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The addition of water to tetrabutylammonium bromide (TBABr)/benzene/sodium bromide ternary component systems induced the separation of TBABr-rich liquid phase (L phase) prior to the appearance of an aqueous phase (W phase). The L phase was assumed to be a bicontinuous phase similar to a microemulsion based on the phase composition. TBABr catalyzed the “solid–liquid” phase-transfer reaction of decyl methanesulfonate with sodium bromide either when the L phase was fully hydrated or after a distinct W phase was formed. The phase-transfer catalytic activity was correlated to the phase behavior of TBABr/benzene/water/NaBr four-component system. The difference and similarity between TBABr and tetrabutylphosphonium bromide (TBPBr) were discussed based on the microstructure of the phases formed by TBABr and TBPBr under the phase-transfer catalytic reaction conditions.

対イオンをドデシル硫酸イオンに交換したトリメチルアンモニオプロピル基を側鎖にもつアクリルアミドゲルの水/有機混合溶媒中での膨潤挙動を検討した. 水/アセトン混合溶媒中では, 溶媒のアセトン含有率を大きくすると, ある含有率で収縮したゲルが急激に体積増加する現象が観察された. さらに含有率が増大すると, ゲルは再収縮する傾向が見られた. その他の有機溶媒を用いたときも, 急激な膨潤を示す点が見られた. この急激な膨潤は, 有機溶媒を加えることによってゲル中に存在していたドデシル硫酸イオンの集合体が破壊されることによって引き起こされていることが示唆された.

The phase behavior and component composition of the coexisting phases in the tetrabutylammonium bromide (TBABr)/benzene/water/NaBr four-component system were strongly influenced by the temperature, TBABr content, and NaBr concentration. The phase-transfer catalytic activity of TBABr for the reaction of decyl methanesulfonate with sodium bromide was closely related to the phase behavior. Under O (oil-rich phase) + L (TBABr-rich liquid phase) + W (aqueous phase) triphase conditions, the influences of temperature and stirring speed on the phase-transfer catalytic activity were small compared with those under O + W biphase conditions. The addition of other quaternary salts that were able to form w/o aggregates in the O phase enhanced the TBABr catalytic activity even under O + W conditions. The relationship between phase behavior and catalytic activity of tetrabutylammonium chloride or iodide (TBACl or TBAI) was also examined. The results strongly suggested that the catalysis of TBAX was attributable to the interfacial reactions of TBAX with the substrate. The interface includes the water-oil microinterface formed in the microemulsion-like L phase as well as the bulk water-oil interface.

Under two-liquid conditions, the third phase formed by linear-polystyrene-based cationic ionomers and the corresponding single-network ionomer gels absorbed the soluble quaternary salts either from the oil phase or from the aqueous solution. Polystyrene-based IPN gels, in which one network contained quaternary salts and another benzyl chlorides, were compared in terms of the feasibility of esterification of the chloromethyl groups in addition to the triphase catalysis (TPC) activities. IPN gels afforded not only very poor TPC activities but also slow esterification. Single-network gels, on the other hand, showed high TPC activities and high esterification rates. When decane was used as the oil, the TPC activity was increased, while the esterification became slower.

トリメチルアンモニウム基を含有するアクリルアミドゲルを合成し, その界面活性剤水溶液中での膨潤挙動と内部状態との関係について検討した. 陽イオン性界面活性剤水溶液中では, ゲル内の界面活性剤濃度は外液の濃度よりも低かったのに対して, 陰イオン性界面活性剤中においては, ゲル中の界面活性剤濃度は外液中の濃度よりも高くなった. また, ドデシル硫酸ナトリウム水溶液中に浸したゲルを純水に浸すと, さらに収縮した. アンモニウム基とスルホ基を併せもつ両性イオン性ゲルでは, アンモニウム基がスルホ基よりも過剰な場合に, アンモニウム基のみを含むゲルと類似の膨潤挙動を示した. これらの結果から, ゲルに界面活性剤が対イオンとして取込まれたときゲルが収縮すること, 高濃度水溶液中では過剰な界面活性剤の取込みが起こり, そのときに体積増加が見られることが明らかになった.

