JP2009161724A - Oligoolefin halogenated at both ends and triblock copolymer produced from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oligoolefin halogenated at both ends which is useful as a raw material for the production of a functional copolymer, and to provide a triblock copolymer produced from the oligoolefin. <P>SOLUTION: An oligoolefin which is halogenated at both ends and is represented by the general formula (1) and a triblock copolymer represented by the general formula (2) are provided. In the formulas, X is a halogen atom; n is an integer of 10-1,000; and A is a vinyl polymer block. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a both-end halogenated oligoolefin having a novel structure, a triblock copolymer using the same, and a production method thereof.

  General-purpose polymers such as polypropylene and poly 1-butene are inexpensive and are used for various applications by utilizing their excellent properties.

  However, because these general-purpose polymers are nonpolar and it is difficult to introduce functional groups, the interaction with other polar substances is poor, and strengthening by mixing with polymers having other polar groups Is difficult. Moreover, it has the problem that it is inferior to coating property and adhesiveness.

  In recent years, research on new functionalized polypropylene to solve these problems has been actively conducted. One of them is synthesis of a diblock copolymer through functionalization of one-end vinylidene polypropylene synthesized by a polymerization reaction using a metallocene catalyst. This is based on the fact that the β-position hydrogen is selectively eliminated at the growth terminal by the selection of the polymerization conditions, and a vinylidene type double bond is formed at one terminal. The single-end double bond can be easily converted into various functional groups, and thus is very useful for functionalization of polypropylene. However, in this case, since the functional group in the molecular chain exists only at one end, there is a limit in improving the physical properties.

Under such a technical background, the present inventors have already synthesized olefin oligomers containing vinylidene bonds at both ends obtained by highly controlled pyrolysis of polyolefin via a functional group conversion of the vinylidene group. Various functional copolymers were provided (see Patent Documents 1 to 3).
JP 2003-292589 A Japanese Patent No. 3959043 JP 2004-107508 A

  It is an object of the present invention to provide a both-end halogenated oligoolefin having a novel structure and usable as a raw material for producing a functional copolymer, a triblock copolymer using the same, and a production method thereof. .

  The present inventors have found that a halogenated oligoolefin at both ends can be obtained by functional group conversion of the vinylidene bond of the oligoolefin containing both ends vinylidene bond obtained by highly controlled pyrolysis. Furthermore, atom transfer radical polymerization (ATRP) can be performed using various vinyl monomers using the both-end halogenated oligoolefin as an initiator, whereby a high molecular weight triblock copolymer can be used. The inventors found that a polymer can be obtained and completed the present invention.

That is, this invention relates to the both-ends halogenated oligoolefin represented by following General formula (1).
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (Independently selected from the group consisting of (CH ₃ ) ₂ , X is a halogen atom, and n is an integer of 10 to 1000.)

Furthermore, the present invention relates to the above-mentioned both-end halogenated oligoolefin, wherein R ³ is —CH ₃ , R ¹ and R ² are all methyl groups, and X is Br.

The present invention also relates to a triblock copolymer represented by the following general formula (2).
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (CH ₃ ) _{2 is} independently selected from the group consisting of ₂ , X is a halogen atom, n is an integer of 10 to 1000. A is a vinyl polymer block, and is represented by the following general formula (3). Is done.
(Wherein, R ⁴ is a methyl group or hydrogen, R ⁵ is —COOCH ₃ , —COOC ₂ H ₅ , —COOnBu, —COOtBu, —CONHCH (CH ₃ ) ₂ , —COOCH ₂ CH ₂ OH, — COOCH ₂ CH ₂ N (CH ₃ ) ₂ , —CN, —COOH or a phenyl group, and m is an integer of 1 to 10,000.)

Moreover, this invention is a both-ends halogenated oligoolefin represented by following General formula (1)
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (Independently selected from the group consisting of (CH ₃ ) ₂ , X is a halogen atom, and n is an integer of 10 to 1000).
Methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-isopropyl (meth) acrylamide, (meth) The present invention relates to a method for producing a triblock copolymer, which comprises atom transfer radical polymerization of 2-hydroxymethyl acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, or styrene.

