JPS63258930A - Aromatic polymer - Google Patents
Aromatic polymerInfo
- Publication number
- JPS63258930A JPS63258930A JP9260787A JP9260787A JPS63258930A JP S63258930 A JPS63258930 A JP S63258930A JP 9260787 A JP9260787 A JP 9260787A JP 9260787 A JP9260787 A JP 9260787A JP S63258930 A JPS63258930 A JP S63258930A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- aromatic
- formula
- aromatic polysulfone
- repeating unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 63
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 46
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 14
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 14
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- -1 gears Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- MIYFPRPQXKJXCC-WGCWOXMQSA-M potassium;(e)-3-(4-hydroxy-3-methoxyphenyl)prop-2-enoate Chemical compound [K+].COC1=CC(\C=C\C([O-])=O)=CC=C1O MIYFPRPQXKJXCC-WGCWOXMQSA-M 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NCTHNHPAQAVBEB-WGCWOXMQSA-M sodium ferulate Chemical compound [Na+].COC1=CC(\C=C\C([O-])=O)=CC=C1O NCTHNHPAQAVBEB-WGCWOXMQSA-M 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は芳香族重合体に関するものであり、更に詳しく
は互いに異なる反復単位を有する２種の芳香族ポリサル
ホンがブロック状に共有結合で結合しているブロックポ
リマーを含有する芳香族重合体に関するものである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an aromatic polymer, and more specifically, to an aromatic polymer in which two types of aromatic polysulfones having mutually different repeating units are bonded in a block form by covalent bonds. This invention relates to aromatic polymers containing block polymers.
（従来技術および問題点）
芳香族ポリサルホンは、化学的及び熱的に耐久性の優れ
たエンジニアリング樹脂として広く使用されている。芳
香族ポリサルホンとしては多くのボリアリールエーテル
サルホンポリマーが知られ、一般にこれらの樹脂は、式
で示される繰り返し単位を含む構造によって特徴づけら
れる。この構造から予想される様に、芳香族ポリサルホ
ンは優れた耐久性、安定性を持つ反面、疎水的な性質を
示す。代表的な芳香族ポリサルホンとして、インペリア
ルケミカルインダストリーズ（ＩＣＩと略す）社よりＶ
１ｃｔｒｅｘ、 ユニオンカーバイド（Ｕ ＣＣと略
す）社よりＵｄｅｌの商品名で、それぞれ市販されてい
るが、吸水率は前者が０．４％、後者が０．３％（いず
れもＡＳＴＭ Ｄ５７０）であり、親水性樹脂として
知られている酢酸セルロース等の１０分の１以下の吸水
率である。この疎水的な性質のため、芳香族ポリサルホ
ンは、［表面が水でぬれに（く乾燥しやすい」、「汚れ
やすい」、「帯電しゃすい］、「接着しにくいｊなど数
多くの問題点かあ゛った。(Prior Art and Problems) Aromatic polysulfone is widely used as an engineering resin with excellent chemical and thermal durability. Many polyarylether sulfone polymers are known as aromatic polysulfones, and these resins are generally characterized by a structure containing repeating units represented by the formula. As expected from this structure, aromatic polysulfone has excellent durability and stability, but exhibits hydrophobic properties. V from Imperial Chemical Industries (abbreviated as ICI) is a representative aromatic polysulfone.
1ctrex and Udel are commercially available from Union Carbide (abbreviated as UCC), and the water absorption rate is 0.4% for the former and 0.3% for the latter (both ASTM D570). The water absorption rate is less than one-tenth that of cellulose acetate, which is known as a hydrophilic resin. Due to this hydrophobic property, aromatic polysulfone has many problems such as the surface is not easily wetted by water and dries easily, it is easily stained, it is not easily charged, and it is difficult to adhere. It was.
この様な問題点を解決するため、親水性の改善された芳
香族ポリサルホンを提供する方法あるいは樹脂製品を親
水化処理する方法が、種々提案されている。最も一般的
で簡便な方法は、グリセリンやポリエチレングリコール
などの親水性物質や界面活性剤、あるいは親水性ポリマ
ーを、芳香族ポリザルポンポリマーと混合し樹脂中に含
有せしめるか、樹脂表面にコーティングする方法である
。In order to solve these problems, various methods have been proposed for providing aromatic polysulfone with improved hydrophilicity or for treating resin products to make them hydrophilic. The most common and simple method is to mix a hydrophilic substance such as glycerin or polyethylene glycol, a surfactant, or a hydrophilic polymer with an aromatic polysarpone polymer and incorporate it into the resin, or coat it on the resin surface. It's a method.
