JP5203603B2 - Hydrophilic thermoplastic copolymer - Google Patents
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- JP5203603B2 JP5203603B2 JP2006355457A JP2006355457A JP5203603B2 JP 5203603 B2 JP5203603 B2 JP 5203603B2 JP 2006355457 A JP2006355457 A JP 2006355457A JP 2006355457 A JP2006355457 A JP 2006355457A JP 5203603 B2 JP5203603 B2 JP 5203603B2
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- 238000006243 chemical reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 17
- 229920002857 polybutadiene Polymers 0.000 claims description 17
- 239000004793 Polystyrene Substances 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 15
- 229920002223 polystyrene Polymers 0.000 claims description 15
- 229920001169 thermoplastic Polymers 0.000 claims description 15
- 239000004416 thermosoftening plastic Substances 0.000 claims description 15
- 229920000428 triblock copolymer Polymers 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000007320 Hoechst-Wacker oxidation reaction Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
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Description
本発明は芳香族ビニル−ジエン共重合体、たとえばポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体にカルボキシル基等の官能基を付加して親水性熱可塑性共重合体を得る技術に関する。 The present invention relates to a technique for obtaining a hydrophilic thermoplastic copolymer by adding a functional group such as a carboxyl group to an aromatic vinyl-diene copolymer, for example, a polystyrene-polybutadiene-polystyrene triblock copolymer.
ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体(以下SBSともいう)等に代表される芳香族ビニル−ジエン共重合体は熱可塑性共重合体として比較的安価に市販されている。SBSは室温でガラス状態のポリスチレン(以下PSともいう)とゴム状態のポリブタジエン（以下PBともいう）を一分子中にブロック状に持ち、ミクロ相分離しているため室温では架硫ゴムの性質を示す。一方、高温ではPSが溶融し流動可能となるため、熱可塑性樹脂に用いられる通常の成形加工法が適用できる。 Aromatic vinyl-diene copolymers represented by polystyrene-polybutadiene-polystyrene triblock copolymers (hereinafter also referred to as SBS) and the like are commercially available as thermoplastic copolymers at a relatively low cost. SBS has polystyrene in the glass state (hereinafter also referred to as PS) and polybutadiene in the rubber state (hereinafter also referred to as PB) in a single molecule in a block form and is microphase-separated. Show. On the other hand, since PS melts and becomes flowable at a high temperature, a normal molding method used for thermoplastic resins can be applied.
前記SBSのPBの主鎖には多量の二重結合が存在し、ここにたとえば付加反応によりカルボキシル基を導入することができれば、熱可塑性共重合体に高度の親水性を付与することが可能であると共に吸水してもPS部分が膨潤を拘束するため、水に溶解することの無い新規な親水性熱可塑性共重合体が得られるものと考えられる。 A large amount of double bonds exist in the main chain of PB of SBS, and if a carboxyl group can be introduced therein by, for example, an addition reaction, it is possible to impart a high degree of hydrophilicity to the thermoplastic copolymer. In addition, since the PS portion restrains the swelling even when water is absorbed, it is considered that a novel hydrophilic thermoplastic copolymer that does not dissolve in water can be obtained.
カルボキシル基を含有するSBSとしては、無水マレイン酸を共重合したものや末端二重結合をカルボキシル化した例があるが、主鎖の二重結合にカルボキシル基を付加した例は知られていない。一方、ポリブタジエンの主鎖の二重結合にカルボキシル基を付加した例が報告されている(P. Narayanan, B. Kaye and D.J. Cole-Hamilton: "Polycarboxylic
Acids via Catalytic Hydrocarboxylation of Polybutadienes", J. Mater.
Chem., Vol. 3, No.1, p. 19 (1993))。しかしその後の報告では、この方法を高分子量のポリブタジエンに適用すると精製中にゲル化して単離できないとされていた。ポリブタジエンにカルボキシル基を付加するこの方法をそのまま市販のSBSに適用すると可逆的に溶媒に可溶な生成物を得ることはできなかった。
Examples of SBS containing a carboxyl group include those copolymerized with maleic anhydride and carboxylated terminal double bonds, but no examples of adding carboxyl groups to the double bonds of the main chain are known. On the other hand, an example in which a carboxyl group is added to the double bond of the main chain of polybutadiene has been reported (P. Narayanan, B. Kaye and DJ Cole-Hamilton: "Polycarboxylic
Acids via Catalytic Hydrocarboxylation of Polybutadienes ", J. Mater.