The solubility of benzyltributylphosphonium salt (BTBPX: X = Cl, Br, or I) in aromatic hydrocarbons was examined as a function of the temperature. The solubility curve had specific features, which were characterized by critical values corresponding to the Krafft point and critical micelle concentration. A slight difference in the oil structure exerted a significant effect on the solubility behavior. The Krafft boundary as well as a liquid–liquid immiscibility gap, on the other hand, featured the solubility behavior of BTBPX in an aqueous solution. The shape of the gap was assumed to be a closed loop and the region of the gap was sharply dependent on the concentration of the added metal halide (MX). The phase behavior of the three- or four-component systems, composed of BTBPX, benzene, water, and MX, has been examined in detail. According to their constituent, composition, and temperature, the system afforded a single- to four-phase state form. There were at least three kinds of liquid phases: a BTBPX-rich...

塩化ビニルベンジルトリブチルポスホニウム (VBTBPCl) は塩化ベンジルトリブチルポスホニウムと同様塩化ナトリウム水溶液中で曇り点を示す特異な溶解挙動をとることがわかった. VBTBPClは水中で重合させることが可能で, 対応する高分子を収率よく合成することができた. その線状高分子も単量体と同様塩化ナトリウム水溶液中で曇り点を示すことがわかった. さらに, ジビニルベンゼンとの共重合体は温度, 塩化ナトリウム濃度に依存して可逆的に膨潤収縮を起こす感熱性ヒドロゲルとなることがわかった. イオン性基が直接感熱基となっているこの体積相転移現象の原因について言及した.

The solubility of tetrabutylammonium salt (TBAX; X = Cl, Br, or I) in benzene was examined as a function of temperature. The solubility curve had specific features, which were characterized by critical values corresponding to the Krafft point and the critical micelle concentration of ionic surfactants in water. Above the critical concentration, TBAX was assumed to aggregate in benzene, based on NMR analyses. A slight difference of the oil structure exerted a significant effect on the solubility behavior. In the presence of sodium halides, TBACl or TBABr with water exhibited a specific temperature that was similar to the cloud point. Above that temperature, TBAX was liberated as a liquid to form a liquid-liquid two-phase. The solubility of TBAI in water was poor. It gave a liquid-solid two-phase at low temperatures or a liquid-liquid two-phase above 69 °C, unless the TBAI concentration was too low. The solubility of TBAX in aqueous solution was also dependent on the metal cation of the inorganic salts.

The phase behavior of four-component systems composed of tetrabutylammonium halide (TBAX; X = Cl, Br, or I), nonpolar benzene, water, and sodium halide (NaX) has been examined in detail. According to their constituents, compositions, and temperatures, the four-component systems afforded from single- to four-phase states. There were at least three kinds of liquid phases: a TBAX-rich phase (M), an aqueous solution phase (W), and an oil solution phase (O). In the M phase, TBAX was assumed to form aggregates, like microemulsions, while, in the latter two solution phases, TBAX was present without any aggregated form. When these three liquid phases coexisted, an O-M-W three-liquid-phase equilibrium state occurred. Depending on the temperature and NaX concentration in the W phase, the system changed its state from the O-M-W to the O-M or M-W two-liquid-phase. In some cases, a solid TBAX phase (Q) or solid NaX phase (S) coexisted with these liquid phases. In the presence of excess sodium halide, an O-M-W-S four-p...

Nucleophilic substitution of nitrobenzene derivatives with various amines was conducted so as to clarify the effects of W/O microemulsion surface on reaction rates. In W/O microemulsions produced in octane by sodium bis (2-ethylhexyl) sulfosuccinate (AOT) or cetyltrimethylammonium bromide (CTAB), water-soluble sodium 2, 4, 6-trinitrobenzenesulfonate or octane-soluble 2, 4-dinitrofluorobenzene was found to react with either a water-soluble amine (sodium β-aminoethane sulfonate, sodium glycine, or sodium phenylalanine), or an octane-soluble amine (benzylamine, 1-phenylethylamine, or octylamine). Reaction rate was dependent on ionic charge of surfactant and reagents, surfactant concentration, and [water] / [surfactant] molar concentration ratio (w). Based on a pseudo-phase model, the present results were explained as arising from local concentrations of nitrobenzene derivative and amine at the microemulsion surface due to electrostatic binding of ionic reactants and amphiphilic binding of neutral reactants.