  Moreover, this invention hydroxylates the both-ends vinylidene bond containing oligoolefin, and also performs an esterification reaction with (alpha) -haloacyl halide, The both-ends halogenated oligoolefin represented by the said General formula (1) characterized by the above-mentioned. Including the manufacturing method.

  In addition, the present invention provides a triblock copolymer obtained by atom transfer radical polymerization of one or two or more types of vinyl monomers using the both-end halogenated oligoolefin represented by the general formula (1) as an initiator. including.

  Furthermore, the present invention includes a multiblock copolymer obtained by subjecting the triblock copolymer represented by the general formula (2) to an atom transfer radical coupling reaction.

  The both-end halogenated oligoolefin according to the present invention can be used as a raw material for producing a functional copolymer because it can act with various monomers as a polymerization initiator for atom transfer radical polymerization to form a triblock copolymer. .

  The triblock copolymer of the present invention is constituted by atom transfer radical polymerization of a vinyl monomer using a halogenated oligoolefin at both ends as an initiator. Such a triblock copolymer has a property in which a block at both ends and a block connecting them are different, so that it is used as a compatibilizing agent for two or more types of polymers having different polarities. be able to.

Both-end halogenated oligoolefin The both-end halogenated oligoolefin according to the present invention has the structure of the above general formula (1).

In general formula (1), the number of repeating units n is not particularly limited, but is usually an integer of 10 to 1000. R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. R ¹ and R ² may all be hydrogen atoms, or at least one of them may be substituted with a functional group other than hydrogen atoms. When two are substituted with a functional group other than a hydrogen atom, these substituents may be the same or different. From the viewpoint of reactivity, it is preferable that R ¹ is hydrogen and R ² is a methyl group, R ¹ is hydrogen and R ² is a phenyl group, or both R ¹ and R ² are methyl groups. X represents a halogen atom, preferably Cl, Br, or I, and Br is most preferable from the viewpoint of reactivity.

In the general formula (1), each R ³ is independently selected from the group consisting of H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH (CH ₃ ) ₂ . That is, the oligoolefin constituting the oligoolefin chain is oligopropylene (R ³ is all —CH ₃ ), oligo 1-butene (R ³ is all —C ₂ H ₅ ), ethylene / propylene copolymer (R ³ is H or _-CH 3), ethylene-1-butene copolymer ^{(R 3} is H or _-C 2 _H 5), propylene-1-butene copolymer ^{(R 3} are, --CH3 or _-C 2 _H 5) or oligo 4-methyl-1-pentene ^{(R 3} are all _{-CH 2 CH (CH 3) 2} ) include like those that are. In addition, regarding a copolymer, both a random copolymer and a block copolymer are included.

  Since the both-end halogenated oligoolefin according to the present invention can act with various vinyl monomers as a polymerization initiator for atom transfer radical polymerization to produce a triblock copolymer, It is particularly useful.

  The vinyl monomer to be polymerized is not particularly limited, and examples thereof include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid. Methacrylic monomers such as 2-hydroxyethyl acid, 2-hydroxypropyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-acrylate Acrylic monomers such as butyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-aminoethyl acrylate, aromatic alkenyl compounds such as styrene, acrylonitrile, methacrylonitrile And vinyl cyanide compounds such like. These can be used alone or in combination of two or more. When two or more types of monomers are used, these can be charged into the system simultaneously or sequentially. When charged simultaneously, a copolymer based on the monomer reactivity ratio can be synthesized. Moreover, if a monomer is added sequentially, it is possible to synthesize a copolymer having different blocks while extending the chain length.

  These vinyl monomers can be selected from those preferable for imparting the performance required for the triblock copolymer. For example, when heat resistance is required, a compound having a relatively high glass transition temperature can be selected. When oil resistance is required, a highly polar compound such as acrylonitrile can be selected. Moreover, when combining a triblock copolymer with a thermoplastic resin, rubber | gum, a filler, etc., a preferable thing can be selected also by compatibility with them.

