JP2007046060A - Amphipathic substance having perfluoroalkyl group - Google Patents
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- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 title claims abstract description 9
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 29
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 6
- -1 polypropylene Polymers 0.000 abstract description 42
- 239000004743 Polypropylene Substances 0.000 abstract description 26
- 229920001155 polypropylene Polymers 0.000 abstract description 26
- 229920000098 polyolefin Polymers 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 24
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 18
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 239000000693 micelle Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 9
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 9
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- VQZMFJVOYYLAHM-UHFFFAOYSA-N buta-1,2,3-trienylbenzene Chemical group C=C=C=CC1=CC=CC=C1 VQZMFJVOYYLAHM-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 4
- 238000002296 dynamic light scattering Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 239000012736 aqueous medium Substances 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 125000006353 oxyethylene group Chemical group 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000006197 hydroboration reaction Methods 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Polyethers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、親ＣＯ2性基であるパーフルオロアルキル（以下「Ｒｆ」とする）基を有する両親媒性物質に関する。 The present invention relates to an amphiphilic substance having a perfluoroalkyl (hereinafter referred to as “Rf”) group which is a parent CO 2 group.
従来から分子中に親水性基と疎水性基を有する両親媒性特性を示すいくつかの化合物が知られており、界面活性剤等へ広く応用されている。 Conventionally, several compounds having amphiphilic properties having a hydrophilic group and a hydrophobic group in the molecule are known and widely applied to surfactants and the like.
本発明は、Ｒｆ基を有する新規な両親媒性物質を提供する。 The present invention provides a novel amphiphile having an Rf group.
（Ａ）本発明は、本発明者が開発したモノマーである、片末端がビニリデン構造であるスチレンオリゴマーを、片末端をヒドロキシル化し、さらにエチレンオキシドとの開環重合により、スチレンオリゴマー−ポリエチレンオキシド共重合体を得たことに基くものである。さらに、これをパーフルオロアルキルカルボン酸と反応させ、親ＣＯ2性基であるパーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体を得ることに成功し本発明を完成させた。 (A) The present invention is a monomer developed by the present inventor, a styrene oligomer having a vinylidene structure at one end, hydroxylated at one end, and ring-opening polymerization with ethylene oxide. This is based on the fact that the coalescence is obtained. Furthermore, this was reacted with perfluoroalkyl carboxylic acid to succeed in obtaining a styrene oligomer-polyethylene oxide copolymer having a perfluoroalkyl group which is a parent CO 2 group, thereby completing the present invention.
すなわち、本発明にかかる共重合体は、下記一般式（１）
また、本発明にかかる共重合体には、一般式（１）におけるスチレン基のベンゼン環部または側鎖部分が種々の置換基で置換されているものも含まれる。具体的にはアルキル、アルコキシ、ハロゲン等が含まれる。また、本発明にかかる共重合体には、一般式（１）におけるエチレンオキシド以外のアルキレンオキシドと開環重合したもの、または複数種類のアルキレンオキシドと開環重合したものも含まれる。具体的にはプロピレンオキシドが挙げられる。 Further, the copolymer according to the present invention includes those in which the benzene ring part or the side chain part of the styrene group in the general formula (1) is substituted with various substituents. Specifically, alkyl, alkoxy, halogen and the like are included. The copolymer according to the present invention includes those obtained by ring-opening polymerization with an alkylene oxide other than ethylene oxide in the general formula (1), or those obtained by ring-opening polymerization with a plurality of types of alkylene oxides. Specific examples include propylene oxide.
（Ｂ）また、本発明者は、ポリプロピレンを高度制御熱分解して得られた単分散性の両末端ビニリデン基含有ポリプロピレンの末端ビニリデン基をヒドロキシ基に変換した両末端ヒドロキシ基含有ポリプロピレンに、エチレンオキシドを開環重合させて得られたポリプロピレン／ポリ（オキシエチレン）・トリブロック共重合体に基くものである。さらに、これをパーフルオロアルキルカルボン酸と反応させ、親ＣＯ2性基であるパーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）・トリブロック共重合体を得ることに成功し、本発明を完成させた。 (B) In addition, the present inventor has also disclosed that the terminal vinylidene group of the monodispersed vinylidene group-containing polypropylene obtained by highly controlled pyrolysis of polypropylene is converted to a hydroxyl group-containing polypropylene having both terminal hydroxyl groups converted to a hydroxy group. Is based on a polypropylene / poly (oxyethylene) .triblock copolymer obtained by ring-opening polymerization. Furthermore, this was reacted with perfluoroalkyl carboxylic acid to obtain a polypropylene / poly (oxyethylene) triblock copolymer having a perfluoroalkyl group which is a parent CO 2 group, and the present invention was completed. I let you.
すなわち、本発明は一般式（２）
本発明のパーフルオロアルキル基を有する両親媒性物質は、一般式（１）及び（２）で表される新規な構造を有する。従って、親水性基・疎水性基を併せ持つ事から、界面活性剤、分散剤、乳化剤、親油性および親水性高分子材料の表面改質剤等としての応用が期待できる。また、水分散液中において、両親媒性物質に多く見られる特異な分子集合体を形成していると考えられることから、この特徴を活かした新機能性材料としての発展が期待できる。さらには、パーフルオロアルキル基を有することから、親ＣＯ2性を発現すると考えられ、超臨界ＣＯ2中における新規界面活性剤への応用も期待できる。 The amphiphilic substance having a perfluoroalkyl group of the present invention has a novel structure represented by the general formulas (1) and (2). Therefore, since it has both a hydrophilic group and a hydrophobic group, it can be expected to be applied as a surfactant, a dispersant, an emulsifier, a lipophilic and hydrophilic polymer material as a surface modifier. In addition, since it is considered that unique molecular aggregates often found in amphiphiles are formed in the aqueous dispersion, development as a new functional material utilizing this feature can be expected. Furthermore, since it has a perfluoroalkyl group, it is considered to exhibit parent CO 2 property, and application to a novel surfactant in supercritical CO 2 can also be expected.
以下、本発明を実施の形態に即して詳細に説明する。
（Ａ）パーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体
本発明にかかる一般式（１）で表される共重合体は、以下を特徴とする。すなわち、スチレンオリゴマーとオリゴ（又はポリ）エチレンオキシドがエーテル基で結合し、末端のヒドロキシル基をパーフルオロカルボン酸エステルに変換した構造である。ここで、スチレンオリゴマーのスチレン分子数（ｎで示される）について特に制限はなく、原料として得られる片末端ビニリデンスチレンオリゴマーにのみ依存する。通常はｎは２〜１０の範囲である。またスチレンオリゴマーはその分子内に種々の置換基で置換されていてもよい。例えば、ベンゼン環がアルキル基、アルコキシ基、ハロゲン等で置換されているもの、−ＣＨ−ＣＨ2−基がアルキル、アルコキシ基等で置換されているものが挙げられる。ここで、パーフルオロアルキル基には、炭素数７〜１８の直鎖パーフルオロアルキル、分枝パーフルオロアルキルが含まれる（以下、パーフルオロアルキル基に関する定義は同様とする）。
Hereinafter, the present invention will be described in detail according to embodiments.
(A) Styrene oligomer-polyethylene oxide copolymer having a perfluoroalkyl group The copolymer represented by the general formula (1) according to the present invention is characterized by the following. That is, it is a structure in which a styrene oligomer and oligo (or poly) ethylene oxide are bonded with an ether group and the terminal hydroxyl group is converted into a perfluorocarboxylic acid ester. Here, there is no restriction | limiting in particular about the number of styrene molecules (it is shown by n) of a styrene oligomer, It depends only on the one terminal vinylidene styrene oligomer obtained as a raw material. Usually n is in the range of 2-10. The styrene oligomer may be substituted with various substituents in the molecule. Examples thereof include those in which the benzene ring is substituted with an alkyl group, an alkoxy group, halogen or the like, and those in which the —CH—CH 2 — group is substituted with an alkyl, alkoxy group or the like. Here, the perfluoroalkyl group includes straight-chain perfluoroalkyl having 7 to 18 carbon atoms and branched perfluoroalkyl (hereinafter, the definition regarding the perfluoroalkyl group is the same).