Chem., Vol. 3, No. 1, p. 19 (1993)). However, in subsequent reports, if this method was applied to high molecular weight polybutadiene, it was gelled during purification and could not be isolated. When this method of adding a carboxyl group to polybutadiene was applied to commercial SBS as it was, a product soluble in a solvent could not be obtained reversibly.
熱可塑性共重合体中、たとえばポリスチレン−ポリプタジエン−ポリスチレントリブロック共重合体（SBS）は、室温では架硫ゴムの性質を示す一方、高温ではポリスチレン（PS）が溶融し流動可能となるため、熱可塑性樹脂に用いられる通常の成形加工法が適用できる特長を有している。このようなSBSのポリブタジエン（PB）鎖の二重結合部分にカルボキシル基を導入すれば、高い強度を有したまま吸水性等を有し、なおかつ吸水しても水に溶解することのない新規な親水性熱可塑性共重合体となり、その結果、溶媒に可溶で、なおかつ通常の熱可塑性樹脂に用いられる成形加工法が適用可能な材料を得ることができるものと考えられるが、そのような改質のための実用レベルの技術は未だ知られていない。
Among thermoplastic copolymers, for example, polystyrene-polyptadiene-polystyrene triblock copolymer (SBS) exhibits the properties of vulcanized rubber at room temperature, while polystyrene (PS) melts and flows at high temperatures. It has the feature that a normal molding method used for a plastic resin can be applied. If a carboxyl group is introduced into the double bond part of such polybutadiene (PB) chain of SBS, it has a high strength and has a water-absorbing property, etc., and it does not dissolve in water even if it absorbs water It is considered that a hydrophilic thermoplastic copolymer is obtained, and as a result, it is possible to obtain a material that is soluble in a solvent and that can be applied with a molding method used for ordinary thermoplastic resins. Practical level technology for quality is not yet known.
本発明によれば、ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体にカルボキシル基の付加により親水性を付与する熱可塑性共重合体において、前記ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体に一酸化炭素、塩酸水溶液を混合し、酸素を加えて触媒の存在下で反応させ、オキソ反応およびヘキスト−ワッカー反応によりポリブタジエン鎖のニ重結合部分にカルボキシル基を付加して前記ポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体を親水性化して得られる親水性熱可塑性共重合体が提供される。
According to the present invention, in the thermoplastic copolymer that imparts hydrophilicity to the polystyrene-polybutadiene-polystyrene triblock copolymer by addition of a carboxyl group, the polystyrene-polybutadiene-polystyrene triblock copolymer has carbon monoxide, Mix hydrochloric acid aqueous solution, add oxygen and react in the presence of catalyst, add carboxyl group to double bond part of polybutadiene chain by oxo reaction and Hoechst-Wacker reaction to add polystyrene-polybutadiene-polystyrene triblock copolymer. There is provided a hydrophilic thermoplastic copolymer obtained by making the coalescent hydrophilic .
本発明においてはオキソ反応およびヘキスト−ワッカー反応を利用することにより、ポリブタジエン鎖の二重結合の部分にカルボキシル基を導入することができ、これは1H-NMRおよびFT-IRスペクトルによって確認される。また得られた生成物の特性としての吸水性、イオン導電性、強度特性などは解析の結果いずれも優れたものである。
In the present invention, by utilizing an oxo reaction and Hoechst-Wacker reaction, a carboxyl group can be introduced into the double bond portion of the polybutadiene chain, which is confirmed by 1 H-NMR and FT-IR spectra. . In addition, as a result of analysis, water absorption, ionic conductivity, strength characteristics, and the like as characteristics of the obtained product are all excellent.
一般にオキソ反応はオレフィンに水素と一酸化炭素を反応させ二重結合部分をアルデヒド化（ホルミル化）する反応であり、ヘキスト−ワッカ−反応はオレフィンを酸素により遷移金属系触媒を用いてカルボニル化合物へ酸化する反応である。本発明においては芳香族ビニル−ジエン共重合体としてのたとえばSBSを改質する反応プロセスにおいて、遷移金属系触媒を用いてポリブタジエンの主鎖の二重結合部分を一酸化炭素の存在下でオキソ法によりアルデヒド基を付加し、更にヘキスト−ワッカ−法によりカルボキシル基とすることにより前記主鎖の二重結合部分にカルボキシル基が付加される。すなわち全体としては下記の反応が生起しているものと考えられる。 In general, the oxo reaction is a reaction in which hydrogen and carbon monoxide are reacted with an olefin to aldehyde (formylate) the double bond portion. The Hoechst-Wacker reaction is a reaction of a olefin to a carbonyl compound with a transition metal catalyst using oxygen. It is a reaction that oxidizes. In the present invention, in the reaction process for modifying, for example, SBS as an aromatic vinyl-diene copolymer, the double bond portion of the main chain of polybutadiene is oxo-processed in the presence of carbon monoxide using a transition metal catalyst. An aldehyde group is added by, and a carboxyl group is further added to the double bond portion of the main chain by converting it to a carboxyl group by Hoechst-Wacker method. That is, as a whole, the following reaction is considered to occur.