Method for Producing Both End Halogenated Oligoolefins The both end halogenated oligoolefins according to the present invention are obtained by hydroxylating both end vinylidene bond-containing oligoolefins and further carrying out an esterification reaction using an appropriate α-haloacyl halide. Can be synthesized.

  The oligoolefin containing a vinylidene bond at both ends as a raw material is obtained as a pyrolysis product of polyolefin by highly controlled pyrolysis (see Macromolecules, 28, 7973 (1995)) developed by the present inventors.

  Taking polypropylene as an example, the pyrolysis product of polypropylene obtained by the highly controlled pyrolysis method has a number average molecular weight Mn of about 1,000 to 50,000, a degree of dispersion Mw / Mn of about 2, and an average of vinylidene groups per molecule The number is about 1.5 to 1.8, and it has the property that the stereoregularity of the raw material polypropylene before decomposition is maintained. The weight average molecular weight of the raw material polypropylene before decomposition is preferably in the range of 10,000 to 1,000,000, more preferably in the range of 200,000 to 800,000.

As the thermal decomposition apparatus, an apparatus disclosed in Journal of Polymer Science: Polymer Chemistry Edition, 21, 703 (1983) can be used. While suppressing the secondary reaction by putting polypropylene in a reaction vessel of a Pyrex ^(R) glass pyrolysis apparatus, bubbling the molten polymer phase vigorously with nitrogen gas under reduced pressure, and extracting a volatile product, A thermal decomposition reaction is performed at a predetermined temperature for a predetermined time. After completion of the thermal decomposition reaction, the residue in the reaction vessel is dissolved in hot xylene, filtered while hot, and then reprecipitated with alcohol for purification. The reprecipitate is collected by filtration and dried in vacuo to obtain oligopropylene containing vinylidene bonds at both ends.

  The thermal decomposition conditions are adjusted by predicting the molecular weight of the product from the molecular weight of polypropylene before decomposition and the primary structure of the final target block copolymer, and taking into consideration the results of experiments conducted in advance. The thermal decomposition temperature is preferably in the range of 300 ° C to 450 ° C. If the temperature is lower than 300 ° C, the thermal decomposition reaction of polypropylene may not proceed sufficiently, and if the temperature is higher than 450 ° C, the degradation of the thermal decomposition product may progress.

  Hydroxylation is achieved by hydroxylating the double bond of the both-end vinylidene bond-containing oligoolefin obtained according to the above-described method by hydroboration followed by an oxidation reaction. For example, tetrahydrofuran is first used as a solvent, and a boronation reagent is first added to hydroborate. As the boration reagent, 9-boranebicyclononane or borane-tetrahydrofuran complex can be used. When a hydrogen peroxide solution is added to the reaction solution after hydroboration to cause an oxidation reaction, a hydroxyl group-containing oligoolefin is obtained.

  Subsequently, the both-end hydroxyl group-containing oligoolefin obtained as described above is subjected to esterification reaction using an appropriate α-haloacyl halide to thereby perform both-end halogenation represented by the general formula (1). Oligoolefin is obtained.

  Here, the α-haloacyl halide means an acyl halide in which the carbon at the α-position is halogenated and can be easily obtained industrially.

  The reaction can be carried out by a normal esterification reaction with an acid halide and an alcohol. Specifically, an α-haloacyl halide and a hydroxyl group-containing oligoolefin may be reacted in the presence of a base such as triethylamine.

Triblock Copolymer The triblock copolymer according to the present invention uses the above-described both-end halogenated oligoolefin as an initiator, and is usually a known vinyl monomer, particularly methyl (meth) acrylate, (meta ) Methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-isopropyl (meth) acrylamide, 2-hydroxymethyl (meth) acrylate, (meth) It is obtained by atom transfer radical polymerization of 2-dimethylaminoethyl acrylate, (meth) acrylonitrile, or styrene, and has the structure of the above general formula (2).

In the general formula (1), R ¹ , R ² , R ³ , n, and X are as defined above, and A is a vinyl polymer block represented by the general formula (3). . The number m of repeating units is not particularly limited, but is usually an integer of 1 to 10,000.