さらに、オリゴ（又はポリ）エチレンオキシド部分はプロピレンオキシド等の他の種々のアルキレンオキシドであってもよい。その繰り返し数（ｍで示される）についても特に制限はなく、以下に説明する開環重合の際に使用する量に依存する。通常はｍは１〜５０の範囲である。 Further, the oligo (or poly) ethylene oxide moiety may be various other alkylene oxides such as propylene oxide. The number of repetitions (indicated by m) is not particularly limited, and depends on the amount used in the ring-opening polymerization described below. Usually, m is in the range of 1-50.
本発明にかかる共重合体の化学構造は、分子量測定、種々の分光学的測定により特徴付けられる。 The chemical structure of the copolymer according to the present invention is characterized by molecular weight measurement and various spectroscopic measurements.
特に、通常公知のゲルパーミエイションクロマトグラフ（以下「ＧＰＣ」とする）によって、得られた重合体の分子量、分子量分布測定が可能である（ｍおよびｎ値が決定される）。さらには必要な場合、特定の部分を分取して詳細な分析（ＩＲ，ＮＭＲ等）のための試料とできる。 In particular, the molecular weight and molecular weight distribution of the obtained polymer can be measured (m and n values are determined) by a generally known gel permeation chromatograph (hereinafter referred to as “GPC”). Furthermore, if necessary, a specific part can be separated and used as a sample for detailed analysis (IR, NMR, etc.).
また、より詳しい化学構造については赤外線吸収スペクトル（以下「ＩＲ」とする）、核磁気共鳴吸収スペクトル（以下「ＮＭＲ」とする）等で決定することが可能である。例えば、ＩＲにおいて、スチレン基に基づく吸収とエ−テル基に基づく吸収が共存することにより本発明の重合体の構造が定性的に確認でき、またスチレン基に基づく吸収強度とエ−テル基に基づく吸収強度と、適当な検量線とを用いてｍ、ｎ値が定量できる。同様にＮＭＲにおいて、スチレン基に基づく吸収（例えば芳香族水素、メチレン基、メチン基）とエ−テル基に基づく吸収（例えばメチレン基）が共存することにより本発明の重合体の構造が定性的に確認でき、またそれらの積分値を用いてｍ、ｎ値が定量できる。 Further, a more detailed chemical structure can be determined by an infrared absorption spectrum (hereinafter referred to as “IR”), a nuclear magnetic resonance absorption spectrum (hereinafter referred to as “NMR”), or the like. For example, in IR, the structure of the polymer of the present invention can be qualitatively confirmed by the coexistence of absorption based on styrene groups and absorption based on ether groups. The m and n values can be quantified using the absorption intensity based on them and an appropriate calibration curve. Similarly, in NMR, the structure of the polymer of the present invention is qualitatively due to the coexistence of absorption based on a styrene group (for example, aromatic hydrogen, methylene group, methine group) and absorption based on an ether group (for example, methylene group). The m and n values can be quantified using their integrated values.
本発明にかかる共重合体の両親媒性については、表面張力の低下能力、分子会合体の形成能力により特徴付けられる。具体的には共重合体水分散液の表面張力を測定し、その濃度依存性を測定することができる。かかる測定により臨界ミセル濃度（以下「ＣＭＣ」という）を決定することができる。さらには共重合体水分散液中におけるミセルの平均粒径を測定し、その濃度依存性を測定することができる。かかる測定により、重合体が特定の大きさの分子集合体を形成することが確認できる。 The amphiphilic property of the copolymer according to the present invention is characterized by the ability to reduce surface tension and the ability to form molecular aggregates. Specifically, the surface tension of the copolymer aqueous dispersion can be measured, and its concentration dependency can be measured. The critical micelle concentration (hereinafter referred to as “CMC”) can be determined by such measurement. Furthermore, the average particle diameter of micelles in the aqueous copolymer dispersion can be measured, and the concentration dependency thereof can be measured. By such measurement, it can be confirmed that the polymer forms a molecular aggregate having a specific size.
本発明の共重合体は上で説明したように、両親媒性を示すことから、親水性・親油性界面活性剤、分散剤、乳化剤、高分子材料の表面改質剤等として応用することが可能である。また、特異な分子集合体形成能を示すことから、新機能性材料への応用が可能である。
パーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体の製造方法
本発明のパーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体は上で説明した新規な化学構造、すなわち、スチレンオリゴマー部分と、エチレンオキシド部分とをエーテル結合により結合し、末端のヒドロキシル基をパーフルオロカルボン酸エステルに変換した構造である。従ってかかる構造を有する共重合体を製造することができる方法であれば特に制限されることはない。
As described above, the copolymer of the present invention exhibits amphiphilic properties, and therefore can be applied as a hydrophilic / lipophilic surfactant, a dispersant, an emulsifier, a surface modifier of a polymer material, and the like. Is possible. In addition, since it exhibits a unique ability to form molecular aggregates, it can be applied to new functional materials.
Process for Producing Styrene Oligomer-Polyethylene Oxide Copolymer Having Perfluoroalkyl Group The styrene oligomer-polyethylene oxide copolymer having a perfluoroalkyl group of the present invention has the novel chemical structure described above, that is, a styrene oligomer part and In this structure, an ethylene oxide moiety is linked by an ether bond, and the terminal hydroxyl group is converted to a perfluorocarboxylic acid ester. Accordingly, there is no particular limitation as long as it is a method capable of producing a copolymer having such a structure.
本発明においては特に、一般式（３）
ここで、原料である末端ビニリデンスチレンオリゴマーの入手方法には特に制限はないが、本発明者の開発した熱分解方法（Ｊｏｕｒｎａｌ ｏｆ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ， Ｐｏｌｙｍ． Ｃｈｅｍ．， ３６， ２０９ （１９９８））により、スチレンモノマ単位の繰り返し数が２〜１０程度の単分散性の片末端ビニリデン基含有オリゴスチレンを得ることができる。 Here, the method for obtaining the terminal vinylidene styrene oligomer as a raw material is not particularly limited, but by the thermal decomposition method developed by the present inventors (Journal of Polymer Science, Polym. Chem., 36, 209 (1998)), Monodispersed one-end vinylidene group-containing oligostyrene having a styrene monomer unit repeating number of about 2 to 10 can be obtained.
また、片末端ビニリデン基含有オリゴスチレン（以下、片末端ビニリデンスチレンダイマーを「ＳＤ」、および片末端ビニリデンスチレントリマーを「ＳＴ」とする）から末端ヒドロキシル化スチレンオリゴマーの入手方法も特に制限はない。通常公知の方法に従ってヒドロホウ素化し、さらに酸化的に分解して一般式（４）で表されるヒドロキシル化スチレンオリゴマーを容易に得ることができる。 Also, there is no particular limitation on the method for obtaining the terminal hydroxylated styrene oligomer from the one-end vinylidene group-containing oligostyrene (hereinafter, the one-end vinylidene styrene dimer is “SD” and the one-end vinylidene styrene trimer is “ST”). A hydroxylated styrene oligomer represented by the general formula (4) can be easily obtained by hydroboration according to a generally known method and further oxidative decomposition.