例えば、特開昭５６−１５５２４３号は、芳香族ポリザ
ルホンポリマーとポリアルキレンオキシドの相溶性ブレ
ンド物により、親水化された芳香族ポリザルホンを提供
する方法を提案している。しかし、この様な水溶性の添
加物は、樹脂が水と接触することにより溶出除去されて
しまう。従って、むしろ添加物を水で抽出除去すること
によって芳香族ポリザルホンの多孔体を作製する目的に
適した方法と言えるが、本質的に親水化された芳香族ポ
リザルホンを得る方法としては不適切であった。For example, JP-A-56-155243 proposes a method for providing hydrophilized aromatic polysulfone using a compatible blend of aromatic polysulfone polymer and polyalkylene oxide. However, such water-soluble additives are eluted and removed when the resin comes into contact with water. Therefore, it can be said that this method is suitable for the purpose of producing a porous body of aromatic polysulfone by extracting and removing additives with water, but it is not suitable as a method for obtaining essentially hydrophilized aromatic polysulfone. Ta.
また、樹脂表面にコーティングする方法も、同じ理由か
ら不適切と言わざるをえなかった。Furthermore, the method of coating the resin surface had to be considered inappropriate for the same reason.
水に溶解しない親水性ポリマーを添加する方法として、
例えば特開昭５７−５０５０７号は、芳香族ポリザルホ
ンポリマーとセルロース誘導体をブレンドした樹脂を提
案している。しかし、芳香族ポリザルホンポリマーは分
子凝集力が大きいため、異種ポリマーを均一にブレンド
することば非常に難しく、この提案でも相溶剤として水
溶性ポリマーであるポリビニルピロリドンをかなり添加
する必要があった。さらに、水に不溶の添加剤は水溶性
添加剤より親水化効果が小さいと思われるため、実質的
に親水化された芳香族ポリザルホンを得るために大量の
異種ポリマーの添加を必要としていた。この様な大量の
異種ポリマーの添加は、得られた樹脂の耐熱性などの物
質の低下を惹き起こすのみならず、均一なブレンド物を
作ることが困難となり、樹脂製品の親水化にむらができ
たり、ひび割れや強度の低下を惹き起こすと考えられた
。As a method of adding hydrophilic polymers that do not dissolve in water,
For example, JP-A-57-50507 proposes a resin that is a blend of an aromatic polysulfone polymer and a cellulose derivative. However, because aromatic polysulfone polymers have a large molecular cohesive force, it is extremely difficult to uniformly blend different types of polymers, and even with this proposal, it was necessary to add a considerable amount of polyvinylpyrrolidone, a water-soluble polymer, as a compatibilizer. Furthermore, since water-insoluble additives are thought to have a smaller hydrophilic effect than water-soluble additives, it has been necessary to add large amounts of different polymers to obtain substantially hydrophilic aromatic polysulfone. Addition of such a large amount of different polymers not only causes a decrease in the heat resistance and other substances of the resulting resin, but also makes it difficult to make a uniform blend, resulting in uneven hydrophilicity of the resin product. It was thought that this would cause cracks and a decrease in strength.
一方、芳香族ポリサルホンポリマー自身に親水基や親水
性ポリマーを導入して、親水化された芳香族ポリサルホ
ンを提供する方法も、種々提案されている。On the other hand, various methods have been proposed for providing hydrophilized aromatic polysulfone by introducing hydrophilic groups or hydrophilic polymers into the aromatic polysulfone polymer itself.
例えば、特公昭５３−１３６７９号、特開昭５９−１９
６３２２号などは、ポリマー主鎖にスルホン酸基を、特
開昭５９−１９６３２１号は、ポリマー主鎖にスルホン
アミド基を、特開昭５７−１７４１０４号はポリマー主
鎖にポリエヂレンイミンポリマーを、それぞれ導入もし
くはグラフ！、することにより親水化された芳香族ポリ
ザルホンを提供する方法を提案している。For example, Japanese Patent Publication No. 53-13679, Japanese Patent Publication No. 59-19
No. 6322 etc. have a sulfonic acid group in the polymer main chain, JP-A-59-196321 has a sulfonamide group in the polymer main chain, and JP-A-57-174104 has a polyethyleneimine polymer in the polymer main chain. , each introduction or graph! We have proposed a method for providing hydrophilized aromatic polysulfone by .
これらの方法はいずれも芳香族ポリザルホンポリマー主
鎖の芳香環に、親水基もしくは親水性ポリマーを共有結
合によりランダムに結合させる改質手段である。このた
め、改質されていない芳香族ポリザルホンポリマーと比
較すると、耐熱性などの物性が低下することは避けられ
なかった。さらに、該ポリマーに対して導入された親水
基の比率が多い場合には、ポリマー主鎖の親水性が増加
し完全に水溶性を示すポリマーにまで改質されてしまう
など、著しい物性の変化を伴なう改質法だと言わざるを
えなかった。All of these methods are modification means in which hydrophilic groups or hydrophilic polymers are randomly bonded by covalent bonds to the aromatic rings of the main chain of the aromatic polysulfone polymer. For this reason, it was inevitable that physical properties such as heat resistance would deteriorate compared to unmodified aromatic polysulfone polymers. Furthermore, if the ratio of hydrophilic groups introduced into the polymer is high, the hydrophilicity of the polymer main chain increases, leading to significant changes in physical properties, such as modification to a polymer that is completely water-soluble. I had to say that it was a reforming method that involved.