In particular, a triblock copolymer of t-butyl acrylate is easily hydrolyzed to give a triblock copolymer with acrylic acid (R ⁴ : H, R ⁵ : -COOH).

In the triblock copolymer of the present invention, the polarities of the blocks at both ends and the block (oligoolefin block) connecting them are different. Therefore, it can be used as a compatibilizer for two or more types of polymers having different polarities. Moreover, since the vinyl polymer block is amphiphilic with respect to a hydrophilic copolymer (for example, in the case of R ⁴ : H, R ⁵ : -COOH), it can be used as a surfactant. .

  In addition, since the triblock copolymer of the present invention has halogen atoms at both ends, it is possible to synthesize a multiblock copolymer having a higher molecular weight by performing an atom transfer radical coupling reaction. .

  Here, the atom transfer radical coupling is a known coupling reaction in which radical reactivity is applied (for example, see e-Polymers 2005, no. 49, pages 1 to 11). In general, when using a triblock copolymer in which a vinyl polymer block is composed of a monomer such as styrene that occurs as a main termination reaction, a recombination reaction should be performed by atom transfer radical coupling. Thus, a multi-block copolymer can be directly synthesized. On the other hand, triblock copolymers composed of monomers that generate two types of recombination and disproportionation as a termination reaction such as methyl methacrylate can undergo recombination reactions such as styrene by atom transfer radical polymerization as necessary. After the monomer to be generated is introduced to the terminal, it can be converted into a multiblock copolymer by atom transfer radical coupling.

Method for Producing Triblock Copolymer The method for producing a triblock copolymer according to the present invention uses the above-described halogenated oligoolefins as described above as initiators, and generally known vinyl monomers, particularly (meth) Methyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-isopropyl (meth) acrylamide, (meth) acrylic acid 2 -Atom transfer radical polymerization of hydroxymethyl, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, or styrene.

  Atom transfer radical polymerization is characterized in that an organic halide or a sulfonyl halide compound is used as an initiator and a metal complex having a group 8 element, group 9, group 10 or group 11 element as a central metal is polymerized as a catalyst. This is a known polymerization method. (For example, Mattyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.), 1995, 117, 5614, Macromolecules, 1995, 28. Vol., 7901, Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721).

  The transition metal complex used as a catalyst for atom transfer radical polymerization is not particularly limited, but preferred are monovalent and zerovalent copper, divalent ruthenium, divalent iron, and divalent nickel. Complex. Among these, a copper complex is preferable from the viewpoint of cost and reaction control.

  Examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. Of these, cuprous chloride and cuprous bromide are preferred from the viewpoint of polymerization control.

  The ligand to be used is not particularly limited, but may be appropriately determined from the relationship of the required reaction rate in consideration of the initiator, the monomer, and the solvent. When a monovalent copper compound is used, 2,2′-bipyridyl and its derivatives (for example, 4,4′-dinolyl-2,2′-bipyridyl, 4,4′-di (5-noryl)) are used as a ligand. 2,2'-bipyridyl compounds such as -2,2'-bipyridyl and the like, 1,10-phenanthroline and its derivatives (for example, 4,7-dinolyl-1,10-phenanthroline, 5,6-dinolyl-1, 1,10-phenanthroline compounds such as 10-phenanthroline), polyamines such as tetramethyldiethylenetriamine (TMEDA), pentamethyldiethylenetriamine (PMDETA), and hexamethyl (2-aminoethyl) amine can be used.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also preferable as a catalyst. When a ruthenium compound is used as a catalyst, aluminum alkoxides may be added as an activator. Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ ) is also preferable as a catalyst.

  The polymerization reaction is usually performed in the range of room temperature to 200 ° C, preferably in the range of 50 to 100 ° C.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In each example, the molecular weight was measured with a GPC analyzer (HLC-8121GPC / HT (manufactured by Tosoh Corporation)). At that time, THF was measured as a mobile phase, and the molecular weight in terms of polystyrene was determined. Moreover, NMR used FT-NMR: JNM-GX400 (made by JEOL Ltd.). The SEM was observed with an acceleration voltage of 15 kV using a Hitachi S-3000N.