さらに得られたヒドロキシル化スチレンオリゴマーを通常公知の触媒系を用いて、例えばエチレンオキシドとの開環重合によりスチレンオリゴマー−ポリエチレンオキシド共重合体が得られる（以下、スチレンダイマとポリエチレンオキシド共重合体を「ＳＤ−ＰＥＯ」とし、スチレントリマ−ポリエチレンオキシド共重合体を「ＳＴ−ＰＥＯ」とする）。アリキレンオキシドの反応量、触媒系の選択、反応時間、温度等の開環重合の条件については、例えば高分子学会編新高分子実験学２「高分子の合成・反応（１）付加縮合系高分子の合成」（１９９５年共立出版）を参照することができる。 Furthermore, a styrene oligomer-polyethylene oxide copolymer is obtained by subjecting the obtained hydroxylated styrene oligomer to a ring-opening polymerization with, for example, ethylene oxide using a generally known catalyst system (hereinafter, a styrene dimer and a polyethylene oxide copolymer are referred to as “ SD-PEO ”and the styrene trimer-polyethylene oxide copolymer as“ ST-PEO ”). Regarding the conditions of ring-opening polymerization such as the reaction amount of alkylene oxide, selection of catalyst system, reaction time, temperature, etc., for example, New Polymer Experiments 2 edited by the Society of Polymer Sciences, “Synthesis / Reaction of Polymers (1) Addition Condensation System High Reference can be made to “Synthesis of molecules” (1995).
そしてさらに得られたスチレンオリゴマー−ポリエチレンオキシド共重合体にパーフルオロカルボン酸を加え、末端のヒドロキシル基をパーフルオロカルボン酸エステルに変換して、パーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体が得られる（以下、パーフルオロアルキル基を有するスチレンダイマとポリエチレンオキシド共重合体を「ＳＤ−ＰＥＯ−Ｒｆ」とし、スチレントリマ−ポリエチレンオキシド共重合体を「ＳＴ−ＰＥＯ−Ｒｆ」とする）。 Further, perfluorocarboxylic acid is added to the obtained styrene oligomer-polyethylene oxide copolymer, the terminal hydroxyl group is converted into a perfluorocarboxylic acid ester, and a styrene oligomer-polyethylene oxide copolymer having a perfluoroalkyl group is obtained. (Hereinafter, the styrene dimer having a perfluoroalkyl group and the polyethylene oxide copolymer are referred to as “SD-PEO-Rf”, and the styrene trimer-polyethylene oxide copolymer is referred to as “ST-PEO-Rf”).
反応のモニタ、生成物の確認については上で説明したように、ＧＰＣ、ＩＲ、ＮＭＲ等を利用することができる。
（Ｂ）両末端にパーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）・トリブロック共重合体
本発明のＢ−Ａ−Ｂ型トリブロック共重合体は、親有機媒体性、すなわち疎水性のポリオレフィン鎖からなるＡセグメント、および親水性のポリ（オキシアルキレン）鎖からなるＢセグメント、さらに両末端のヒドロキシル基をパーフルオロカルボン酸エステルに変換した構造、からなり両親媒性を示す。
As described above, GPC, IR, NMR, etc. can be used for monitoring the reaction and confirming the product.
(B) Polypropylene / poly (oxyethylene) -triblock copolymer having perfluoroalkyl groups at both ends The B-A-B type triblock copolymer of the present invention has a hydrophilic property, that is, a hydrophobic property. It has amphiphilic properties, consisting of an A segment composed of a polyolefin chain, a B segment composed of a hydrophilic poly (oxyalkylene) chain, and a structure in which hydroxyl groups at both ends are converted into perfluorocarboxylic acid esters.
Ａセグメントのポリオレフィン鎖を構成するモノマー単位は、一般式（２）中のＲ1が−ＣＨ3であるプロピレン・モノマー、またはＲ1が−ＣＨ3と−Ｈおよび／または−Ｃ2Ｈ5との混合基であるプロピレンとエチレンおよび／または１−ブテンとの混合モノマーである。すなわち、Ａセグメントは、プロピレン単独重合体鎖、またはプロピレンとエチレンおよび／または１−ブテンとのプロピレン系共重合体鎖である。一般式（１）にｎで表わされるモノマー単位の繰り返し数は、共重合体の使用目的、有機媒体の種類などにより、通常、１５〜１００の範囲で変化させることができる。 The monomer unit constituting the polyolefin chain of the A segment is a propylene monomer in which R 1 in the general formula (2) is —CH 3 , or R 1 is —CH 3 and —H and / or —C 2 H 5 Is a mixed monomer of propylene and ethylene and / or 1-butene. That is, the A segment is a propylene homopolymer chain or a propylene-based copolymer chain of propylene and ethylene and / or 1-butene. The number of repeating monomer units represented by n in the general formula (1) can usually be changed in the range of 15 to 100 depending on the purpose of use of the copolymer, the kind of the organic medium, and the like.
Ｂセグメントのポリ（オキシアルキレン）鎖を構成する単位は、エチレンオキシドまたはプロピレンオキシドを開環させた一般式（２）中のＲ2が−Ｈであるオキシエチレン基またはＲ2が−ＣＨ3であるオキシプロピレン基である。オキシアルキレン単位の繰り返し数は、共重合体の使用目的、それに付与すべき親水性の程度などにより、一般式（２）中のｌとｍとの合計の前記オレフィンモノマー単位の繰り返し数ｎに対する比［(ｌ＋ｍ）／ｎ］として、通常、０．１〜１０の範囲で変化させることができる。 The unit constituting the poly (oxyalkylene) chain of the B segment is an oxyethylene group in which R 2 is —H in the general formula (2) obtained by ring opening of ethylene oxide or propylene oxide, or R 2 is —CH 3 . It is an oxypropylene group. The number of repeating oxyalkylene units depends on the purpose of use of the copolymer and the degree of hydrophilicity to be imparted to the ratio of the total of l and m in the general formula (2) to the number of repeating olefin monomer units n. [(L + m) / n] can usually be changed within a range of 0.1 to 10.
本発明のＢ−Ａ−Ｂ型トリブロック共重合体は、Ａ、Ｂ両セグメントの長さを調節して種々の特性を変化させることが可能であることにより、たとえば洗剤、乳化剤、染色助剤、分散剤、表面処理剤などノニオン界面活性剤として広範な用途への使用が期待できる。
両末端にパーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）・トリブロック共重合体の製造方法
本発明のパーフルオロアルキル基を有するＢ−Ａ−Ｂ型トリブロック共重合体は、前記ポリオレフィン鎖の両末端にヒドロキシ基を有するオレフィン重合体のヒドロキシ基にアルキレンオキシドを開環縮合させ、さらにエステル化反応により両末端のヒドロキシル基をパーフルオロカルボン酸エステルに変換する公知の方法により容易に製造することができる。
The B-A-B type triblock copolymer of the present invention can change various properties by adjusting the lengths of both the A and B segments. It can be expected to be used in a wide range of applications as a nonionic surfactant such as a dispersant and a surface treatment agent.
Process for Producing Polypropylene / Poly (oxyethylene) / Triblock Copolymer Having Perfluoroalkyl Groups at Both Ends B-A-B Triblock Copolymer Having Perfluoroalkyl Groups of the Present Invention It is easily produced by a known method in which an alkylene oxide is ring-opened and condensed to a hydroxy group of an olefin polymer having hydroxy groups at both ends, and further, a hydroxyl group at both ends is converted to a perfluorocarboxylic acid ester by an esterification reaction. be able to.