2,2,6,6-テトラメチルピペリジン-1-オキシル (TEMPO) を用いるリビングラジカル重合によりクロロメチルスチレンブロック鎖長の比較的短いスチレン-クロロメチルスチレンブロック共重合体 (PS-block-PCMS) を合成し, これをさらにジメチルアルキルアミンまたはトリブチルホスフィンの第4級化反応によってブロック型カチオン性イオノマーを得た. それらのトルエンーメタノールまたはテトラヒドロフラン (THF) -水混合溶媒中への溶解性は, 第4級化反応前のPS-block-PCMSに類似し, 主にスチレンブロックの溶解性に支配されることがわかった. また, これらの混合溶媒中での希薄溶液粘度挙動を調べ, 以下の結果を得た. ブロック型イオノマーの還元粘度は, 少量のメタノールまたは水の添加により急激に低下し極小を迎えた. さらにメタノールおよび水が添加されると, イオンブロック長が長い場合, 還元粘度は増加し, イオンブロック長の短い場合, やや増加した後減少した. またこの粘度挙動は第4級塩に結合しているアルキル鎖の大きさによっても影響を受けることがわかった. これらの結果をイオンブロックの会合, 第4級塩の極性溶媒による溶媒和と解離によって説明した.

トリメチルアンモニオプロピル基を有するポリアクリルアミドゲルについてその界面活性剤水溶液中での膨潤挙動を検討した. ドデシル硫酸ナトリウム (SDS) 溶液中ではSDS濃度が10-4mol dm-3付近で大きな体積変化を示し, 8×10-4mol dm-3で極小となった. しかし, 変化濃度以上では体積は著しく小さくなったが, その領域内では濃度の増加とともに体積が増加した. これらの挙動はゲル中でのSDSとゲルのイオン性解離基間の静電的相互作用とともに, 高分子鎖との疎水性相互作用が関与していることを示していると思われる.

Examination was made of interionic reactions of hydrophobic sodium 2, 4, 6-trinitrobenzenesulfonate with sodium β-aminoethanesulfonate, sodium glycine, or sodium phenylalanine in w/o microemulsions produced in octane by sodium bis (2-ethylhexyl) sulfosuccinate (AOT) or cetyltrimethylammonium bromide (CTAB). Reaction rate was dependent on the ionic charge of the surfactant, concentrations of ionic reactants in water droplets, [water] / [surfactant] molar concentration ratio (w), and hydrophobicity of the ionic reactant. These features were compared with those of reactions in aqueous solution and could be explained as due to the [ionic reactant] / [water droplet] ratio and binding of ionic reactants to the droplet surface.

塩化ビニルベンジルヘキサデシルジメチルアンモニウム (VBHDAC) の重合をベンゼン中w/o形ミクロエマルション形成下で行った. 重合収率は水添加量, モノマー濃度にほとんど依存しないが, 非重合性界面活性剤の塩化ベンジルヘキサデシルジメチルアンモニウム (BHDAC) を加えることにより変化した. また, w/oミクロエマルション形成下では, 収率は低いが開始剤がなくとも重合した. 生成ポリマーの種々の条件下での溶液粘度挙動を調べることにより, VBHDACのw/oミクロエマルション形成下での重合挙動について考察した.

A novel method for preparing ceramic precursors via homogeneous mixing of different metal ions from aqueous solutions is presented. Using sodium polyacrylate-polyethyleneimine interpolymer complex, precursor coprecipitates containing 99-95mol% zirconium and 1-5mol% yttrium ion were prepared. Yttrium-stabilized zirconium oxides synthesized from the precursors were produced by heating at 800°C for 5h. This method was exemplified to be convenient and useful for the preparation of some ceramic precursors.

オクタン中でエーロゾルOT (AOT) が形成する逆ミセルに水とともに種々の遷移金属塩を可溶化させた。これら金属塩は油溶性のアラニンデシルエステル (AlaODC) の加水分解を促進することがわかった。金属塩として酢酸銅を用いた場合に, 加水分解の初期基質濃度に強く依存した。初期速度は両者の濃度が高いほど大きくなった。しかし, 転化率が金属塩と初期基質量の比の2倍に達すると, 反応は減速した。同様な反応速度挙動が他の金属塩を用いても観察された。多数の金属錯体の存在とそれらの間の平衡安定性からこの反応系のメカニズムを考察した。

Solution Viscosity Behavior and Swelling Behavior of Polystyrene-Based Cationic Ionomers. Effects of Added Salts and Counterion