Example 1 Synthesis of Both-Terminal Brominated Oligopropylene (iPP-Br) Both-end brominated oligopropylene (iPP-Br) was synthesized by the method shown in (1) to (3) below.

(1) Synthesis of both-terminal vinylidene bond-containing oligopropylene (iPP-TVD) A lab scale highly controlled pyrolyzer having a sample amount of 5 kg was used as a pyrolyzer. 2 kg of commercially available isotactic polypropylene (Novatech PP (manufactured by Nippon Polypropylene Co., Ltd.), grade: EA9A, melt flow index (MFR): 0.5 g / 10 min) was charged into the reactor, and the system was purged with nitrogen to 2 mmHg. Under reduced pressure, the reactor was heated to 200 ° C. to melt. Thereafter, the reactor was submerged in a metal bath set at 390 ° C., and pyrolysis was performed. During the thermal decomposition, the system was kept at a reduced pressure of about 2 mmHg and stirred by bubbling nitrogen gas discharged from the capillary into which the molten polymer was introduced. After 3 hours, the reactor was lifted from the metal bath, cooled to room temperature, the reaction system was brought to normal pressure, the residue in the reactor was dissolved in hot xylene, and then added dropwise to methanol for reprecipitation purification. The obtained polymer had a yield of 77%, a number average molecular weight (Mn) of 7500, a dispersity (Mw / Mn) of 1.78, and an average number of terminal double bonds per molecule (fTVD) of 1.78. It was.

(2) Synthesis of both-end hydroxylated oligopropylene (iPP-OH) Both-end vinylidene bond-containing oligopropylene obtained by highly controlled pyrolysis (Mn: 1000, Mw / Mn: 1.1, fTVD: 1.80) 20 g and 200 ml of tetrahydrofuran (THF) were charged into the reactor, and after substitution with nitrogen, 60 ml of borane-tetrahydrofuran complex (BH ₃ -THF) in THF (1M) was added and heated under reflux for 3 hours. Thereafter, 60 ml of 5N aqueous sodium hydroxide solution was added in an ice bath, followed by 60 ml of 30% aqueous hydrogen peroxide solution, and heated at reflux for 15 hours. After the reaction, the reaction mixture was poured into methanol and purified by reprecipitation to obtain a both-end hydroxylated oligopropylene (iPP-OH).

(3) Synthesis of both-end brominated oligopropylene (iPP-Br) 10 g of the above-mentioned both-end hydroxylated oligopropylene (iPP-OH, Mn: 1000), 5.6 ml of triethylamine and chloroform were charged into the reactor, and the nitrogen substitution was performed. Thereafter, a chloroform solution of 2-bromoisobutyryl bromide (BiBB) (BiBB / CHCl ₃ = 5 ml / 20 ml) was added dropwise and stirred at room temperature for 24 hours. After the reaction, the reaction solution was poured into 1N HCl / methanol solution and purified by reprecipitation to synthesize both-end brominated oligopropylene (iPP-Br).

  FIG. 1 shows proton NMR of iPP-Br (FIG. 1a), iPP-OH (FIG. 1b), and iPP-TVD (FIG. 1c) obtained above. FIG. 2 shows proton NMR of iPP-Br having various number average molecular weights.

(Example 2): Synthesis of polymethyl methacrylate-polypropylene triblock copolymer 0.635 g of both ends brominated oligopropylene and 0.1435 g of copper (I) bromide were charged into a Schlenk tube, and after nitrogen substitution, 4.26 ml of degassed methyl methacrylate, 10 ml of o-xylene, and 209 μl of 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA) were added and stirred at room temperature for 30 minutes, and then heated and stirred at 80 ° C. for 6 hours. did. After completion of the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The obtained triblock copolymer had Mn of 10700 and Mw / Mn of 1.50.

(Example 3): Synthesis of polystyrene-polypropylene triblock copolymer 1.275 g of both ends brominated oligopropylene and 0.2869 g of copper (I) bromide were charged into a Schlenk tube, deaerated after being purged with nitrogen. 23 ml of styrene, 60 ml of toluene and 418 μl of PMDETA were added and stirred at room temperature for 30 minutes, and then heated and stirred at 80 ° C. for 6 hours. After completion of the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The obtained triblock copolymer had Mn of 8700 and Mw / Mn of 1.24.