安定した特性を有するトリブロック共重合体を製造するために、原料として、オレフィンモノマー単位の繰り返し数のばらつきが小さい、すなわち分子量分布幅（Ｍｗ／Ｍｎ）の狭い単分散性の両末端ヒドロキシ基含有オレフィン重合体を使用することが要求される
上記単分散性の両末端ヒドロキシ基含有オレフィン重合体は、前記Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ， ２８， ８１７ （１９９６）に記載されるポリプロピレンの高度制御熱分解法と同様の方法を採用して両末端ビニリデン基含有オレフィン重合体を製造し、その両末端ビニリデン基を常法により酸化することにより容易に製造することができる。たとえば、両末端ビニリデン基含有オレフィン重合体をヒドロホウ素化し、次いで酸化剤を用いて酸化することにより製造することができる。
In order to produce a triblock copolymer having stable characteristics, the raw material contains monodispersed hydroxy groups at both ends having a small variation in the number of repeating olefin monomer units, that is, a narrow molecular weight distribution width (Mw / Mn). It is required to use an olefin polymer. The monodispersed both-terminal hydroxy group-containing olefin polymer is the same as the highly controlled pyrolysis method of polypropylene described in Polymer Journal, 28, 817 (1996). The method can be used to easily produce a vinylidene group-containing olefin polymer having both ends and to oxidize the vinylidene groups at both ends by a conventional method. For example, it can be produced by hydroborating a vinylidene group-containing olefin polymer at both ends and then oxidizing with an oxidizing agent.
両末端ヒドロキシ基含有オレフィン重合体の有機溶媒溶液に、たとえばナトリウムメトキシドなどの触媒の存在下、アルキレンオキシドを滴下することにより、両末端ヒドロキシ基含有オレフィン重合体にアルキレンオキシドを開環縮合させることができる。 Ring-opening condensation of alkylene oxide to a hydroxy group-containing olefin polymer by dropwise addition of alkylene oxide to the organic solvent solution of the hydroxy group-containing olefin polymer in the presence of a catalyst such as sodium methoxide, for example. Can do.
エステル化反応は、トリブロックコポリマーと片末端カルボキシル化パーフルオロアルキル（ＲｆＣＯＯＨ）、触媒としてｐ−トルエンスルホン酸を用い、トルエン溶媒中で行った。 The esterification reaction was performed in a toluene solvent using a triblock copolymer, one-terminal carboxylated perfluoroalkyl (RfCOOH), and p-toluenesulfonic acid as a catalyst.
各反応生成物のキャラクタリゼーションは、ＩＲ、ＧＰＣ、ＮＭＲ、動的光散乱光度計（ＤＬＳ）、及び表面張力測定装置等で行った。 Each reaction product was characterized by IR, GPC, NMR, dynamic light scattering photometer (DLS), surface tension measuring device, and the like.
以下、本発明を実施例に即して詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
（Ａ）パーフルオロアルキル基を有するスチレンオリゴマー−ポリエチレンオキシド共重合体
EXAMPLES Hereinafter, although this invention is demonstrated in detail according to an Example, this invention is not limited to these Examples.
(A) Styrene oligomer-polyethylene oxide copolymer having a perfluoroalkyl group
実施例１
ＳＤ、ＳＴの合成
ポリスチレンを、３７０℃で３時間熱分解して、ＳＤ及びＳＴをそれぞれ２０ｗｔ％、３０ｗｔ％の収率で得た。
ヒドロキシル化
得られたＳＤ（又はＳＴ）を蒸留ＴＨＦ中に溶解し、ボランＴＨＦ錯体−ＴＨＦ溶液を加えて、７０℃で５時間攪拌しながら反応させた。得られたヒドロホウ素化ＳＤ（又はＳＴ）のＴＨＦ溶液に、過酸化水素水、水酸化ナトリウムを加え、温度５０℃で２０時間反応させた。
エチレンオキシド開環重合
得られた片末端ヒドロキシル化スチレンダイマー（ＳＤ−ＯＨ）あるいは片末端スチレントリマー（ＳＴ−ＯＨ）と、重合開始剤としてナトリムメトキシド−メタノール溶液、溶媒として蒸留トルエンを加え、１３０℃、窒素雰囲気下で内圧を制御しながら、エチレンオキシド（ＥＯ）を滴下し、それぞれＳＤ−ＰＥＯ−１、ＳＤ−ＰＥＯ−２及びＳＴ−ＰＥＯを試料として得た。
Example 1
Synthetic polystyrene of SD and ST was pyrolyzed at 370 ° C. for 3 hours to obtain SD and ST in yields of 20 wt% and 30 wt%, respectively.
The SD (or ST) obtained by hydroxylation was dissolved in distilled THF, a borane THF complex-THF solution was added, and the mixture was reacted at 70 ° C. with stirring for 5 hours. Hydrogen peroxide water and sodium hydroxide were added to the obtained THF solution of hydroborated SD (or ST) and reacted at a temperature of 50 ° C. for 20 hours.
Ethylene oxide ring-opening polymerization One- terminal hydroxylated styrene dimer (SD-OH) or one-terminal styrene trimer (ST-OH) obtained, a sodium methoxide-methanol solution as a polymerization initiator and distilled toluene as a solvent were added, and 130 ° C. While controlling the internal pressure in a nitrogen atmosphere, ethylene oxide (EO) was added dropwise to obtain SD-PEO-1, SD-PEO-2, and ST-PEO as samples, respectively.
表１にその結果をまとめた。 Table 1 summarizes the results.
各サンプルのＧＰＣ測定により、ＳＤ−ＰＥＯ−１、ＳＤ−ＰＥＯ−２おびＳＴ−ＰＥＯいずれにおいても、原料（ＳＤ−ＯＨおよびＳＴ−ＯＨ）と比べ、大きく分子量が増大したことが分かった。 From the GPC measurement of each sample, it was found that the molecular weight was greatly increased in each of SD-PEO-1, SD-PEO-2 and ST-PEO as compared with the raw materials (SD-OH and ST-OH).
ＳＤ−ＰＥＯ−１では、Ｍｎ：１５００付近、Ｍｎ：４００付近および原料のＳＤ−ＯＨと考えられるＭｎ：２２０付近に溶出ピークが現れた。Ｍｎ：１５００付近およびＭｎ：４００付近の溶出ピークは、リサイクル型ＧＰＣで分離し、ＩＲスペクトルで構造解析した結果、Ｍｎ：１５００付近の溶出ピークをナトリウムメトキシドの溶媒として用いたメタノールのＯＨ基を開始点として生成するＰＥＯホモポリマー、Ｍｎ：４００付近の溶出ピークをＳＤ−ＰＥＯと帰属できる。 In SD-PEO-1, an elution peak appeared in the vicinity of Mn: 1500, Mn: 400, and Mn: 220 considered to be the raw material SD-OH. The elution peaks near Mn: 1500 and Mn: 400 were separated by recycle GPC and analyzed by IR spectrum. As a result, the OH group of methanol was obtained using the elution peak near Mn: 1500 as a solvent for sodium methoxide. The elution peak around PEO homopolymer Mn: 400 generated as a starting point can be attributed to SD-PEO.
ＳＤ−ＰＥＯ−２においても同様に、Ｍｎ：２８００付近にＰＥＯホモポリマー、Ｍｎ：９００付近にＳＤ−ＰＥＯ、Ｍｎ：２２０付近にＳＤ−ＯＨのピークが現れ、分離精製した。 Similarly, in SD-PEO-2, PEO homopolymer was observed near Mn: 2800, SD-PEO was observed near Mn: 900, and SD-OH peaks were observed near Mn: 220, which were separated and purified.
ＳＴ−ＰＥＯにおいても同様に、Ｍｎ：９７０付近にＳＴ‐ＰＥＯ、Ｍｎ：３２０付近にＳＴ‐ＯＨのピークが現れ、分離精製した。 Similarly, in ST-PEO, ST-PEO appears in the vicinity of Mn: 970 and ST-OH peaks in the vicinity of Mn: 320, which are separated and purified.