そのため、芳香族ポリサルホンポリマーの物性を損なわ
ず、本質的な樹脂表面の親水化を行なうために、例えば
、特開昭５９−１８６６０４号では、ポリザルホン製メ
ンブレンフィルターを陽光柱プラズマ処理する方法が提
案されている。しかし、この様な方法は、メンブレンフ
ィルターの如く小型で比較的単純な形状物で、かつ成形
が終了した樹脂の表面のみの改質を特徴とする特殊な方
法であり一般的ではなかった。Therefore, in order to essentially make the resin surface hydrophilic without impairing the physical properties of the aromatic polysulfone polymer, for example, JP-A-59-186604 proposes a method of subjecting polysulfone membrane filters to positive column plasma treatment. ing. However, such a method is a special method that is characterized by modifying only the surface of a resin that is small and relatively simple in shape, such as a membrane filter, and has been molded, and is therefore not common.
（問題点を解決するための手段）
本発明者らは、上記に鑑みて鋭意研究した結果、化学的
に改質されにくいポリエーテルサルホンと化学的に改質
されやすい芳香族ポリザルホンとをブロック状に結合せ
しめたブロックポリマーを用いることにより、芳香族ポ
リサルホンの耐熱性や機械的強度を低下させることなく
親水化できることを見い出し、本発明を完成するに至っ
た。(Means for Solving the Problems) In view of the above, as a result of intensive research, the present inventors have discovered that polyethersulfone, which is difficult to modify chemically, and aromatic polysulfone, which is easy to modify chemically, are blocked. The present inventors have discovered that aromatic polysulfone can be made hydrophilic without reducing its heat resistance or mechanical strength by using a block polymer bonded in a shape, and have completed the present invention.
すなわち本発明は、反復単位、
を有するポリエーテルサルポン（これをＡとする）の末
端部位と、下記の式（ＩＩ）〜（ＩＶ）から選ばれる少
なくとも１種の反復単位又はこれをスルホン化した反復
単位を式ＣＩ）の反復単位とともに有する芳香族ポリサ
ルホン（これをＢとする）の末端部位とが共有結合によ
って結合したブロックポリマーを含（ｒすることを特徴
とする芳香族重合体である。That is, the present invention relates to a terminal portion of a polyether sulfone (hereinafter referred to as A) having a repeating unit, and at least one repeating unit selected from the following formulas (II) to (IV) or a sulfonated repeating unit thereof. An aromatic polymer characterized by comprising a block polymer in which a terminal portion of an aromatic polysulfone (hereinafter referred to as B) having a repeating unit of the formula CI) is bonded by a covalent bond. .
ごこで（１）の反復単位は既に特開昭５９−７４１２８
号等で示されているように化学的に改質されにくい。例
えば、スルホン化においては濃硫酸によっては実質的に
スルホン化されず、発煙硫酸やクロロスルホン酸のよう
な強力なスルホン化剤を用いて初めてスルホン化される
。一方（ＴＩ）〜（ＩＶ）は（１）に比べると化学的に
改質されやすく、例えば（ＩＩりや（■）は、スルホン
化においては濃硫酸によって急速にスルホン化されてし
まう。The repeating unit of Gokode (1) has already been published in JP-A-59-74128.
It is difficult to be chemically modified as shown in the No. For example, in sulfonation, it is not substantially sulfonated by concentrated sulfuric acid, but is sulfonated only by using a strong sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid. On the other hand, (TI) to (IV) are more easily modified chemically than (1); for example, (II Riya (■)) is rapidly sulfonated by concentrated sulfuric acid.
また、（ＩＩ）についてはクロロスルホン酸のような強
力なスルホン化剤が一般に用いられるが、（■）との共
重合体では実質的にスルホン化を受けるのは反復単位（
ＩＩ）であることが知られている （例えば、Ｊ ｏｕ
ｒｎａｌ ｏｒ Ｐ ｏｌｙ＋ａｅｒ Ｓ ｃｌｅｎｃ
ｅ、 ２２１７２１〜７３７（１９８４））。In addition, for (II), a strong sulfonating agent such as chlorosulfonic acid is generally used, but in the copolymer with (■), the repeating unit (
II) is known to be (for example, J ou
rnal or poly+aer sclenc
e, 221721-737 (1984)).