Crosslinked polystyrene resins containing a low level of either basic or acidic groups were used for supports of α-chymotrypsin (CT), which catalyzed the transesterification of N-acetyl-L-phenylalanine ethyl ester (AcPheOEt) with propanol in toluene. With a minimal amount of water, CT was sorbed to the resins, basic or acidic groups of which were partly or fully neutralized by several soluble acids or bases. With an increasing degree of neutralization of basic resins by free acids, the rate of disappearance of AcPheOEt was decreased, whereas the by-product formation of AcPheOH, due to hydrolysis, was considerably suppressed, compared with the ester-exchange product, AcPheOPr. The pKa value of the neutralizing acid was also important for both CT activity and reaction selectivity. AcPheOPr was selectively produced at a certain range of pKa values. On the other hand, the neutralization of acidic resins with free amines enhanced the CT activity but a strong base promoted the formation of hydrolysis product. © 1995 John Wiley & Sons, Inc.

The dilute solution viscosity was investigated for several polystyrene-based cationic io-nomers. It was found that intramolecular aggregation among the ionic groups was strongly dependent on the sizes of quaternary onium groups and counter anions. The extent of the aggregation was controled by the solvent polarity and the solvation to the ionic groups. When there was a strong selective soivation to small counter ions, the structure of onium groups shows a minor effect on the viscosity behavior, indicating little aggregation among the ionic groups. A strong solvation to small quaternary cations also eliminates the intra-molecular aggregation and the influence of counter ions was barely observable. When the selective solvation to counter ions was disabled by the enlarged size of the counter ions, however, the viscosity depended on onium group structure or spacer chain length. If the solvent solvates neither counter ions nor quaternary groups, the smaller the sizes of onium cation and counter anion, the lower the reduced viscosity due to an enhancement of the ionic aggregate formation. © 1995 John Wiley & Sons, Inc.

Simple nucleophilic substitutions were done under liquid–liquid phase-transfer reaction conditions using water-insoluble alcohols as organic solvents. The reactions proceeded at considerable rates even in the absence of any catalysts, depending on the alcohol, inorganic salt, and the aqueous concentration of the salts. An addition of single- or double-chained onium salts enhanced the reaction rate almost linearly with the amount of the onium salts. The concentrations of inorgainc salts and water in the alcohol phase were analyzed and the relationship between these concentrations and the observed rate constant was discussed. An interfacial reaction mechanism explains the kinetics of this reaction system better than the conventional ion-pair mechanism assumed by most research using hydrocarbon solvents.

The reactions of alanine decyl ester (AlaODc) with nucleophiles were catalyzed by a crosslinked polystyrene-supported ethylenediamine–copper(II) ion complex (Cu en-PS) under toluene/resin two-phase conditions or toluene/aqueous buffer/resin three-phase conditions. In the two-phase reactions with octylamine, the rate was increased with a decreasing metal content of the resin. The catalytic efficiency was also dependent on other factors, that is, metal ion, ligand structure, and substrate structure. In the three-phase reactions with water, the hydrolysis was very fast when acetate ions were present in the aqueous phase. It has been suggested that the reactions proceed via a substrate-coordinated intermediate complex under both conditions.

カルボキシル基結合橋かけポリスチレン (PS-COOH) あるいはスルホ基結合橋かけポリスチレン (PS-SO3H) を用い, 触媒である銅 (II) イオンを水相から反応場である樹脂内に相間移動によって移動させ, アラニンデシルエステル (AlaODc) の加水分解をトルエン/銅塩水溶液/樹脂の三相系で行った. PS-SO3HよりPS-COOHを用いた方が反応は速く進行した. また, 樹脂の酸性基導入量を増すこと, 銅塩として酢酸銅 (II) を用い銅塩水溶液の濃度を増すことによって反応は加速した. アルコールあるいはトリブチルアミンを添加することにより反応は促進され, 加水分解生成物であるアラニンは反応を阻害することが分かった. 以上の結果を基にこの三相系におけるAlaODcの加水分解の反応機構を考察した.