また、ＰＥＯホモポリマー、ＳＤ−ＰＥＯ−１の各ＩＲスペクトル測定により、ＳＤ−ＰＥＯ−１において、ＰＥＯホモポリマーと考えられるピークを分離して解析した結果、１１００ｃｍ-1付近のエーテル結合に起因する吸収が明瞭に出現し、１８００〜２０００ｃｍ-1付近のスチレンユニットのフェニル基に起因する吸収の減少が認められる。一方、ＳＤ−ＰＥＯ−１と考えられるピークを分離して解析した結果では、１１００ｃｍ-1付近のエーテル結合に起因する吸収が明瞭に出現し、１８００〜２０００ｃｍ-1付近のスチレンユニットのフェニル基に起因する吸収の減少は認められなかった。また、ＳＤ−ＰＥＯ−２およびＳＴ−ＰＥＯにおいても同様な結果が得られる。このことから、目的の共重合体が合成されたことがわかる。 Moreover, as a result of separating and analyzing the peak considered to be a PEO homopolymer in SD-PEO-1 by each IR spectrum measurement of PEO homopolymer and SD-PEO-1, it originates in the ether bond of 1100 cm < -1 > vicinity. Absorption appears clearly, and a decrease in absorption due to the phenyl group of the styrene unit near 1800 to 2000 cm −1 is observed. On the other hand, the results of analysis by separating the peaks considered SD-PEO-1 emerges clearly that absorption due to an ether bond at around 1100 cm -1, the phenyl group of styrene unit in the vicinity 1800～2000Cm -1 There was no decrease in absorption due to it. Similar results are obtained with SD-PEO-2 and ST-PEO. This shows that the target copolymer was synthesized.
図１にＳＤ−ＰＥＯ−１の1Ｈ−ＮＭＲスペクトル示す。１．５〜３ｐｐｍ付近にスチレンモノマーユニットの脂肪族に起因するシグナル、３．５ｐｐｍ付近にエーテル結合の隣のスチレンモノマーユニットに起因するシグナル、７ｐｐｍ付近にスチレンモノマーユニットの芳香族に起因するシグナル、３．５〜４ｐｐｍ付近にＥＯモノマーユニットに起因するシグナルがそれぞれ現れた。 FIG. 1 shows the 1 H-NMR spectrum of SD-PEO-1. A signal due to the aliphatic of the styrene monomer unit at around 1.5 to 3 ppm, a signal due to the styrene monomer unit next to the ether bond at around 3.5 ppm, a signal due to the aromatic of the styrene monomer unit at around 7 ppm, Signals attributed to the EO monomer unit appeared in the vicinity of 3.5 to 4 ppm.
また、1Ｈ−ＮＭＲスペクトルの積分強度から求めたスチレンモノマーユニット：ＥＯモノマーユニットのモル組成比は、２：５であった。ＳＤ−ＰＥＯ−２およびＳＴ−ＰＥＯにおいても、ＳＤ−ＰＥＯ−１と同様の結果が得られ、それぞれのスチレンモノマーユニット：ＥＯモノマーユニットのモル組成比は、ＳＤ−ＰＥＯ−２は２：１７、ＳＴ−ＰＥＯは３：２９であった。以上のことから、目的共重合体が合成されたことが分かる。
共重合体水分散液による表面張力測定
合成した各共重合体の水分散液を１０−４（ｇ／Ｌ）〜０．５（ｇ／Ｌ）の濃度になるように調製し、プレート法による全自動表面張力測定装置（共和界面科学(株)製自動表面張力計ＣＢＶＰ−Ｚ）を用いて測定した。
The molar composition ratio of the styrene monomer unit: EO monomer unit determined from the integrated intensity of the 1 H-NMR spectrum was 2: 5. In SD-PEO-2 and ST-PEO, the same results as in SD-PEO-1 were obtained. The molar composition ratio of each styrene monomer unit: EO monomer unit was 2:17 for SD-PEO-2. ST-PEO was 3:29. From the above, it can be seen that the target copolymer was synthesized.
Measurement of surface tension with aqueous copolymer dispersion An aqueous dispersion of each copolymer synthesized was prepared so as to have a concentration of 10 −4 (g / L) to 0.5 (g / L). It measured using the fully automatic surface tension measuring apparatus (Kyowa Interface Science Co., Ltd. automatic surface tension meter CBVP-Z).
図２に各共重合体水分散液による表面張力の濃度依存性を示した。各共重合体いずれにおいても、濃度が上昇するにつれ、表面張力は減少し、ＳＤ−ＰＥＯ−１では０．３ｇ／Ｌ、ＳＤ−ＰＥＯ−２では０．２ｇ／Ｌ、ＳＴ−ＰＥＯでは０．１ｇ／Ｌに臨界ミセル濃度（ＣＭＣ）の存在が確認できた。スチレンモノマーユニットが同様であるＳＤ−ＰＥＯ−１とＳＤ−ＰＥＯ−２を比較すると、１分子中のＥＯユニットが多いものほど低濃度領域での表面張力低下能に優れていることがわかる。また、各モノマーユニットの組成比が同程度なＳＤ−ＰＥＯ−２とＳＴ−ＰＥＯを比較すると、スチレンユニットが多いものほど、低濃度領域での表面張力低下能に優れていることがわかる。 FIG. 2 shows the concentration dependence of the surface tension of each copolymer aqueous dispersion. In each of the copolymers, as the concentration increases, the surface tension decreases, 0.3 g / L for SD-PEO-1, 0.2 g / L for SD-PEO-2, and 0.2 for ST-PEO. The presence of critical micelle concentration (CMC) at 1 g / L was confirmed. Comparing SD-PEO-1 and SD-PEO-2 in which the styrene monomer units are the same, it can be seen that the more EO units in one molecule, the better the surface tension lowering ability in the low concentration region. Further, when SD-PEO-2 and ST-PEO having the same composition ratio of each monomer unit are compared, it can be seen that the more styrene units, the better the surface tension reducing ability in a low concentration region.
これらより、各モノマーユニットの組成比が、表面張力低下能に影響していることが示される。
共重合体水分散液によるミセルの粒径測定
合成した各共重合体の水分散液を０．１（ｇ／Ｌ）〜０．５（ｇ／Ｌ）の濃度になるように調製し、動的光散乱装置（大塚電子(株)製ＤＬＳ７０００ｓｅｒｉｅｓ）を用いて測定を行った。
From these, it is shown that the composition ratio of each monomer unit affects the surface tension lowering ability.
Measurement of micelle particle size with aqueous copolymer dispersion The aqueous dispersion of each synthesized copolymer was prepared to a concentration of 0.1 (g / L) to 0.5 (g / L). The measurement was performed using an automatic light scattering device (DLS7000 series, manufactured by Otsuka Electronics Co., Ltd.).
図３には各共重合体分散液中におけるミセルの平均粒径の濃度依存性を示した。各共重合体いずれにおいても濃度が上昇するにつれ、粒径が減少するが、ＣＭＣ以降粒径が増加する。各共重合体分散液中のミセルの平均粒径は、ＳＤ−ＰＥＯ−１は約１４０ｎｍ、ＳＤ−ＰＥＯ−２は約７０ｎｍ、ＳＴ−ＰＥＯは約１３０ｎｍであり、各共重合体分子の伸長鎖長の２７倍、５倍、６倍と極めて大きな分子集合体を形成していると考えられる。粒径測定の結果から、形成される分子集合体は、スチレンユニットの疎水性相互作用が因子として働き、単純なミセル構造ではなく、親水基と疎水基が何重にも重なり、極めて大きな分子集合体を形成していると考えられる。その構造として、２分子膜もしくはそれ以上の多分子膜を形成していると考えられる。 FIG. 3 shows the concentration dependency of the average particle size of micelles in each copolymer dispersion. In any copolymer, the particle size decreases as the concentration increases, but the particle size increases after CMC. The average particle size of micelles in each copolymer dispersion is about 140 nm for SD-PEO-1, about 70 nm for SD-PEO-2, and about 130 nm for ST-PEO. It is considered that a very large molecular assembly of 27 times, 5 times and 6 times the length is formed. From the results of particle size measurement, the molecular assembly formed is based on the hydrophobic interaction of the styrene units, and is not a simple micelle structure. It is thought that the body is formed. As its structure, it is considered that a bimolecular film or a multi-molecular film is formed.