本発明では、化学的に安定な（１）から成るポリエーテ
ルザルホン八と化学的に改質されやすい（ＩＩ）〜（Ｉ
Ｖ）を含む芳香族ポリサルホンＢとがブロック状に結合
していることが重要である。化学的に安定な反復単位と
化学的変化を受けやすい反復単位とから成るランダム共
重合体型の芳香族ポリサルホンは特開昭５９−７４１２
８号等に公知であるが、このような共重合体を、例えば
、スルホン化した場合にはランダムに、かつ、ポリマー
全体に平均的にスルホン化されてしまうため、全体とし
て機械的強度や耐熱性が著しく低下することになる。し
かし、本発明のようなブロックポリマーであれば、スル
ホン化の場合でもスルホン化されたＢ成分とスルホン化
されないＡ成分とがミクロ相分離を起こす為、実質的に
ポリマー全体の機械的強度や耐熱性はほとんど低下しな
い。In the present invention, chemically stable polyether sulfone 8 consisting of (1) and easily chemically modified (II) to (I
It is important that aromatic polysulfone B containing V) is bonded in a block form. A random copolymer-type aromatic polysulfone consisting of chemically stable repeating units and repeating units susceptible to chemical changes is disclosed in Japanese Patent Application Laid-Open No. 59-7412.
No. 8, etc., but when such a copolymer is sulfonated, the sulfonation occurs randomly and evenly over the entire polymer, resulting in poor mechanical strength and heat resistance as a whole. This will result in a significant decline in performance. However, with the block polymer of the present invention, even in the case of sulfonation, microphase separation occurs between the sulfonated B component and the non-sulfonated A component, which substantially reduces the mechanical strength and heat resistance of the entire polymer. Sexuality hardly decreases.
本発明のブロックポリマーの合成法としては、（１）ポ
リエーテルザルホンＡを従来法（例えば特公昭４７
Ｇ１７号や特公昭４２−７７９９号に開示されている方
法）に従って合成し、反応を停止せずにその活性末端を
重合開始点として引き続き公知の方法（例えばカナダ特
許第８４７９６３号）により（ＩＩ）〜（ＩＶ）のモノ
マーを（Ｉ）のモノマーとともに共重合させる方法。As a method for synthesizing the block polymer of the present invention, (1) Polyethersulfone A is synthesized by a conventional method (for example, Japanese Patent Publication No. 47
(II) by a known method (e.g. Canadian Patent No. 847963) using the active end as a polymerization initiation point without stopping the reaction. A method of copolymerizing the monomers (IV) to (IV) together with the monomers (I).
（２）市販のポリエーテルザルホンへの末端基（−〇／
又は−０１（）をそのまま用いるか又は別の官能基に変
えて、公知の有機化学反応によって活性末端を有する芳
香族ポリザルホンＢと反応させる方法。(2) Terminal group (-〇/
Or a method of using -01() as it is or changing it to another functional group and reacting it with aromatic polysulfone B having an active end by a known organic chemical reaction.
の大きく分けて２つの方法が挙げられる。これらの方法
によって合成されたポリマーは一般式、Ｉ３／ −（
−Ａ−１３）Ｉｌｌ ・・・・・・・・・（Ｖ）
又は Δ／ −（Ｂ−Ａ ）、 −−−（Ｖｌ
）（ここで！はＯ又は、１．ａ＋、ｎは１以上の整数）
で表わされるブロックポリマーを含有している。There are two main methods. Polymers synthesized by these methods have the general formula, I3/-(
-A-13) Ill ・・・・・・・・・(V)
or Δ/-(B-A), ---(Vl
) (where ! is O or 1.a+, n is an integer greater than or equal to 1)
Contains a block polymer represented by:
ここでのブロックポリマーの純度は１００％である必要
はなく、未反応の芳香族ポリザルホンＢや未反応のポリ
エーテルザルホンＡが混在していても不都合はない。The purity of the block polymer here does not need to be 100%, and there is no problem even if unreacted aromatic polysulfone B and unreacted polyethersulfone A are mixed.
また、未反応の芳香族ポリサルホンＢは親水化反応にお
いて選択的にほぼ完全に親水化されるため水洗等により
抽出除去することができる。In addition, unreacted aromatic polysulfone B is selectively and almost completely hydrophilized in the hydrophilization reaction, so that it can be extracted and removed by washing with water or the like.
さらに、上記のブロックポリマーと従来の芳香族ポリザ
ルホン（好ましくは（１）の反復単位を有するポリエー
テルサルホン）とを任意の割合で混合してもかまわない
。Furthermore, the above block polymer and conventional aromatic polysulfone (preferably polyethersulfone having the repeating unit (1)) may be mixed in any proportion.
また、ブロックポリマーについては次式で定義されるブ
ロック率が２％以上、８０％以下であることが好ましい
。ブロック率が２％未満であると親水化処理しても親水
性が改善されにくい。Further, for the block polymer, it is preferable that the block rate defined by the following formula is 2% or more and 80% or less. When the block rate is less than 2%, it is difficult to improve hydrophilicity even if the hydrophilic treatment is performed.
一方８０％を越える場合は現水化処理後の機械的強度や
耐熱性が著しく損なわれる。On the other hand, if it exceeds 80%, the mechanical strength and heat resistance after the hydrolysis treatment will be significantly impaired.