R-CH=CH-R' + PdCl2 + CO + 2H2O = R-CH-H(COOH)-R' + Pd + ２HCl + 1/2O2 R-CH = CH-R '+ PdCl 2 + CO + 2H 2 O = R-CH-H (COOH) -R' + Pd + 2HCl + 1 / 2O 2
この場合反応に関与した塩化パラジウム（II）は金属パラジウムとなるが、これは次式のように酸化銅（II）等により酸化されて塩化パラジウムとなる。
Pd + 2CuCl２ ＝ PdCl２ ＋Cu2Cl２
Cu２Cl2 + 2HCl + 1/2O2 = 2CuCl2 + H2O
In this case, palladium (II) chloride involved in the reaction becomes metallic palladium, which is oxidized by copper (II) oxide or the like as in the following formula to become palladium chloride.
Pd + 2CuCl 2 = PdCl 2 + Cu 2 Cl 2
Cu 2 Cl 2 + 2HCl + 1 / 2O 2 = 2CuCl 2 + H 2 O
これらの反応はほとんど同時に進行するが、この場合、反応系内に存在する水の量を極力減少させて反応を行うことがエステルやケトンを生成する副反応を抑制する上で好ましいことが判明した。 Although these reactions proceed almost simultaneously, it has been found that in this case, it is preferable to reduce the amount of water present in the reaction system as much as possible in order to suppress side reactions that produce esters and ketones. .
水は前記反応の際に必要な原料であるが、通常は前記反応にHClを水溶液として用いる際に導入される水の量のみで十分である。系内の水が消費されてカルボキシル化反応が進行しなくなると考えられるような場合には水を追加してもよいが、この場合にもその量は前記系内に最初に存在する水の量を越えないことが好ましい。 Water is a necessary raw material for the reaction, but usually only the amount of water introduced when HCl is used as an aqueous solution in the reaction is sufficient. Water may be added in cases where it is considered that the carboxylation reaction will not proceed due to consumption of water in the system, but in this case as well, the amount is the amount of water initially present in the system. Is preferably not exceeded.
反応はほぼ常温,常圧でも進行する。具体的には、たとえば一酸化炭素をバブリングしたテトラヒドロフラン（THF）中に各種触媒等とSBSを加えた後、マグネティックスタラーで攪拌して反応を行う。所定時間反応後、塩酸水溶液を加えて反応生成物を析出させる。これらの反応条件は反応生成物についてのフ−リエ変換赤外線分光（FT−IR）スペクトルおよび核磁気共鳴（NMR）スペクトル測定によるポリマーの化学構造を解析して最適化される。得られたポリマーは吸水性・イオン伝導性・強度特性・熱特性など基本的な特性解析に優れている。 The reaction proceeds almost at room temperature and normal pressure. Specifically, for example, various catalysts and SBS are added to tetrahydrofuran (THF) in which carbon monoxide is bubbled, and then the reaction is performed by stirring with a magnetic stirrer. After reacting for a predetermined time, an aqueous hydrochloric acid solution is added to precipitate the reaction product. These reaction conditions are optimized by analyzing the chemical structure of the polymer by measuring the Fourier transform infrared spectroscopy (FT-IR) spectrum and nuclear magnetic resonance (NMR) spectrum of the reaction product. The obtained polymer is excellent in basic characteristics analysis such as water absorption, ion conductivity, strength characteristics, and thermal characteristics.
芳香族ビニル−ジエン共重合体として典型的に知られているものは前記SBSであり、この他たとえばジエンブロック部分がイソプレンであるポリスチレンーポリイソプレンーポリスチレントリブロック共重合体その他の芳香族ビニル−ジエン共重合体があげられる。 What is typically known as an aromatic vinyl-diene copolymer is the above-mentioned SBS, and for example, a polystyrene-polyisoprene-polystyrene triblock copolymer in which the diene block portion is isoprene, and other aromatic vinyl- Examples include diene copolymers.