(Example 4): Synthesis of polyethyl acrylate-polypropylene triblock copolymer 0.0635 g of both ends brominated oligopropylene (Mn: 1000) and 0.0143 g of copper (I) bromide were charged into a Schlenk tube, and nitrogen was added. After replacement, 1.1 ml of degassed ethyl acrylate, 3 ml of toluene, and 20.9 ul of PMDETA were added, and the mixture was stirred at room temperature for 30 minutes and then heated and stirred at 120 ° C. for 3 hours. After the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The obtained triblock copolymer was Mn: 10700 and Mw / Mn: 1.57.

(Example 5) Synthesis of polyacrylic acid n-butyl-polypropylene triblock copolymer Both ends brominated oligopropylene (Mn: 1000) 0.0635 g, copper (I) bromide 0.0143 g was charged into a Schlenk tube, After replacement with nitrogen, 1.4 ml of degassed n-butyl acrylate, 3 ml of toluene and 20.9 ul of PMDETA were added, and the mixture was stirred at room temperature for 30 minutes and then heated and stirred at 120 ° C. for 3 hours. After the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The obtained triblock copolymer was Mn: 10400 and Mw / Mn: 2.25.

(Example 6) Synthesis of poly (t-butyl acrylate-polypropylene) triblock copolymer 0.0635 g of both ends brominated oligopropylene (Mn: 1000) and 0.0143 g of copper (I) bromide were charged into a Schlenk tube. After replacement with nitrogen, 1.5 ml of degassed t-butyl acrylate, 3 ml of toluene and 20.9 ul of PMDETA were added, and the mixture was stirred at room temperature for 30 minutes and then heated and stirred at 120 ° C. for 3 hours. After the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The obtained triblock copolymer was Mn: 12100 and Mw / Mn: 1.63.

Example 7 Conversion of poly (acrylic acid) t-butyl-polypropylene triblock copolymer to polyacrylic acid-polypropylene triblock copolymer by hydrolysis Poly (t-butyl-polypropylene triblock copolymer) (Mn : 10000) 1 g was charged into the flask, and after nitrogen substitution, 1 ml of trifluoroacetic acid and 5 ml of dehydrated chloroform were added, and the mixture was stirred at room temperature for 24 hours. After the reaction, the solvent, trifluoroacetic acid and t-butyl alcohol were removed by distillation to obtain a polyacrylic acid-polypropylene triblock copolymer.

(Example 8) Synthesis of polystyrene-polypropylene multiblock copolymer by atom transfer radical coupling of polystyrene- polypropylene triblock copolymer 0.87 g of polystyrene-polypropylene triblock copolymer (Mn: 8700), copper (0 ) 0.1272 g and copper (I) bromide 0.0287 g were charged into the reactor, and after nitrogen substitution, 1 ml of degassed o-xylene and 460 μl of PMDETA were charged and stirred at 80 ° C. for 5 hours. After the reaction, the reaction solution was poured into methanol and purified by reprecipitation to obtain a multi-block copolymer having a repeating unit represented by the following formula (4). It was Mn: 25000 and Mw / Mn: 3.66 of the multiblock copolymer.

(Example 9) Evaluation of compatibilization performance of triblock copolymer A triblock copolymer (PMMA-iPP-PMMA) was synthesized by the method shown in (1) below, and the compatibilization performance was evaluated.

(1) Synthesis of polymethyl methacrylate-polypropylene triblock copolymer (PMMA-iPP-PMMA) 0.7 g of brominated oligopropylene at both ends (Mn = 14000) and 0.0143 g of copper bromide (I) were Schlenk tubes Then, 3.19 ml of degassed methyl methacrylate, 5 ml of o-xylene, and 20.9 μl of PMDETA were added, and the mixture was stirred at room temperature for 30 minutes and then heated and stirred at 120 ° C. for 5 hours. After completion of the reaction, the reaction solution was poured into methanol and purified by reprecipitation. The composition of the triblock copolymer obtained by proton NMR was iPP: PMMA = 1: 0.89.