本発明の芳香族重合体は以上のようなブロックポリマー
を含有しており、最終的に親水化処理が施される。この
れｌ水化処理すなわち親木基の導入はブロックポリマー
を合成する際に用いる芳香族ポリザルホンＢ又はそのモ
ノマーの段階で行なって６よく、また、ブロックポリマ
ーの合成に引き続いて行なってらよい。もらろん、各種
成形物に成形後親水化処理してもよい。最も好ましい親
水化処理はスルホン化である。スルホン化反応は、例え
ば、濃硫酸に本発明の芳香族重合体を浸漬したり、発煙
硫酸やクロロスルホン酸の蒸気に接触さＵ・たりする公
知の方法によって実施できる。The aromatic polymer of the present invention contains the above-described block polymer, and is finally subjected to a hydrophilic treatment. This hydration treatment, that is, the introduction of the parent group may be carried out at the stage of aromatic polysulfone B or its monomer used in the synthesis of the block polymer,6 or it may be carried out subsequent to the synthesis of the block polymer. After molding, various molded products may be subjected to hydrophilic treatment. The most preferred hydrophilic treatment is sulfonation. The sulfonation reaction can be carried out by a known method, for example, by immersing the aromatic polymer of the present invention in concentrated sulfuric acid, or by contacting it with vapors of fuming sulfuric acid or chlorosulfonic acid.
ただし、ブロックポリマーのイオン交換容量は０ 、
ｌ、ｍｅｑ／ｇ以上４ 、 Ｏｍｅｑ／ｇ以下に制御す
ることが親水性と耐水性の面から好ましい。また、未改
質の芳香族ポリザルホンポリマーとのブレンド物におい
てはイオン交換容量が０ 、１ ｍｅｑ／ｇ 〜４ 、
０ ｍｅｑ／ｇであることが、親水性と耐熱性、耐久性
の点で好ましい。このようにしてスルホン化された本発
明の芳香族重合体はブロックポリマー中の芳香族ポリザ
ルホンＢの反復単位の一部又は全部に一８Ｏ，Ｈ基が導
入された構造を有するが、もちろん、−ｓｏ、ｅＭ■（
Ｍはアルカリ金属、もしくはＮＲ４（Ｒはアルキル基）
）のような塩に転化させてもよい。However, the ion exchange capacity of the block polymer is 0,
From the viewpoint of hydrophilicity and water resistance, it is preferable to control the content to 1.1 meq/g or more and 4.0 meq/g or less. In addition, in blends with unmodified aromatic polysulfone polymer, the ion exchange capacity is 0.1 meq/g to 4.
0 meq/g is preferable in terms of hydrophilicity, heat resistance, and durability. The aromatic polymer of the present invention sulfonated in this manner has a structure in which 18O,H groups are introduced into some or all of the repeating units of aromatic polysulfone B in the block polymer, but of course - so,eM■(
M is an alkali metal or NR4 (R is an alkyl group)
) may be converted into salts such as
（発明の効果）
本発明の芳香族重合体により、芳香族ポリザルホンの持
つ優れた物性をほとんど損なわずに良好な親水化処理が
行なえる樹脂、又は樹脂成形物が得られる。また、親水
化処理（特にスルホン化処理）された本発明の芳香族重
合体は各種成形物、例えば、電気、１ｒ１子分野の各種
部品、液晶表示体用等の透明導電性フィルム、ハウジン
グ類、自動車部品、航空機内装材、ギヤ、歯科用材料、
蒸気滅菌容器など広範な分野に用いることができ、従来
の芳香族ポリサルホン製成形物の問題点［表面が水でぬ
れにくく乾燥しゃずい」、「汚れやすい」。(Effects of the Invention) The aromatic polymer of the present invention makes it possible to obtain resins or resin moldings that can be subjected to good hydrophilic treatment without substantially impairing the excellent physical properties of aromatic polysulfone. In addition, the aromatic polymer of the present invention which has been subjected to hydrophilic treatment (particularly sulfonation treatment) can be used in various molded products, such as various parts in electrical and 1R1 fields, transparent conductive films for liquid crystal displays, housings, etc. Automotive parts, aircraft interior materials, gears, dental materials,
It can be used in a wide range of fields such as steam sterilization containers, and has the problems of conventional aromatic polysulfone molded products: the surface is difficult to get wet with water and dries easily, and is easily stained.
「帯電しやすい」、「接着しにくい」などを大１］に改
善することができる。特に逆浸透膜、限外濾過膜、メン
ブレンフィルターなどの分離膜を形成する膜素材として
、充分な耐熱性と親水性を併せ持っだ本発明の樹脂は好
適な材料であると言える。Problems such as ``easiness to charge up'' and ``difficulty in adhesion'' can be greatly improved. In particular, the resin of the present invention can be said to be a suitable material as it has both sufficient heat resistance and hydrophilicity as a membrane material for forming separation membranes such as reverse osmosis membranes, ultrafiltration membranes, and membrane filters.
（実施例）
次に実施例によってこの発明をさらに具体的に説明ずろ
。(Examples) Next, the present invention will be explained in more detail with reference to Examples.
実施例１
末端が水酸基である（１）式の反復単位を有するポリエ
ーテルサルホン（ＶｉｃＬｒｅｘ ５００３ Ｐ。Example 1 Polyether sulfone (VicLrex 5003 P) having a repeating unit of formula (1) whose terminal is a hydroxyl group.