実施例２
ＳＤ−ＯＨの合成
還流器、窒素風船を装着した反応容器にＳＤを採取し、窒素置換した後、ＴＨＦおよびボランＴＨＦ錯体ＴＨＦ溶液を加え、約７０℃で５時間反応させた。その後、１Ｎ水酸化ナトリウム水溶液を徐々に加えた後、過酸化水素水を徐々に滴下し、約５０℃で２０時間反応させた。反応後、飽和食塩水を加え、ＴＨＦ層を回収し、溶媒を留去してＳＤ−ＯＨを得た。
ＳＤ−ＰＥＯの合成
耐圧ガラス製オートクレーブに試料（ＳＤ−ＯＨ）、触媒ナトリウムメトキシド、溶媒蒸留トルエンを採取し、エチレンオキシド（ＥＯ）を反応温度１３０℃、窒素雰囲気下で内圧を制御しながら滴下し、所定時間反応させた。反応後、トルエンを除去し、リサイクルＧＰＣで分取してＳＤ−ＰＥＯを得た。
ＳＤ−ＰＥＯ−Ｒｆの合成
ＳＤ−ＰＥＯ：Ｒｆ（ＲｆＣＯＯＨ）：ｐ−トルエンスルホン酸のモル比が１：１：０．２となるようにそれぞれを採取し、トルエンに溶解し、反応系外に水を除去しながら２４時間加熱還流することにより行った。反応後、クロロホルムおよび炭酸ナトリウム水溶液を加え、クロロホルム層を回収し、溶媒を留去してＳＤ−ＰＥＯ−Ｒｆを得た。
ＳＤ−ＯＨの合成結果
ＳＤ−ＯＨのＩＲスペクトルにおいて、原料ＳＤの末端ビニリデン基に起因する１６５０および８９５ｃｍ−１付近の吸収が消失し、３４００ｃｍ−１１付近のヒドロキシル基由来のブロードな吸収が現れた。また１Ｈ−ＮＭＲスペクトルでは、原料ＳＤに現れる５．０〜５．５ｐｐｍ付近の末端ビニリデン基に起因するシグナルがほぼ完全に消失し、３．５〜４．０ｐｐｍ付近にヒドロキシル基隣接メチレンに由来するシグナルが現れた。ヒドロキシル化はほぼ定量的に進行した。
ＳＤ−ＰＥＯの合成結果
表２に示されるように、ＳＤ−ＰＥＯのＭｎは０．９１×１０３、Ｍｗ／Ｍｎは１．０９であった。ＳＤ−ＰＥＯのＩＲスペクトルにおいて、１１００ｃｍ−１付近のエーテル結合に起因する吸収が明瞭に出現し、また１Ｈ−ＮＭＲスペクトルでは、３．５〜４．０ｐｐｍ付近にＥＯモノマーユニットに起因するシグナルが、１３Ｃ−ＮＭＲスペクトルにおいても、６０ｐｐｍ付近にエーテル結合の隣のスチレンモノマーユニットに起因するシグナルがそれぞれ現れた。スチレンモノマーユニットとＥＯモノマーユニットのモル組成比は２：１７であった。
Example 2
The SD was collected in a reaction vessel equipped with a synthesis reflux condenser and a nitrogen balloon of the SD-OH , purged with nitrogen, THF and a borane / THF complex THF solution were added, and the mixture was reacted at about 70 ° C. for 5 hours. Thereafter, a 1N sodium hydroxide aqueous solution was gradually added, and then a hydrogen peroxide solution was gradually dropped and reacted at about 50 ° C. for 20 hours. After the reaction, saturated brine was added, the THF layer was recovered, and the solvent was distilled off to obtain SD-OH.
A sample (SD-OH), catalytic sodium methoxide, and solvent-distilled toluene were collected in a pressure-resistant glass autoclave of SD-PEO , and ethylene oxide (EO) was dropped while controlling the internal pressure in a nitrogen atmosphere at a reaction temperature of 130 ° C. And allowed to react for a predetermined time. After the reaction, toluene was removed and fractionated with recycled GPC to obtain SD-PEO.
Synthesis of SD-PEO-Rf Each sample was collected so that the molar ratio of SD-PEO: Rf (RfCOOH): p-toluenesulfonic acid was 1: 1: 0.2, dissolved in toluene, and removed from the reaction system. This was carried out by heating under reflux for 24 hours while removing water. After the reaction, chloroform and an aqueous sodium carbonate solution were added, the chloroform layer was recovered, and the solvent was distilled off to obtain SD-PEO-Rf.
As a result of the synthesis of SD-OH, in the IR spectrum of SD-OH, absorption near 1650 and 895 cm −1 due to the terminal vinylidene group of the raw material SD disappeared, and broad absorption derived from hydroxyl group near 3400 cm -11 appeared. . In the 1 H-NMR spectrum, the signal due to the terminal vinylidene group near 5.0 to 5.5 ppm that appears in the raw material SD disappears almost completely, and the hydroxyl group is adjacent to methylene near 3.5 to 4.0 ppm. Signal appeared. Hydroxylation proceeded almost quantitatively.
Synthesis results of SD-PEO As shown in Table 2, the Mn of SD-PEO was 0.91 × 10 3 and Mw / Mn was 1.09. In the IR spectrum of SD-PEO, absorption due to an ether bond near 1100 cm −1 clearly appears, and in the 1 H-NMR spectrum, a signal due to an EO monomer unit is present in the vicinity of 3.5 to 4.0 ppm. In the 13 C-NMR spectrum, signals due to the styrene monomer unit adjacent to the ether bond appeared in the vicinity of 60 ppm. The molar composition ratio of the styrene monomer unit to the EO monomer unit was 2:17.
ＳＤ−ＰＥＯ−Ｒｆの分子量分布は単峰性であり、ＳＤ−ＰＥＯと比較して全体的に高分子量側にシフトした。表２に示されるように、そのＭｎは１．２８×１０３、Ｍｗ／Ｍｎは１．０７であった。また、図４に示されるように、ＳＤ−ＰＥＯ−ＲｆのＩＲスペクトルにおいて、３４００ｃｍ−１付近のヒドロキシル基由来のブロードな吸収が減少し、１２４０および１７８０ｃｍ−１付近にエステル基に起因する吸収、また１２１０ｃｍ−１付近にフッ素基に起因する吸収が現れた。
表面張力
図５にＳＤ−ＰＥＯおよびＳＤ−ＰＥＯ−Ｒｆ水分散液の表面張力を示した。濃度の増加とともに、どちらの場合も表面張力は低下し、臨界ミセル濃度（ＣＭＣ）が確認された。ＣＭＣはＳＤ−ＰＥＯで０．３ｇ／Ｌ付近、ＳＤ−ＰＥＯ−Ｒｆで０．１ｇ／Ｌ付近であるが、その表面張力は、それぞれ約４４および約２８ｍＮ／ｍであった。表面張力低下に対する末端Ｒｆ基の大きな疎水性相互作用が認められた。
（Ｂ）パーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）・トリブロック共重合体
Surface Tension FIG. 5 shows the surface tension of SD-PEO and SD-PEO-Rf aqueous dispersion. As the concentration increased, the surface tension decreased in both cases, confirming the critical micelle concentration (CMC). CMC was around 0.3 g / L for SD-PEO and around 0.1 g / L for SD-PEO-Rf, but the surface tensions were about 44 and about 28 mN / m, respectively. A large hydrophobic interaction of the terminal Rf group on surface tension reduction was observed.
