a polyfunctional coupling agent such as silicon tetrachloride, branched,
A radial block copolymer is obtained. others,
Any vinyl aromatic compound-conjugated diene compound block copolymer obtained by any production method can be used as long as it falls within the above-mentioned limits. As the above-mentioned block copolymer, it is possible to use not only one kind but also a combination of two or more kinds of block copolymers having different polymer structures such as styrene content, molecular weight, number of blocks, etc. Next, the modified block copolymer of the present invention is obtained by subjecting the block copolymer to an addition reaction with an unsaturated dicarboxylic acid or a derivative thereof, and these unsaturated dicarboxylic acids or derivatives thereof are At the position of its active unsaturated bond,
It is added to the conjugated diene moiety of the block copolymer.
These are 1 to 1 per molecule of block copolymer.
50 pieces, preferably 1 to 30 pieces, more preferably 1 to 30 pieces
The addition of 20 is necessary for the composition to have the desired properties. If the amount added is less than 1, the effect of improving the physical properties will not be sufficient compared to the unmodified one, and even if it exceeds 50, the improvement effect will be less than if the amount added is less than that. The amount of molecular units containing a dicarboxylic acid group or its derivative group in the modified block copolymer can be determined by measuring the dicarboxylic acid group or its derivative group in the modified block copolymer obtained by the method described below using an infrared spectrophotometer. It can be easily measured by methods such as or titration. Examples of the unsaturated dicarboxylic acids or derivatives thereof are maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-
Examples include dicarboxylic acids such as 1,2-dicarboxylic acid and endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, and acid anhydrides and esters of these dicarboxylic acids. Among unsaturated dicarboxylic acids or derivatives thereof, maleic acid, fumaric acid, and maleic anhydride are preferred. The modified block copolymer of the present invention can be obtained by grafting an unsaturated dicarboxylic acid or a derivative thereof to the block copolymer in a molten state or a solution state, with or without the use of a radical initiator. can get. The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or may have poor flowability and poor processability. It is not preferable to use a production method that results in a poor reaction quality, and it is preferable, for example, to carry out the graft reaction under melt-mixing conditions such as an extruder that substantially does not generate radicals. Such a reaction can be carried out using radicals such as peroxides and azone compounds, as described in Japanese Patent Application No. 1983-99102 (filed on August 16, 1978), filed earlier by the present applicant. It is carried out without adding an initiator to the reaction system, and by adding known stabilizers such as phenol-based, phosphorus-based, and amine-based stabilizers to suppress free radicals generated under heating or high shear during the reaction. be able to. Next, the polar group-containing oligomer of component (b) of the present invention will be described in detail. The above oligomer is a low molecular weight polymer, and has a number average molecular weight of 100 to 10,000, preferably 500.
More than 5,000 but less than 5,000. Here, the polar group is a polar group selected from an amino group, a hydroxyl group, an epoxy group, and an isocyanate group, and reacts with a dicarboxylic acid group or its derivative group contained in the modified block copolymer. These reactive polar groups react with the molecular unit containing the dicarboxylic acid group or its derivative group of component (a), resulting in a reaction product of component (a) and component (b). The composition of the present invention preferably contains a reaction product of these components (a) and (b). The reaction product of component (a) and component (b) above is determined by the number of reactive groups contained in the oligomer of component (b) or (a)
By adjusting the molar ratio between the reactive group of the component and the functional group of the component (b), component (a) can be used as the main component and (b)
a graft copolymer in which components are bonded as branch components;
Or a crosslinked polymer in which component (a) is crosslinked with component (b), or a mixture thereof. It is preferable that the reaction composition contains a graft copolymer, and it is particularly preferable that the reaction composition contains only a graft copolymer. In order for components (a) and (b) to form a graft copolymer, the oligomer of component (b) must contain one reactive polar group per molecule, preferably one at one end. This is effective. The polar group-containing oligomer used as component (b) is explained in detail in "Oligomer Handbook" (published by Kagaku Kogyo Nippo Co., Ltd.).
Examples of these are conjugated diene-based oligomers such as terminally aminated conjugated diene-based oligomers, terminally hydroxylated conjugated diene-based oligomers, isocyanated conjugated diene-based oligomers, and epoxidized conjugated diene-based oligomers. Oligomers such as 1,2-polybutadiene,
It is derived from 1,4-polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, etc. Examples of polyether oligomers include polyethylene glycol, polypropylene glycol, polybutylene glycol, and mono- or diesters thereof. Examples of polyester-based oligomers include saturated polyesters produced by condensation of aliphatic dibasic acids and diols, and polycaprolactone. Other examples of polyamide-based oligomers include dimer acid-based polyamides, polyisocyanate oligomers, and polyethyleneimine oligomers, and examples of epoxy-based oligomers include polyepoxy oligomers such as copolymers of glycidyl methacrylate. Among the various oligomers mentioned above, examples suitable for the composition of the present invention having a reactive group at one end include:
Alkyl, aryl or aralkyl ethers at one end of dihydroxy oligomers such as dihydroxy polyethers and dihydroxy polyesters, polyamide oligomers containing amino groups at one end,
Examples include oligomers containing an isocyanate group at one end. Furthermore, even if the oligomer contains more than one reactive group in the molecule, an excessive number of moles of the reactive group may be added to the number of moles of the reactive group contained in the modified block copolymer. By using oligomers and adjusting the reaction conditions and reaction method, component (a) and (b)
It is possible to obtain a composition containing a graft copolymer with the component. The above oligomers can be used alone or in a mixture of two or more. The composition of component (a) and component (b) of the composition of the present invention is:
The amount of component (b) is 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight, relative to 100 parts by weight of component (a). If the amount of component (b) is too large, the mechanical properties of the composition will deteriorate, which is undesirable. Furthermore, in the composition of the present invention, component (a) and (b)
Even if the components can react, the reaction does not proceed completely, or the molar ratio of either component (a) or component (b) is excessive, leaving unreacted components. It can also include things like. In such cases, the composition still has its properties. Incidentally, by-products produced by the reaction between component (a) and component (b), such as water produced by the esterification reaction between a dicarboxylic acid group and a hydroxyl group, may be removed from the above composition, or , unreacted components may be removed. The composition of the present invention is characterized by the composition range of component (a) and component (b), the content of the vinyl aromatic compound of component (a),
It can be adjusted by changing the type of oligomer of component (b), but in any case, it has properties that the corresponding modified block copolymer of component (a) does not have, such as , compatibility with polar high molecular weight polymers, oil resistance, processing properties, surface properties, air resistance properties, abrasion resistance, etc. The composition of the present invention can be obtained by using (a) and (b) a method of dissolving both components in a suitable solvent and mixing them, a mixing roll, a kneader, a mixer such as a Brabender Plastograph, a Banbury mixer, a single screw or There is a method of mixing components (a) and (b) in a molten state using ordinary mixing equipment such as a multi-screw extruder.
In order to efficiently advance the reaction with the components, heating or addition of a catalyst can also be carried out. The composition of the present invention includes, as additives, stabilizers,
It is also possible to add fillers, lubricants, flame retardants, colorants, etc. as necessary. Moreover, it can also be made into a composition with various thermoplastic polymers. The composition of the present invention is a novel composition and can be used in various fields, including applications for molded products where conventional thermoplastic elastomers are used, and applications for adhesives and pressure-sensitive adhesives. , laminates, paints, surface treatment agents, etc., and molded products, films, sheets, and other fields in which thermoplastic resins are used. Some Examples are shown below, but these are intended to explain the present invention more specifically, and it goes without saying that the scope of the present invention is not limited thereto. Reference Example 1 [Preparation of modified block copolymer] Using Sample P, which is a thermoplastic elastomer of styrene-butadiene block copolymer, a modified block copolymer (Sample P) to which maleic anhydride was grafted was prepared by the method shown below. ) was obtained. Note that sample p was obtained using n-butyllithium as a polymerization catalyst in a hexane solution,
Based on the polymerization method and analysis results, it is thought to have the following structure. Polymer structure: B ₁ - S ₁ - B ₂ - S ₂ (linear) B ₁ = 18% by weight, [B] / [S] = 16/2 (tapered) S ₁ = 17% by weight [B] / [S] = 0/17 B ₂ = 49% by weight [B] / [S] = 46/3 (Tapered) S ₂ = 16% by weight [B] / [S] = 0/16 However, B _o ... Budadiene Polymer block mainly composed of S _o ...Polymer block mainly composed of styrene The integer n represents the order along the molecular chain. [B]... Butadiene content (% by weight relative to the entire block copolymer) [S]... Styrene content (% by weight relative to the entire block copolymer) The same descriptions will be used in the following examples. Styrene content: 38% by weight Block styrene content: 33% by weight Weight average molecular weight (Mw): 81000 Number average molecular weight (Mn): 62000 Melt index: 11.0g/10min (JIS-K-6870, load 5Kg 200℃) 2.5 parts by weight of maleic anhydride and 0.3 parts by weight of BHT as an anti-gelling agent for 100 parts by weight of sample p.
(butyl hydroxytoluene) and 0.2 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full-flight screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 200 to 230°C. Unreacted maleic anhydride was removed from the obtained polymer by drying under reduced pressure. The analysis results of the modified block copolymer (sample P) are as follows:
The index was 7.1 g/10 min, the toluene insoluble content was 0.05% by weight, and the amount of maleic anhydride added was 1.30 parts by weight per 100 parts by weight of the block copolymer, as determined by titration with sodium methylate. Further, the content of maleic anhydride molecular units calculated from the measured values was about 8.2 on average per molecule of the block copolymer. Example 1 and Comparative Example 1 Modified block copolymer of component (a) (sample P) 100
Polyethylene glycol nonyl phenyl ether (NOF Co., Ltd., Nonion NS-220, degree of polymerization of polyethylene glycol 20, number average molecular weight
A composition was prepared using 15 parts by weight of 1100) in the following manner. After the component (a) was put into a Brabender Plastograph whose temperature was adjusted to 170°C and melted, the component (b) was added little by little over 20 minutes, and kneading was continued for an additional 10 minutes. The resulting composition (Example 1) was transparent;
When analyzed with an infrared spectrophotometer, the absorption of dicarboxylic acid anhydride in the modified block copolymer almost disappeared around 1785 cm ^-1 , and a new absorption appeared around 1730 cm ^-1 .
Absorption of ester appeared, and it was confirmed that the acid anhydride group and the terminal hydroxyl group of component (b) reacted to form a graft copolymer. It was confirmed by extraction with a solvent that about 10% of component (b) was unreacted. For comparison, a similar composition (Comparative Example 1) was prepared using sample p of an unmodified block copolymer.
An attempt was made to carry out the same mixing operation as in Example 1 in order to obtain this product, but the miscibility of both components (a) and (b) was poor and only a small amount of component (b) could be added. Also, this composition was opaque. Table 1 shows the physical property values of the composition of Example 1 and sample p of an unmodified block copolymer for comparison. The composition of Example 1 showed almost no decrease in mechanical strength such as tensile strength and hardness compared to Sample P, and further improved oil resistance while maintaining the rubber elasticity and fluidity of Sample P. Therefore, it can be said that it is a useful composition. Further, although the blending amounts were different, the composition of Comparative Example 1 showed a significant decrease in tensile strength and the like.