Ｉｃ１社製、平均分子ｆｆ１ｔ ２．Ｏｏ Ｏ） ６０
ｇをジメチルスルホキシド（以下ＤＭＳ Ｏ）４００ｎ
／と塩化ベンゼン（以下ＰｂＣ／）２００ｍ／の混合溶
媒に室温で溶解し、これに０．５ＮのＮａ０ＩＩ水溶液
１３ｍ／を加えて室温で２ｈｒ反応させ、末端がナトリ
ウムフェルレート塑のポリエーテルザルホンの溶液を得
た。Manufactured by Ic1, average molecular ff1t 2. Oo O) 60
g to 400n of dimethyl sulfoxide (hereinafter referred to as DMSO)
/ and benzene chloride (hereinafter referred to as PbC/) in a mixed solvent of 200 m/ at room temperature, and 13 m/ of a 0.5N Na0II aqueous solution was added thereto and reacted for 2 hours at room temperature to obtain polyether sulfone with sodium ferulate plastic terminals. A solution of was obtained.
これにαα′αジーロロー１）−キシレン１．５ｇを加
え室温で１ｈｒ、７０℃で２ｈｒ反応さＵｏてポリマ上
末端に活性クロロメチル基を導入した。この反応混合物
の溶液をＡ液とする。To this was added 1.5 g of αα'α Zirolow 1)-xylene, and the reaction was carried out for 1 hour at room temperature and 2 hours at 70° C. to introduce an active chloromethyl group into the upper end of the polymer. The solution of this reaction mixture is referred to as Solution A.
一方、公知の方法によって式（ＩＶ）および式（１）の
反復単位をモル比ｌ：ｌで有しかつ、末端がカリウムフ
ェルレート型の芳香族ポリサルホンを合成した。すなわ
ち、ヒドロキノン５．５ｇ、４３％Ｋ ＯＨ水溶液１３
ｇ、ＤＭＳ０５０ｍ／及びベンゼン６ｍ／を仕込みＮ、
ガスを吹き込んだ。混合物を３〜４ｈｒにわたって還流
させ、水を連続的にベンゼンとの共沸混合物として除去
し、そして、１３０℃付近でベンゼンを充分留去した。On the other hand, an aromatic polysulfone having repeating units of formula (IV) and formula (1) in a molar ratio of 1:1 and having potassium ferulate terminals was synthesized by a known method. i.e. 5.5 g of hydroquinone, 43% KOH aqueous solution 13
g, DMS050m/and benzene 6m/N,
I blew gas. The mixture was refluxed for 3-4 hr, water was continuously removed as an azeotrope with benzene, and benzene was fully distilled off at around 130°C.
この混合物を冷却し、４．４′−ジクロロジフェニルス
ルホン１４．４ｇ及び無水ＤＭＳ０４０ｍ／をＮ、雰囲
気下で加えた。この混合物を１３０℃に加熱し、充分撹
拌しつつ１３０〜１４０℃で６ｈｒ保った。この反応混
合物を水３００ｍ／中に注ぎ白色重合体をｆ別水洗し、
次いで、減圧乾燥し目的の芳香族ポリサルホンを得た。The mixture was cooled and 14.4 g of 4,4'-dichlorodiphenylsulfone and 40 m/s of anhydrous DMS were added under an atmosphere of N. This mixture was heated to 130°C and maintained at 130-140°C for 6 hours with thorough stirring. This reaction mixture was poured into 300 m of water, and the white polymer was washed with water.
Next, it was dried under reduced pressure to obtain the desired aromatic polysulfone.
この芳香族ポリサルホン１５ｇをＤＭＳ０５０ｍｌとＰ
ｈＣ／２０ｍ／の混合溶媒に溶解し、この溶液を前述の
Ａ液に加え室温でｌｈｒ、７０℃で２ｈｒ反応させた後
、濃硫酸を加えて反応を停止した。Add 15g of this aromatic polysulfone to 050ml of DMS and P
It was dissolved in a mixed solvent of hC/20m/h, and this solution was added to the above-mentioned solution A, and the reaction was carried out at room temperature for 1 hour and at 70°C for 2 hours, and then concentrated sulfuric acid was added to stop the reaction.
反応混合物をメタノール／水（８／２（容積比））にて
再沈後、重合体をｆ別し水洗し、次いで減圧乾燥した。After the reaction mixture was reprecipitated with methanol/water (8/2 (volume ratio)), the polymer was separated, washed with water, and then dried under reduced pressure.