Polystyrene-based crosslinked cationic ionomers containing ammonium or phosphonium chlorides (AxRCl and PxBuCl) were reacted with decyl methanesulfonate. The kinetic data were correlated with the swelling behavior of the ionomers and the solution viscosity of the corresponding linear ionomers. The reactivity of the ionomers was independent of the particle size of the ionomer beads, indicating no diffusion control of the reaction. The solvent and the ion content of the ionomers greatly affect the reactivity. In nonpolar solvents with a low acceptor number, A N , such as toluene, the aggregation of ionic groups with an increasing ion content reduces the reactivity. A solvent with a high value of A N , such as chloroform, led a very low reactivity independent of the ion content

Lightly crosslinked polystyrenes with ammonium chlorides were ion-exchanged to a fluoride form. The fluoride polymers functioned as good catalysts for several base-catalyzed reactions, such as cyanoethylation, Knoevenagel reaction, Claisen condensation and Michael addition. Their catalytic activity was comparable to that of tetrabutylammonium fluoride (TBAF). The factors controlling the catalytic efficiency for the reaction between ethyl acetoacetate and benzaldehyde were examined in detail. Ionic loading and ammonio structure of the fluoride polymers hardly affected the catalytic efficiency. The reaction was fast in a non-polar solvent, such as octane or toluene. The solvent effect was very similar to that of nucleophilic substitution reactions. These results suggest that the rate-determining step of the base-catalyzed reaction is not the formation of a conjugate base from the reagent acid, but the attack of the nucleophilic anion on electrophiles.

Dilute-solution viscosities of polystyrene-based cationic ionomers containing ammonio or phosphonio groups were measured in several solvents. In polar solvents with dielectric constant (er) beyond 10, the ionomers showed a typical polyelectrolyte behavior, indicating that a large part of ionic groups were dissociated into ions. In nonpolar solvents with low er, the reduced viscosity of the ionomers linearly decreased with a decreasing ionomer concentration. At low polymer concentrations, every ionomer gave a reduced viscosity lower than that of the corresponding chloromethylated polystyrene. With an increasing ion content, the intrinsic viscosity progressively decreased if the nonpolar solvents had a low acceptor number (AN), such as toluene or tetrahydrofran (THF). In the halogenated solvents with high AN value, such as chloroform, however, the intrinsic viscosity was hardly dependent on the ion content. This indicates that the intramolecular aggregation among the ionic groups is inhibited in the halogenated solvents due to a strong anion solvation. An addition of a protic solvent to a nonpolar solvent eliminates the aggregation between ionic groups and leads to polyelectrolyte behavior. © 1994 John Wiley & Sons, Inc.

橋かけ高分子相間移動触媒を酵素包括担体とする新規な非水系酵素反応の方法を検討した. 第四級アンモニウム塩 (QX) が結合したゲル型ポリスチレン (PS) 樹脂を有機溶媒で膨潤した状態でα-キモトリプシン (α-CT) 水溶液を吸収させ, N-アセチル-L-フェニルアラニンエチルエステル (AcPhoOEt) のn-プロピルアルコール (PrOH) とのエステル交換反応ならびにn-プロピルアミン (PrNH2) によるアミド化反応の触媒として用いた. その結果, これら樹脂固定α-CTは両反応について非固定系と比ベ高活性を示し, トルエンなど樹脂を良く膨潤する非極性溶媒を用いるとき最もα-CTの活性は高くなった. また, 求核基質の濃度, 水量には最適値が存在することが分かった. さらに, 吸収させるα-CT水溶液のpH及び使用する緩衝液の濃度などが樹脂固定α-CTの活性をどのように支配するかを詳細に検討し, 樹脂固定α-CTの基本的性質を明らかにした.

Recent developments of triphase catalysis are reviewed. First, applications of ion-exchange resins to organic synthesis as reagents and catalysts are described in connection with polymeric phase transfer catalysts. Subsequently, polymeric phase transfer catalysts are classified into three typical groups, namely, onium salts type, crown ethers and cryptands type, and cosolvents type. Their specific features in triphase catalysis are demonstrated. Activity-determining factors and mechanistic aspects of triphase catalysis are also discussed.