[Table] Reference Example 2 [Production of modified block copolymer resin] KR-01, a commercially available styrene-butadiene block copolymer resin (manufactured by Philips Petroleum Co., Ltd., styrene content 78% by weight, melt index 5.3g) A resin-like modified block copolymer (sample Q) to which maleic anhydride was added was obtained by a modification method using an extruder similar to that used to obtain sample P. The melt index of sample Q is 4.1g/
The amount of maleic anhydride added for 10 minutes was 1.1 parts by weight per 100 parts by weight of the block copolymer. The content of maleic anhydride molecular units calculated from this measured value is approximately
There were 10.1 pieces. Example 2, Example 3 and Comparative Example 2 Polycaprolactam oligomer with terminal amino groups (this is obtained by polymerizing ε-caprolactam using n-butylamine as a molecular weight regulator, and analysis of terminal amino groups) (an oligomer with a number average molecular weight of 950), and the modified block copolymers Sample P and Sample Q with the composition shown in Table 2 at a temperature of 200°C for 5 minutes in a Brabender plastograph. The compositions of Examples 2 and 3 were obtained by kneading. All of these compositions were transparent, and analysis using an infrared spectrophotometer confirmed the reaction between the acid anhydride group in the modified block copolymer and the amine-terminated oligomer. On the other hand, as Comparative Example 2, a composition was obtained by kneading the commercially available styrene-butadiene block copolymer resin KR-01 without modification with the polycaprolactam oligomer having terminal amino groups in the same manner. Table 3 shows the physical properties of the composition of Example 2,
Compared to sample p of the reference example in Table 1, mechanical properties and oil resistance are improved. In addition, as shown in Table 4,
The modified block copolymer resin composition of Example 3 has superior transparency and mechanical strength compared to the composition of Comparative Example 2, and also has transparency equivalent to that of the unmodified block copolymer resin of Reference Example. and impact resistant. As described above, the composition of the present invention can be said to be a useful composition.