２７０Ｍ１−１ｚの’ Ｉ−１−Ｎ Ｍ Ｉｔ分析およ
び有機溶媒系ゲルパーミエーシジンクロマトグラフィー
による分子量分布の測定から、この重合体は反復ｌｉ位
（１）を有するポリエーテルサルホンに、反復単位（［
）及び（ｒ’／）を等モルで有する芳香族ポリザルホン
がベンジルエーテル結合を介してブロック状に結合した
ブロックポリマーであることが確認された。また、この
ポリマーのブロック率は２０％であった。From the 'I-1-N M It analysis of 270M1-1z and the measurement of the molecular weight distribution by organic solvent-based gel permeacydin chromatography, this polymer has a polyether sulfone with a repeating li position (1) and a repeating unit. ([
It was confirmed that the aromatic polysulfone having equimolar amounts of ) and (r'/) is a block polymer in which the aromatic polysulfone is bonded in a block form through benzyl ether bonds. Moreover, the block rate of this polymer was 20%.
実施例２
実施例１のブロックポリマー２０ｇを濃硫酸１００ｍ／
とともに１８ｈｒ振とうし、更に濃硫酸５０ｍ／を添加
し＋８ｈｒ振とうし続けた。次に、この溶液を５０％Ｙ
／Ｗ希硫酸中に注ぎ白色沈澱をｆ別し水洗し、次いで減
圧乾燥した。この沈澱は実質的に実施例１のブロックポ
リマー中の反復単位（ＩＶ）がモノスルホン化されてい
るブロックポリマーであることが、２７０ＭＩ−Ｔｚ’
ｔｆ−ＮＭＲ分析によって確認された。また、イオン交
換容量は０ 、 Ｇ ｍｅａｌｔｔであったへ
このスルホン化ブロックポリマ−２０１１ｒｆｆ１部を
ＤＭＳ０８０重量部に溶解し、ガラス板上に厚み４００
μ巾で流延した後８０℃にて徐々にＤＭＳ Ｏを蒸発さ
せた。得られた非多孔性フィルムをガラス板から剥離し
、５０％Ｖ／Ｖエタノール水溶液に２４時間浸漬して残
存ＤＭＳＯを完全抽出した。Example 2 20g of the block polymer of Example 1 was added to 100ml of concentrated sulfuric acid.
The mixture was shaken for 18 hours, and then 50 m/ml of concentrated sulfuric acid was added and continued shaking for +8 hours. Next, add this solution to 50% Y
/W diluted sulfuric acid, the white precipitate was separated, washed with water, and then dried under reduced pressure. This precipitate is essentially a block polymer in which the repeating unit (IV) in the block polymer of Example 1 is monosulfonated.
Confirmed by tf-NMR analysis. Further, 1 part of sulfonated block polymer 2011rff, which had an ion exchange capacity of 0 and G meltt, was dissolved in 80 parts by weight of DMS, and the solution was spread on a glass plate to a thickness of 400 mm.
After casting in μ width, DMSO was gradually evaporated at 80°C. The obtained non-porous film was peeled off from the glass plate and immersed in a 50% V/V ethanol aqueous solution for 24 hours to completely extract residual DMSO.
このフィルムを５０℃で減圧乾燥後、エルマ社製ゴニオ
メータ一式接触角計で水との接触角を測定したところ、
４０℃という著しい濡れ性を示した。After drying this film under reduced pressure at 50°C, the contact angle with water was measured using a goniometer set contact angle meter manufactured by Elma.
It showed remarkable wettability of 40°C.
また、このフィルムを９０℃の熱水に３０日間浸漬した
が、寸法変化は見られなかった。Further, this film was immersed in hot water at 90° C. for 30 days, but no dimensional change was observed.
比較例１
実施例１で得た式（■）と式（１）の反復単位を等モル
で有する芳香族ポリサルホンを実施例２の方法によって
スルホン化した。得られたポリマーは’Ｈ−ＮＭＲ分析
により、反復単位（１’／）がモノスルホン化されてい
ることが確認された。このポリマーのイオン交換容量は
３ 、１ ｍｅｑ／ｇであったが、水に完全に溶解する
ポリマーであった。Comparative Example 1 The aromatic polysulfone having equimolar amounts of repeating units of formula (■) and formula (1) obtained in Example 1 was sulfonated by the method of Example 2. It was confirmed by 'H-NMR analysis of the obtained polymer that the repeating unit (1'/) was monosulfonated. The ion exchange capacity of this polymer was 3.1 meq/g, but it was a polymer completely soluble in water.