反応に用いる遷移金属系触媒としてはＰｄ、Ｃｏ，Ｎｉ，Ｆｅ，Ｍｎ等の塩化物を用いることができ、塩化パラジウムを用いることが特に好ましい。 As the transition metal catalyst used in the reaction, chlorides such as Pd, Co, Ni, Fe, and Mn can be used, and palladium chloride is particularly preferable.
テトラヒドロフラン（以下THF）40ml中に、一酸化炭素15ml/minをバブリングし、塩化パラジウム（II）0.13g、塩化銅（II）0.26gおよび35％塩酸1mlを適宜溶解し、SBS 0.5gを加えた後、O2 15ml/minをバブリングしながら30°Cにてマグネティックスタラーで攪拌して反応を行った。 所定時間反応後、溶液と等量の6mol/L塩酸水溶液を加え生成物を析出させた後、沈殿物をテトラヒドロフランに溶解した。この操作を２度行った後、THFを揮発させて反応生成物を得た。 Carbon monoxide (15 ml / min) was bubbled into 40 ml of tetrahydrofuran (hereinafter THF), 0.13 g of palladium (II) chloride, 0.26 g of copper (II) chloride and 1 ml of 35% hydrochloric acid were appropriately dissolved, and 0.5 g of SBS was added. Thereafter, the reaction was carried out by stirring with a magnetic stirrer at 30 ° C. while bubbling O 2 at 15 ml / min. After reacting for a predetermined time, a 6 mol / L hydrochloric acid aqueous solution equivalent to the solution was added to precipitate the product, and the precipitate was dissolved in tetrahydrofuran. After performing this operation twice, THF was volatilized to obtain a reaction product.
オキソ反応およびヘキスト−ワッカ−反応を同時に利用することにより、ブタジエン部分のみにカルボキシル基が導入されたことを1H-NMRおよびFT-IRスペクトルによって確認した。図１、図２に示すように原料SBSと反応生成物の核磁気共鳴（NMR）スペクトルにおいては、低磁場側のスチレンに由来するピークはいずれの場合についても変化が無いのに対して、生成物のスペクトルを示す図２の高磁場側のブタジエンに由来するピークは大きく減少し、反応がポリブタジエンのみに起こっていることが明らかになった。 By simultaneously using the oxo reaction and Hoechst-Wacker reaction, it was confirmed by 1 H-NMR and FT-IR spectra that a carboxyl group was introduced only into the butadiene moiety. As shown in FIG. 1 and FIG. 2, in the nuclear magnetic resonance (NMR) spectra of the raw material SBS and the reaction product, the peak derived from styrene on the low magnetic field side is not changed in any case, but generated. The peak derived from butadiene on the high magnetic field side in FIG. 2 showing the spectrum of the product was greatly reduced, and it became clear that the reaction occurred only in polybutadiene.
さらに図３に示すようにフーリエ変換赤外線分光（FT-IR）スペクトルでは、1700〜1800cm-1にカルボニル基に基づくピークと3000cm-1付近には水酸基に基くブロードなピークが観測された。また、反応生成物のTHF溶液を6mol/Lの水酸化ナトリウム水溶液で処理した後、固形分のFT-IRスペクトルを測定すると、図６に示すように1705cm-1と1795cm-1のピークが消失することから、それぞれカルボン酸とカルボン酸無水物の存在が立証され、PBの主鎖の二重結合部分へカルボキシル基が付加されたことが確認された。 In yet Fourier transform infrared spectroscopy (FT-IR) spectrum as shown in FIG. 3, in the vicinity of the peak and 3000 cm -1 based on the carbonyl group 1700～1800Cm -1 broad peak based on the hydroxyl group was observed. Moreover, when the THF solution of the reaction product was treated with a 6 mol / L sodium hydroxide aqueous solution and the FT-IR spectrum of the solid content was measured, the peaks at 1705 cm −1 and 1795 cm −1 disappeared as shown in FIG. Thus, the existence of carboxylic acid and carboxylic anhydride was proved, respectively, and it was confirmed that a carboxyl group was added to the double bond portion of the main chain of PB.