(2) Evaluation of compatibilization performance 2.5 g of iPP (manufactured by Nippon Polypro, NOVATEC PP EA9, Mn: 160,000) and PMMA (manufactured by Aldrich, Mn: 80,000) and PMMA-iPP- synthesized above 0.5 g of PMMA was collected and stirred with heating at 140 ° C. in an eggplant flask together with 200 ml of xylene. After complete dissolution, the solution was slowly dropped into 2000 ml of methanol, and the produced precipitate was collected and dried by heating under reduced pressure to obtain a blend powder. The blended powder was melt-kneaded at 200 ° C. and then heat pressed at 200 ° C. to prepare a sheet. The obtained sheet was cooled with liquid nitrogen, and after fracture, the PMMA phase was etched under reflux of chloroform, and then the fracture surface was observed by SEM. The obtained SEM image is shown in FIG. For comparison, an experiment was performed under the same conditions as described above except that PMMA-iPP-PMMA was not added, and an SEM image was observed for a sample manufactured under the same conditions. The obtained SEM is shown in FIG.

  By comparing FIG. 3 (a) with FIG. 3 (b), in the sample to which the triblock copolymer of the present invention was added, a significant decrease in the pore size derived from PMMA was confirmed. It can be seen that the triblock copolymer has a very high compatibilization performance.

  The both-end halogenated oligoolefin according to the present invention can be used as a polymerization initiator for atom transfer radical polymerization to react with various monomers to form a triblock copolymer. , A copolymer having amphiphilicity, adhesiveness, impact resistance, biocompatibility, and the like.

  The triblock copolymer of the present invention can be used as a compatibilizer for two or more types of polymers having different polarities.

FIG. 1 shows proton NMR (400 MHz, CDCl ₃ ) of iPP-Br (FIG. 1a), iPP-OH (FIG. 1b) and iPP-TVD (FIG. 1c). FIG. 2 shows proton NMR (400 MHz, CDCl ₃ ) of iPP-Br having various number average molecular weights. 3 is an SEM image obtained in Example 9, FIG. 3 (a) shows an SEM image of a sample to which PMMA-iPP-PMMA is added, and FIG. 3 (b) is an example to which PMMA-iPP-PMMA is added. It is a SEM image of the sample prepared without doing.

Claims (4)

Both-end halogenated oligoolefin represented by the following general formula (1).
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (CH ₃ ) _{2 is} independently selected from the group consisting of ₂ , X is a halogen atom, and n is an integer of 10 to 1000. The both-end halogenated oligoolefin according to claim ¹ , wherein R ³ is -CH ₃ , R ¹ and R ² are all methyl groups, and X is Br. A triblock copolymer represented by the following general formula (2).
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (CH ₃ ) _{2 is} independently selected from the group consisting of ₂ , X is a halogen atom, n is an integer of 10 to 1000. A is a vinyl polymer block, and is represented by the following general formula (3). Is done.
(Wherein, R ⁴ is a methyl group or hydrogen, R ⁵ is —COOCH ₃ , —COOC ₂ H ₅ , —COOnBu, —COOtBu, —CONHCH (CH ₃ ) ₂ , —COOCH ₂ CH ₂ OH, — _{COOCH 2 CH 2 N (CH 3} ) 2, -CN, represents -COOH or a phenyl group. Further, m is an integer of 1 to 10,000.)). Both-end halogenated oligoolefin represented by the following general formula (1)
(In the formula, R ¹ and R ² each independently represent hydrogen, a methyl group, or a phenyl group. Also, each R ³ represents H, —CH ₃ , —C ₂ H ₅ , and —CH ₂ CH. (Independently selected from the group consisting of (CH ₃ ) ₂ , X is a halogen atom, and n is an integer of 10 to 1000).
Methyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, N-isopropyl (meth) acrylamide, (meth) A process for producing a triblock copolymer, characterized by atom transfer radical polymerization of 2-hydroxymethyl acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylonitrile, or styrene.