(B) Polypropylene / poly (oxyethylene) triblock copolymer having a perfluoroalkyl group
実施例３
パーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）トリブロック共重合体の製造１
数平均分子量（Ｍｎ）が１１１×１０３、Ｍｗ／Ｍｎが８．３９のアイソタクッチック・ポリプロピレン（ｍｍ：ｍｒ：ｒｒ＝９８：１：１）の高度制御熱分解による揮発生成物から蒸留、再沈殿により、数平均分子量（Ｍｎ）が１．４３×１０３、Ｍｗ／Ｍｎが１．１１の単分散性の両末端ビニリデン基含有ポリプロピレンを得た。
Example 3
Production of polypropylene / poly (oxyethylene) triblock copolymer having perfluoroalkyl group 1
Distillation from volatile products by highly controlled pyrolysis of isotactic polypropylene (mm: mr: rr = 98: 1: 1) having a number average molecular weight (Mn) of 111 × 10 3 and Mw / Mn of 8.39, By reprecipitation, a monodispersed bi-terminal vinylidene group-containing polypropylene having a number average molecular weight (Mn) of 1.43 × 10 3 and Mw / Mn of 1.11.
得られた両末端ビニリデン基含有ポリプロピレンをＴＨＦ溶媒に分散させ、ＢＨ3−ＴＨＦ錯体・ＴＨＦ溶液を滴下し、窒素ガス雰囲気下でヒドロホウ素化した後、ＮａＯＨ水溶液および過酸化水素水により酸化して、末端ビニリデン基をヒドロキシ基に変換させ、両末端ヒドロキシ基含有ポリプロピレンを得た。 The obtained vinylidene group-containing polypropylene at both ends was dispersed in a THF solvent, a BH 3 -THF complex / THF solution was added dropwise, hydroborated in a nitrogen gas atmosphere, and then oxidized with an aqueous NaOH solution and a hydrogen peroxide solution. The terminal vinylidene group was converted to a hydroxy group to obtain a both-end hydroxy group-containing polypropylene.
両末端ヒドロキシ基含有ポリプロピレンをトルエンに溶解した溶液に触媒としてナトリウムメトキシドを分散させ、窒素ガス雰囲気下、反応温度１３０℃で内圧を制御しながらオレフィン重合体１モル当たり、エチレンオキシドを滴下し反応させた。得られた反応生成物をアセトン還流下に加熱した後、室温でアセトン可溶成分と不溶成分に分別した。次いでアセトン可溶成分からリサイクルＧＰＣにより重合体を分取した。 Sodium methoxide is dispersed as a catalyst in a solution in which both end hydroxy group-containing polypropylene is dissolved in toluene, and ethylene oxide is dropped and reacted per mole of the olefin polymer while controlling the internal pressure at a reaction temperature of 130 ° C. in a nitrogen gas atmosphere. It was. The obtained reaction product was heated under reflux of acetone and then separated into an acetone soluble component and an insoluble component at room temperature. Next, the polymer was separated from the acetone-soluble component by recycled GPC.
得られた重合体のＩＲスペクトルは、エチレンオキシドのエーテル結合に起因する吸収が１１００ｃｍ−１に現れ、ＮＭＲスペクトルはオキシエチレンブロックのメチレンに起因するシグナル１Ｈ：３.５〜４.０ｐｐｍ、１３Ｃ：７０〜７１ｐｐｍ（ＴＭＳ基準）が出現し、重合体がプロピレン／ポリ（オキシエチレン）トリブロック共重合体であることを確認した。 In the IR spectrum of the obtained polymer, an absorption due to the ether bond of ethylene oxide appears at 1100 cm −1 , and the NMR spectrum shows a signal 1 H due to methylene in the oxyethylene block: 3.5 to 4.0 ppm, 13 C : 70-71 ppm (TMS standard) appeared, and it was confirmed that the polymer was a propylene / poly (oxyethylene) triblock copolymer.
得られたトリブロック重合体の１Ｈ−ＮＭＲの積算強度比から算出したプロピレン単位に対するオキシエチレン単位の比［(ｌ＋ｍ)／ｎ］は０．８６であった。また、ＧＰＣによる数平均分子量（Ｍｎ）（ポリスチレン換算）は２．１５×１０３、Ｍｗ／Ｍｎは１．０７であり、ＤＳＣによる融点（Ｔｍ）は１０４〜１２４℃であった。 The ratio [(l + m) / n] of the oxyethylene unit to the propylene unit calculated from the integrated intensity ratio of 1 H-NMR of the obtained triblock polymer was 0.86. Moreover, the number average molecular weight (Mn) by GPC (polystyrene conversion) was 2.15 * 10 < 3 >, Mw / Mn was 1.07, and melting | fusing point (Tm) by DSC was 104-124 degreeC.
得られたトリブロック共重合体（ｉＰＰ−ｂ−ＰＥＯ）のＧＰＣ、ＤＳＣおよび１３Ｃ−ＮＭＲによる特性評価結果を、出発原料ポリプロピレン（ｉＰＰ）、両末端ビニリデン基含有ポリプロピレン（ｉＰＰＶ）および両末端ヒドロキシ基含有ポリプロピレン（ｉＰＰＯＨ）の評価結果と共に表３に示す。 The results of characterization by GPC, DSC and 13 C-NMR of the obtained triblock copolymer (iPP-b-PEO) are shown as starting material polypropylene (iPP), both-end vinylidene group-containing polypropylene (iPPV) and both-end hydroxy. Table 3 shows the evaluation results of the group-containing polypropylene (iPPOH).
また、トリブロック共重合体（ｉＰＰ−ｂ−ＰＥＯ）、両末端ビニリデン基含有ポリプロピレン（ｉＰＰＶ）および両末端ヒドロキシ基含有ポリプロピレン（ｉＰＰＯＨ）のＧＰＣ曲線を図６に、両末端ヒドロキシ基含有ポリプロピレン（ｉＰＰＯＨ）およびトリブロック共重合体（ｉＰＰ−ｂ−ＰＥＯ）の１３Ｃ−ＮＭＲスペクトルを図７に示す。 The GPC curves of the triblock copolymer (iPP-b-PEO), both-end vinylidene group-containing polypropylene (iPPV) and both-end hydroxy group-containing polypropylene (iPPOH) are shown in FIG. 6, and both-end hydroxy group-containing polypropylene (iPPOH). ) And the 13 C-NMR spectrum of the triblock copolymer (iPP-b-PEO) are shown in FIG.
実施例４
両親媒性物質としての評価１
実施例３で得られたトリブロック共重合体の両親媒性物質としての特性評価のために希薄水溶液の表面張力および水媒体中の粒径分布を測定した。
Example 4
Evaluation as amphiphile 1
In order to evaluate the characteristics of the triblock copolymer obtained in Example 3 as an amphiphile, the surface tension of the dilute aqueous solution and the particle size distribution in the aqueous medium were measured.
表面張力：ジュヌーイ（ｄｕ Ｎｏｕｙ）の表面張力計を用いて２０℃で測定した表面張力を、図８に示す。 Surface Tension: FIG. 8 shows the surface tension measured at 20 ° C. using a Du Nouy surface tension meter.
図８において縦軸は表面張力計の目盛りの読み取り値、横軸は水溶液中のトリブロック共重合体の濃度（ｍｇ／ｍｌ）を表わす。 In FIG. 8, the vertical axis represents the reading of the surface tension meter scale, and the horizontal axis represents the concentration (mg / ml) of the triblock copolymer in the aqueous solution.
図８の縦軸は水を基準にした相対的な表面張力を表わすがトリブロック共重合体のわずかな量で水溶液の表面張力が大幅に低下することを示す。 The vertical axis in FIG. 8 represents the relative surface tension based on water, but shows that the surface tension of the aqueous solution is greatly reduced with a small amount of the triblock copolymer.