図７に示すDSC曲線には水の融解および蒸発による吸熱ピークが観測される。これらのことから得られた熱可塑性共重合体が親水性を有することが確認された。溶媒を揮発させるとカルボキシル化したSBSのフィルムが得られた。このフィルムは再び溶媒に溶解し、またこのフィルムを水中に浸漬すると、吸水して白濁する。 In the DSC curve shown in FIG. 7, an endothermic peak due to melting and evaporation of water is observed. It was confirmed that the thermoplastic copolymer obtained from these has hydrophilicity. When the solvent was volatilized, a carboxylated SBS film was obtained. This film is dissolved again in the solvent, and when this film is immersed in water, it absorbs water and becomes cloudy.
一方、反応温度、反応時間等の反応条件を種々に変更して検討した結果、反応系における水分を減少させることによって副反応を抑制できることが見出された。水を積極的に供給しなかった前記実施例（水分量０ml：図３)に対して反応系に水を夫々１ｍｌおよび０．５ｍｌ仕込んで同様な反応を行わせた場合のFI-IRチャート図４、図５に示す。水分を減少させるほど１７０５ｃｍ−３のピークに対して１７３５ｃｍ−３のピークが減少しており副生物が抑止されることが示されている。
On the other hand, as a result of studying various reaction conditions such as reaction temperature and reaction time, it was found that side reactions can be suppressed by reducing water in the reaction system. FI-IR chart when the same reaction is carried out by charging 1 ml and 0.5 ml of water into the reaction system for the above example (
比較例
テトラヒドロフラン（THF）40ml中に、一酸化炭素15ml/minをバブリングし、塩化パラジウム（ＰｄＣｌ２（II））0.13g、35%塩酸1mlおよび水1mlを適宜溶解し、SBS 0.5gを加えた後、酸素の非存在下で30°Cにてマグネティックスタラーで攪拌して反応を行った。所定時間反応後、溶液と等量の6mol/L塩酸水溶液を加え生成物を析出させた後、沈殿物をテトラヒドロフランに溶解した。この操作を2度行った後、THFを揮発させて反応生成物を得た。
Comparative Example Carbon monoxide 15 ml / min was bubbled into 40 ml of tetrahydrofuran (THF), 0.13 g of palladium chloride (PdCl 2 (II)), 1 ml of 35% hydrochloric acid and 1 ml of water were appropriately dissolved, and 0.5 g of SBS was added. Thereafter, the reaction was conducted by stirring with a magnetic stirrer at 30 ° C. in the absence of oxygen. After reacting for a predetermined time, a 6 mol / L hydrochloric acid aqueous solution equivalent to the solution was added to precipitate the product, and the precipitate was dissolved in tetrahydrofuran. After performing this operation twice, THF was volatilized to obtain a reaction product.
SBSと反応生成物の核磁気共鳴（NMR）スペクトル（図示せず）を比較すると、低磁場側のスチレンに由来するピークは変化が無いのに対して、高磁場側のブタジエンに由来するピークは大きく減少し、反応がブタジエンのみに起こっていることは実施例と同様であった。しかし、FT-IRスペクトルでは、1700〜1800cm-1のカルボニル基に基くピークは、エステル化等の副反応によるピークのみが増大し、ブタジエン部分にカルボキシル基は付加されていないことが示され、親水性熱可塑性共重合体を得ることができなかった。 Comparing the nuclear magnetic resonance (NMR) spectra (not shown) of SBS and the reaction product, the peak derived from styrene on the low magnetic field side is unchanged, whereas the peak derived from butadiene on the high magnetic field side is unchanged. It was the same as in the example that it was greatly reduced and the reaction occurred only in butadiene. However, in the FT-IR spectrum, the peak based on the carbonyl group at 1700 to 1800 cm -1 increased only by the side reaction such as esterification, and it was shown that no carboxyl group was added to the butadiene moiety. A thermoplastic thermoplastic copolymer could not be obtained.
本発明によればポリスチレン−ポリブタジエン−ポリスチレントリブロック共重合体のポリブタジエン鎖のニ重結合の部分にカルボキシル基が導入されているので本来のこの種熱可塑性共重合体の特性に加えて親水性機能が付与されたとえば、イオン交換膜、電池用電解質膜、塗料、インク、接着剤、および各所成形材料等新たな応用が期待される。
According to the present invention, since a carboxyl group is introduced into the double bond portion of the polybutadiene chain of the polystyrene-polybutadiene-polystyrene triblock copolymer, the hydrophilic function is added to the properties of the original thermoplastic copolymer. For example, new applications such as ion exchange membranes, battery electrolyte membranes, paints, inks, adhesives, and molding materials are expected.
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