Quaternary ammonium salts of poly [2- (N, N-dimethylamino) ethyl methacrylate] (cationic polymer) were prepared by the reaction of poly [2- (N, N- dimethylamino) ethyl methacrylate] (PAEM) with various alkyl bromides with a view of obtaining good flocculants. The flocculating ability for aqueous suspensions of kaolin was investigated with respect to the structure of quaternary ammonium salt polymers by measuring the sedimentation velocity, sedimentation volume, and residual turbidity.The results obtained are as follows.1) The sedimentation velocity of cationic polymer (QPC2X) prepared from PAEM and ethyl bromide was independent of the degree of quaternization and maximum sedimentation velocity showed 3.03.2 cm/min. Of other cationic polymers (QPC6X, QPC12X, QPC18X) obtained from PAEM and higher alkyl bromides (hexyl bromide, dodecyl bromide, and stearyl bromide), cationic polymers of the lower degree of quaternization displayed the larger rate of sedimentation and the maximum rate of sedimentation showed 2.33.2 cm/min at the optimum dosage of 610 ppm. 2) The bulky precipitation was obtained with cationic polymer of the medium degree of quaternization (5070%). 3) The clearest supernatant gave 2550 ppm turbidity at the dosage of 810 ppm. 4) Cationic polymers were most effective for flocculation with the increase of acidity. 5) The sedimentation velocity decreased rapidly at the concentration of 2.55.0% of kaolin suspension. 6) Cationic polymers derived from PAEM and various alkyl bromides were more effective with the commercial flocculants such as Sumifloc-FC, Himoloc-Neo 600, and PAS-A.

Several ionene bromides were used as reagents for the displacement of decyl methanesulfonate into 1-bromodecane. They were very reactive when adsorbed by silica gel. The enhanced activities of the ionenes were hardly dependent on their structures and molecular weights but decreased gradually with increasing the amount of ionene adsorbed by silica gel. Ionene chlorides exhibited a similar enhancement of reactivity when adsorbed by silica gel. However, unlike the ionenes, a large increase in activity due to adsorption was not observed with pendant-type polycations such as poly(4-vinylpyridinium bromide) and poly[(4-vinylbenzyl)tributylammonium chloride]. The silica gel-supported ionenes also exhibited excellent catalytic activities for solid–liquid–solid triphase substitution reactions, particularly for the reactions between 1-bromodecane and such inorganic salts as consisted of relatively hard-basic nucleophilic anions.

The kinetics of the biphase hydrolysis of 1-bromoadamantane and 1-phenylethyl chloride in toluene–water and decane–water systems have been investigated. Evidence has been obtained for the first examples of ratelimiting SN1 reactions occurring at a hydrocarbon–water phase boundary, based on (1) the influence of temperature, mild stirring, interfacial area, reaction volume, and pH on the observed first-order rate constants, (2) comparison of absolute rates and activation energies with analogous homogeneous hydrolysis reactions, (3) the temperature dependence of the initial rate of diffusion of tritiated 1-methoxyadamantane from toluene into water, and (4) the initial rate of diffusion of 3H2O into toluene.

The reactions of ethylene with chloroform initiated by alkylamine-ferrous chloride systems were examined in detail. Two main products, α,α,α-trichloroalkanes (I) and α,α,ω-trichloroalkanes (II), were obtained. Their composition was independent of the kind of amine but dependent upon the total carbon number of alkylamine. When amines having higher alkyl groups were used, the main product was α,α,ω-trichloropropane (II-1). When lower alkylamines were used, the main products were α,α,α-trichloroalkanes which contained considerable amounts of higher telomers. The results support the view that the reactions proceed according to the “caged free radical” process.

アミノ基を有するポリスチレン樹脂を担体としてα-キモトリプシン (α-CT) によるN-アセチル-L-フェニルアラニンエチルエステル (AcPheOEt) のプロピルアルコール (PrOH) とのエステル交換反応をトルエン中で行った. アミノ基の導入量が小さい場合には担体としての有効性は低いが, 樹脂にさらに第四アンモニウム塩 (QX) あるいはテトラエチレングリコール (TEG) を結合させ親水性を与えるとα-CTは非常に高い活性を示した. しかし, 樹脂へのアミン導入量の増加は加水分解生成物AcPheOHの増大をもたらし, エステル交換生成物AcPheOPrの収率はアミン含有量の小さい樹脂ほどむしろ大きかった. また, アミノ基をあらかじめAcPheOHで中和した樹脂を担体として用いるとAcPheOPrの生成速度ならびに収率は極めて高くなった. 以上の結果を基礎にしてアミノ基ならびに親水基の役割を考察した.