【table】

【table】

[Table] Examples 4 to 7 and Comparative Examples 3 to 6 Using the various polar oligomers shown in Table 5, compositions of these and a modified block copolymer (sample P) were prepared in the same manner as in the previous example. . Similarly, compositions of these polar oligomers and the unmodified block copolymer sample p were obtained. These physical properties were measured and the results are shown in Table 5. As is clear from the tensile strength and oil resistance results shown in Table 5, each of the compositions of Examples 4 to 7 had lower
The physical properties were improved, indicating that polar oligomers are effective in improving block copolymers.

【table】

Claims (1)

[Claims] 1 (a) Component: The content of vinyl aromatic compound is 5
Consisting of a block copolymer consisting of ~95% by weight of a vinyl aromatic compound and a conjugated diene compound, 1 to 50 molecular units containing a dicarboxylic acid group or its derivative group are bonded per molecule of the block copolymer. 100 parts by weight of a modified block copolymer; (b) Component: 0.5 to 100 parts by weight of an oligomer having a number average molecular weight of 100 to 10,000 and containing a polar group selected from amino groups, hydroxyl groups, epoxy groups, and isocyanate groups. A polymer composition comprising: 2. The composition according to claim 1, wherein the dicarboxylic acid derivative group of component (a) is a dicarboxylic anhydride group or a dicarboxylic acid monoester group. 3 The number average molecular weight of the oligomer of component (b) is 500
The composition according to claim 1, which has a molecular weight of 5,000 or more. 4 The polar group of the oligomer is a polar group that reacts with a dicarboxylic acid group or its derivative group, and the composition is
Any one of claims 1 to 3, which contains a reaction product of component (a) and component (b).
The composition described in Section. 5. The reaction product of component (a) and component (b) is a graft copolymer in which component (a) is a main component and component (b) is a branch component. Composition. 6. The composition according to claim 5, wherein component (b) contains one polar group per molecule. 7. Claim 1, wherein component (b) is an oligomer having a primary or secondary amino group as a terminal group,
The composition according to item 5 or 6. 8. The composition according to claim 7, wherein component (b) is a polyamide oligomer having primary or secondary amino groups as terminal groups. 9. The composition according to claim 1, 5 or 6, wherein component (b) is an oligomer having a hydroxyl group as a terminal group. 10. The composition of claim 9, wherein component (b) is a monoalkyl ether, monoaryl ether or monoaralkyl ether of a dihydroxy oligomer. 11. The composition according to claim 10, wherein the dihydroxy oligomer is selected from dihydroxy polyether oligomers, dihydroxy polyester oligomers, and dihydroxy polyconjugated diene oligomers. 12. The composition according to claim 1 or 5, wherein component (b) is a polyepoxy oligomer. 13. The composition according to claim 12, wherein the polyepoxy oligomer is an epoxidized polyconjugated diene oligomer. 14. The composition according to claim 12, wherein the polyepoxy oligomer is a copolymer of glycidyl methacrylate and another monomer copolymerizable therewith. 15. The composition according to claim 1 or 5, wherein component (b) is a polyisocyanate oligomer.