Claims (5)
I ） を有するポリエーテルサルホン（これをＡとする）の末
端部位と、下記の式（II）ないし（IV）から選ばれる少
なくとも１種の反復単位又はこれをスルホン化した反復
単位を式（ I ）の反復単位とともに有する芳香族ポリ
サルホン（これをＢとする）の末端部位とが共有結合に
よって結合したブロックポリマーを含有することを特徴
とする芳香族重合体。 ▲数式、化学式、表等があります▼−−−−−−−−（
II） ▲数式、化学式、表等があります▼−−−−−−−−（
III） ▲数式、化学式、表等があります▼−−−−−−−−（
IV）(1) Repeating units, ▲Mathematical formulas, chemical formulas, tables, etc.▼−−−−−−−−(
I) and at least one repeating unit selected from the following formulas (II) to (IV) or a repeating unit obtained by sulfonating the terminal part of a polyether sulfone (hereinafter referred to as A) having the formula (I). An aromatic polymer characterized by containing a block polymer in which the repeating unit of I) and the terminal portion of an aromatic polysulfone (hereinafter referred to as B) are bonded by covalent bonds. ▲There are mathematical formulas, chemical formulas, tables, etc.▼−−−−−−−−(
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼−−−−−−−−(
III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼−−−−−−−−(
IV)
芳香族ポリサルホンＢの平均分子量をＭ＿Ｂとしたとき ブロック率（％）＝［Ｍ＿Ｂ／（Ｍ＿Ａ＋Ｍ＿Ｂ）］×
１００の式で定義されるブロック率が２％以上、８０％
以下の値を有するブロックポリマーであり、かつスルホ
ン化後のイオン交換容量が０．１ｍｅｑ／ｇ以上４．０
ｍｅｑ／ｇ以下である特許請求の範囲第１項記載の芳香
族重合体。(2) The average molecular weight of polyether sulfone A is M_A,
When the average molecular weight of aromatic polysulfone B is M_B, block rate (%) = [M_B/(M_A+M_B)]×
Block rate defined by formula 100 is 2% or more, 80%
A block polymer having the following values, and an ion exchange capacity after sulfonation of 0.1 meq/g or more and 4.0
The aromatic polymer according to claim 1, which has a molecular weight of not more than meq/g.
される特許請求の範囲第１項記載の芳香族重合体。(3) The block polymer has the general formula B_l-(A-B)_m......(V) or A_l-(B-A)_n...(VI) (where l is 0 or 1, m, n is an integer of 1 or more).
）ないし（IV）から選ばれる少なくとも１種の反復単位
を式（ I ）の反復単位とともに有する共重合体が前記
ブロックポリマーと混合されている特許請求の範囲第１
項記載の芳香族重合体。(4) Homopolymer of repeating units of formula (I) or formula (II)
Claim 1, wherein a copolymer having at least one repeating unit selected from ) to (IV) together with the repeating unit of formula (I) is mixed with the block polymer.
Aromatic polymers described in .
ｅｑ／ｇ以下である特許請求の範囲第４項記載の芳香族
重合体。(5) Ion exchange capacity of 0.1 meq/g or more 2.0 m
The aromatic polymer according to claim 4, which has a molecular weight of not more than eq/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9260787A JPS63258930A (en) | 1987-04-15 | 1987-04-15 | Aromatic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9260787A JPS63258930A (en) | 1987-04-15 | 1987-04-15 | Aromatic polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63258930A true JPS63258930A (en) | 1988-10-26 |
Family
ID=14059127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9260787A Pending JPS63258930A (en) | 1987-04-15 | 1987-04-15 | Aromatic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63258930A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005126684A (en) * | 2003-09-30 | 2005-05-19 | Sumitomo Chemical Co Ltd | Block copolymer and its use |
| US7258941B2 (en) | 2001-05-08 | 2007-08-21 | Ube Industries, Ltd. | Polymer electrolyte for solid polymer type fuel cell and fuel cell |
| WO2009136631A1 (en) | 2008-05-08 | 2009-11-12 | 東洋紡績株式会社 | Novel sulfonic acid group-containing segmentalized block copolymer, use thereof, and method for producing novel block copolymer |
| EP2147947A1 (en) | 2001-11-29 | 2010-01-27 | Ube Industries, Ltd. | Process for preparing an aromatic polyether sulfone blockcopolymer |
| WO2011016444A1 (en) | 2009-08-03 | 2011-02-10 | 東洋紡績株式会社 | Novel sulfonic acid group-containing segmented block copolymer and use thereof |
| US8211576B2 (en) | 2003-09-30 | 2012-07-03 | Sumitomo Chemical Company, Limited | Block copolymers and use thereof |
-
1987
- 1987-04-15 JP JP9260787A patent/JPS63258930A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7258941B2 (en) | 2001-05-08 | 2007-08-21 | Ube Industries, Ltd. | Polymer electrolyte for solid polymer type fuel cell and fuel cell |
| EP2147947A1 (en) | 2001-11-29 | 2010-01-27 | Ube Industries, Ltd. | Process for preparing an aromatic polyether sulfone blockcopolymer |
| JP2005126684A (en) * | 2003-09-30 | 2005-05-19 | Sumitomo Chemical Co Ltd | Block copolymer and its use |
| US8211576B2 (en) | 2003-09-30 | 2012-07-03 | Sumitomo Chemical Company, Limited | Block copolymers and use thereof |
| WO2009136631A1 (en) | 2008-05-08 | 2009-11-12 | 東洋紡績株式会社 | Novel sulfonic acid group-containing segmentalized block copolymer, use thereof, and method for producing novel block copolymer |
| WO2011016444A1 (en) | 2009-08-03 | 2011-02-10 | 東洋紡績株式会社 | Novel sulfonic acid group-containing segmented block copolymer and use thereof |
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