2-ビニルピリジンービニルアルコール共重合体 (2VP-VA) の4級アンモニウム塩 (ポリマ-) を2VP-VAへの種々の奥化アルキルの反応により得た. 5%カオリン懸濁液に対する凝集能を沈降速度, 沈降容積そして残留濁度を測定することによりポリマーの構造との関連において研究した. 得られた結果は次の通りであった. 1) いずれのポリマーを用いた場合でも, ポリマー添加濃度が6～20ppmの範囲で良好な凝集効果が得られ, また, これらの条件下で, カオリン粒子の電気泳動移動度は比較的小さい値を示した. 2) 凝集能はi) 幹ポリマーの分子愚の増加に伴って増加し, アルキル化剤の種類よりも幹ポリマーの分子量への依存性は高かった. ii) 水酸基のイオン性基の割合, すなわち (α/FV▲) の増加に伴って増加した, 3) より鎖長の短い臭化アルキルから得られたポリマーが良好な凝集効果を示す傾向がみられた. 4) 凝集作用に適当なpHの値は2～10の範囲であった.

Polyurethaneamine (PUA) was prepared from N-methyldiethanolamine and hexamethylenediiso-cyanate. A variety of quaternary ammonium salts of PUA (cationic polymer) were prepared from PUA and alkyl bromides of various chain length (C2C12) with a view of obtaining good flocculants. In alkylating PUA with alkyl bromides, it was found that alkylation occured to urethane-N as well as quaternization reaction, and using low molecule of urethane as model compound prepared from ethanol and hexamethylenediisocyanate, alkylation to urethane-N was ascertained by the reaction of urethane and dodecyl bromide. The flocculation ability for aqueous suspension of kaoline was investigated in the relation to the structure of cationic polymers by measuring the sedimentation velocity, sedimentation volume, and turbidity. Cationic polymer obtained from PUA and the higher alkyl bromide showed good flocculation effect. The suitable range of degree of quaternization was 4060%. Cationic polymer was most effective for flocculation with increase of acidity. The most clarity of supernatant gave 40ppm turbidity at the dosage of 50ppm using cationic polymer (degree of quaternization 84.4%) obtained from PUA and dodecyl bromide. Interraction (metachromasia) between methyl orange and cationic site of a number of cationic polymers were examined, and cationic polymers with the higher degree of quaternization derived from the higher alkyl bromides and PUA were shown large metachro-masia. Cationic polymers derived from the higher alkyl bromides showed good flocculating ability which are not inferior that of typical commercial products.

N-Chloroalkylamines initiate the telomerization of ethylene with chloroform to give α,α,α-trichloroalkanes CCl3(C2H4)nH(I), which are the same products as those obtained by peroxide-initiated reactions. The N-chloro-alkylamine–iron and N-chloroalkylamine–ferrous chloride systems also initiate the reaction of ethylene with chloroform to afford α,α,ω-trichloroalkanes CHCl2(C2H4)nCl (II) as the main product, and a small amount of I along with other teJomers. The rate of the reaction and the composition of the products vary widely with the kind of N-chloroalkylamine. The reaction mechanism was discussed, a “caged radical” mechanism being proposed for the N-chloroalkylamine-ferrous chloride system.

By using various N-chloroalkylamines, the telomerization of ethylene with carbon tetrachloride was carried out in a stainless steel autoclave at 130 °C. It was found that the yields and the compositions of telomers varied widely according to the kinds and the structures of N-chloroalkylamines. When N-chloromonoalkylamines or N-chlorodialkylamines were used, the total yield of telomers was high compared with the case using N,N-dichloroalkylamines. In the presence of both N-chloromonoalkylamines and N-chlorodialky]amines, the total yield of telomers became higher and the greater part of the telomers was 1:1 adduct (n=1 telomer CCl3CH2CH2Cl) of ethylene with carbon tetrachloride.

Die Titelreaktion der Verbindungen (I) und (II), die in verschiedenen F eC12-Amin- Systemen unter Einsatz der Amine (VII)-(X) durchgefuhrt wird, wird detailliert untersucht.

Recent developments of triphase catalysis are reviewed. First, applications of ion-exchange resins to organic synthesis as reagents and catalysts are described in connection with polymeric phase transfer catalysts. Subsequently, polymeric phase transfer catalysts are classified into three typical groups, namely, onium salts type, crown ethers and cryptands type, and cosolvents type. Their specific features in triphase catalysis are demonstrated. Activity-determining factors and mechanistic aspects of triphase catalysis are also discussed.