粒径分布：水性媒体中のトリブロック共重合体分散体について、Ｈｅ−Ｎｅレーザーによる動的光散乱光（ＤＬＳ）を測定するキュムラント法により２５℃で測定した粒径分布を図９に示す。 Particle size distribution: FIG. 9 shows the particle size distribution of a triblock copolymer dispersion in an aqueous medium measured at 25 ° C. by a cumulant method for measuring dynamic light scattered light (DLS) by a He—Ne laser.
図８および９の結果は、トリブロック共重合体の臨界ミセル濃度（ｃ．ｍ．ｃ）がほぼ０．０４ｍｇ／ｍｌであることを示す。 The results in FIGS. 8 and 9 indicate that the critical micelle concentration (cmc) of the triblock copolymer is approximately 0.04 mg / ml.
実施例５
パーフルオロアルキル基を有するポリプロピレン／ポリ（オキシエチレン）トリブロック共重合体の製造２
ナス型フラスコに、ｉＰＰ−ｂ−ＰＥＯ（Ｍｎ：１６００ Ｍｗ／Ｍｎ：１．２０）を１．００ｇ（６．５×１０−４ｍｏｌ）、ＲｆＣＯＯＨを１．２４ｇ（２．７×１０−３ｍｏｌ）、ｐ−トルエンスルホン酸（ｐ−ＴＳＡ）を０．０１ｇ（５．３×１０−５ｍｏｌ）および溶媒として２０ｍｌの蒸留トルエンを仕込んだ（ｉＰＰ−ｂ−ＰＥＯ：ＲｆＣＯＯＨ：ｐ−ＴＳＡ＝１：４．１：０．０８（モル比）となるよう採取）。これに水分定量受器、ジムロート式冷却管、及び窒素ガス風船を装着した。生成する水を反応系外に除去しながら、反応温度１４０℃で、１２時間反応させた。
Example 5
Production of polypropylene / poly (oxyethylene) triblock copolymer having perfluoroalkyl group 2
In an eggplant-shaped flask, 1.00 g (6.5 × 10 −4 mol) of iPP-b-PEO (Mn: 1600 Mw / Mn: 1.20) and 1.24 g (2.7 × 10 −3 of RfCOOH) were obtained. mol), 0.01 g (5.3 × 10 −5 mol) of p-toluenesulfonic acid (p-TSA) and 20 ml of distilled toluene as a solvent (iPP-b-PEO: RfCOOH: p-TSA = 1: 4.1: 0.08 (molar ratio)). This was equipped with a moisture meter, a Dimroth condenser, and a nitrogen gas balloon. The reaction was carried out at a reaction temperature of 140 ° C. for 12 hours while removing the produced water from the reaction system.
得られた反応溶液を２４時間静置後、ろ別し、トルエン可溶成分と不溶成分に分別した。可溶成分からトルエンを留去し、得た合成混合物をクロロホルムに溶解後、リサイクル型ＧＰＣにて分離・精製し、ｉＰＰ−ｂ−ＰＥＯ：Ｒｆ（Ｍｎ：１８００ Ｍｗ／Ｍｎ：１．１５）を得た。 The obtained reaction solution was allowed to stand for 24 hours, and then filtered to separate into a toluene soluble component and an insoluble component. Toluene was distilled off from the soluble component, and the resultant synthesis mixture was dissolved in chloroform, and then separated and purified by recycle GPC, and iPP-b-PEO: Rf (Mn: 1800 Mw / Mn: 1.15) was obtained. Obtained.
実施例６
両親媒性物質としての評価２
イソタクチックオリゴプロピレンとオリゴ（エチレンオキシド）とのトリブロックコポリマー（ｉＰＰ‐ｂ‐ＰＥＯ、Ｍｎ：１．５×１０３、Ｍｗ／Ｍｎ：１．１８）は、水分散系において巨大な分子会合体が形成され、ＤＬＳより測定した粒径は、ＥＯセグメントの割合が増大することにより、大きくなる傾向を示した。
Example 6
Evaluation 2 as an amphiphile
A triblock copolymer of isotactic oligopropylene and oligo (ethylene oxide) (iPP-b-PEO, Mn: 1.5 × 10 3 , Mw / Mn: 1.18) is a large molecular aggregate in an aqueous dispersion. The particle diameter measured by DLS tended to increase as the proportion of EO segments increased.
図１０に示されるように、このｉＰＰ−ｂ−ＰＥＯとＣ８Ｆ１７ＣＯＯＨを用いたエステル化反応における生成物のＩＲスペクトルにおいて、ｉＰＰ−ｂ−ＰＥＯの末端ヒドロキシル基由来の吸収（３４００ｃｍ−１付近）が著しく減少し、カルボニル由来（１８００ｃｍ−１付近）、及びフッ素基由来（１２００ｃｍ−１付近）の吸収が新たに現れた。 As shown in FIG. 10, in the IR spectrum of the product in the esterification reaction using iPP-b-PEO and C 8 F 17 COOH, absorption from the terminal hydroxyl group of iPP-b-PEO (3400 cm −1 near) is significantly reduced, near carbonyl-derived (1800 cm -1), and the absorption derived from the fluorine group (1200 cm around -1) newly appeared.
またＧＰＣにおいて分子量の増加が認められたことから、エステル化反応によるブロック共重合体（ｉＰＰ‐ｂ‐ＰＥＯ‐Ｒｆ）の生成が確認できた。ｉＰＰ‐ｂ‐ＰＥＯ‐ＲｆはｉＰＰ‐ｂ‐ＰＥＯと同様に水に良く分散し、その状態を長時間安定に保った。 In addition, since an increase in molecular weight was observed in GPC, it was confirmed that a block copolymer (iPP-b-PEO-Rf) was formed by an esterification reaction. Like iPP-b-PEO, iPP-b-PEO-Rf was well dispersed in water and kept its state stable for a long time.
図１１に示した通り、またこの系において、ｉＰＰ‐ｂ‐ＰＥＯ‐Ｒｆの表面張力は、ｉＰＰ‐ｂ‐ＰＥＯに比較して著しく減少した。 As shown in FIG. 11, and in this system, the surface tension of iPP-b-PEO-Rf was significantly reduced compared to iPP-b-PEO.
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| JPS621725A (en) * | 1985-06-28 | 1987-01-07 | Teijin Ltd | Production of polyester |
| JPH03179027A (en) * | 1989-12-07 | 1991-08-05 | Shin Etsu Chem Co Ltd | Production of high-molecular weight organopolysiloxane |
| JPH06172539A (en) * | 1992-12-04 | 1994-06-21 | Mitsubishi Cable Ind Ltd | Hydrophilic elastomer |
| JP2002097378A (en) * | 2000-07-21 | 2002-04-02 | Sanyo Chem Ind Ltd | Filler-containing antistatic resin composition |
| JP2002321314A (en) * | 2001-02-21 | 2002-11-05 | Sanyo Chem Ind Ltd | Antistatic resin film |
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| JPS621725A (en) * | 1985-06-28 | 1987-01-07 | Teijin Ltd | Production of polyester |
| JPH03179027A (en) * | 1989-12-07 | 1991-08-05 | Shin Etsu Chem Co Ltd | Production of high-molecular weight organopolysiloxane |
| JPH06172539A (en) * | 1992-12-04 | 1994-06-21 | Mitsubishi Cable Ind Ltd | Hydrophilic elastomer |
| JP2002097378A (en) * | 2000-07-21 | 2002-04-02 | Sanyo Chem Ind Ltd | Filler-containing antistatic resin composition |
| JP2002321314A (en) * | 2001-02-21 | 2002-11-05 | Sanyo Chem Ind Ltd | Antistatic resin film |
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