JPS6335659B2 - - Google Patents
Info
- Publication number
- JPS6335659B2 JPS6335659B2 JP8216080A JP8216080A JPS6335659B2 JP S6335659 B2 JPS6335659 B2 JP S6335659B2 JP 8216080 A JP8216080 A JP 8216080A JP 8216080 A JP8216080 A JP 8216080A JP S6335659 B2 JPS6335659 B2 JP S6335659B2
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- molecular weight
- complex catalyst
- alkylene oxide
- block copolymer
- 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.)
- Expired
Links
- 239000003054 catalyst Substances 0.000 claims description 28
- 125000002947 alkylene group Chemical group 0.000 claims description 18
- 229920001400 block copolymer Polymers 0.000 claims description 15
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 238000012661 block copolymerization Methods 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical group C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical group C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- LDYLHMQUPCBROZ-UHFFFAOYSA-N diethyl(methoxy)alumane Chemical compound [O-]C.CC[Al+]CC LDYLHMQUPCBROZ-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- FSYXETIPNHLFLQ-UHFFFAOYSA-M diethylalumanylium;hydroxide Chemical compound [OH-].CC[Al+]CC FSYXETIPNHLFLQ-UHFFFAOYSA-M 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、分子量分布の狭いアルキレンオキシ
ドのブロツクコポリマーを製造する方法に関す
る。
アルキレンオキシドのブロツクコポリマーをア
ニオン重合により効率よく製造することは一般に
困難であり、例えブロツクコポリマーが得られる
としても分子量分布が広く、収率が低い、分子量
調節が困難であるなどの欠点があつた。本発明者
は、分子量分布の狭いアルキレンオキシドのブロ
ツクコポリマーをアニオン重合により製造するこ
とを目的に種々検討を重ねた結果、本発明者がア
ルキレンオキシドのホモポリマーの製造触媒とし
て発見し、すでに第28回高分子学会（昭和54年11
月１日〜３日）で発表した錯体触媒が前記目的の
ために好適であることを見出し本発明に到達した
のである。すなわち本発明は、有機アルミニウム
化合物とテトラフエニルポルフイリンとを反応し
て得られる錯体触媒を用いてアルキレンオキシド
のブロツク共重合を行うことを特徴とするブロツ
クコポリマーの製造方法である。
本発明のブロツク共重合は、不活性気体の雰囲
気下、無溶媒もしくは溶媒の存在下、錯体触媒を
用いてアルキレンオキシドの重合を行つてプレポ
リマーを得、ついで第二のアルキレンオキシドを
加えて重合を続行することにより実施される。ブ
ロツク数を増やすときは、前記方法を繰返すだけ
で十分である。第一のアルキレンオキシドの重合
を行つた後、可及的速やかに第二のアルキレンオ
キシドの重合を行うのが好ましい。この際、重合
系の粘度の上昇度に応じてあらたに溶媒を加える
のが特に好ましい。
一般には重合終了後、生成混合物にメタノール
を加え、メタノール可溶分とメタノール不溶分と
に分離する。メタノール可溶分はシリカゲルカラ
ムを通して精製し、低分子量ブロツクコポリマー
を回収する一方、メタノール不溶分はベンゼン―
メタノール混合溶媒を用いて再結晶精製し、高分
子量ブロツクコポリマーを回収する。
不活性気体としては窒素が好適である。溶媒と
してはベンゼン、トルエン、キシレンのような炭
化水素、塩化メチレン、クロロホルム、ジクロロ
エタンのようなハロゲン化炭化水素が使用され
る。溶媒の使用量は任意で選択できる。
重合は常温で十分進行するが、加温重合するこ
ともできる。
本発明が適用されるアルキレンオキシドはエチ
レンオキシド、プロピレンオキシド、１―ブチレ
ンオキシド、エピクロルヒドリンのような未端三
員環エポキシ基を有する脂肪族アルキレンオキシ
ド、シクロヘキセンオキシド、シクロペンテンオ
キシドのような三員環エポキシ基を有する脂環族
アルキレンオキシド、スチレンオキシドのような
三員環エポキシ基を有する芳香族アルキレンオキ
シドであるが、脂肪族アルキレンオキシドが好ま
しく、エチレンオキシド、プロピレンオキシドが
特に好ましい。エチレンオキシドとプロピレンオ
キシドの組合せが代表的である。
ブロツクコポリマーの分子量およびブロツク組
成比は、ブロツク共重合に使用するアルキレンオ
キシドの全量および各アルキレンオキシドの割合
によつてほぼ自動的に決まる。通常アルキレンオ
キシドの使用量は任意に選択できるが、例えば錯
体触媒に対し100倍モルないし1000倍モルである。
第一アルキレンオキシドと第二アルキレンオキ
シドの使用割合は任意に選択できるが、例えば
10：１ないし１：10の範囲である。
錯体触媒は、有機アルミニウム化合物とテトラ
フエニルポルフイリンとを反応して得られるもの
であるが、該反応生成物をさらに変性して得られ
る錯体触媒をも包含する。錯体触媒の構造は、例
えば有機アルミニウム化合物としてジエチルアル
ミニウムクロリドを使用した場合、次のように推
定されている。
錯体触媒は、不活性気体の雰囲気下、溶媒の存
在下テトラフエニルポルフイリンに約等モルの有
機アルミニウム化合物を加え、室温で反応させる
ことにより調製される。錯体触媒の変性は前記の
ように調製した錯体触媒を、メタノールのような
アルコールや水を用いて実施される。
有機アルミニウム化合物としてはジエチルアル
ミニウムクロリド、ジエチルアルミニウムブロミ
ドのようなジアルキルアルミニウムハライド、ジ
エチルアルミニウムメトキシド、ジエチルアルミ
ニウムエトキシドのようなジアルキルアルミニウ
ムアルコキシド、ジエチルアルミニウムヒドロキ
シドがあげられる。
触媒調製に使用される溶媒は、本発明の重合溶
媒として使用される溶媒と同種のものであるが、
触媒調製時と重合時の溶媒種を一致させる必要は
ない。不活性気体は窒素が適当である。
錯体触媒の調製原料であるテトラフエニルポル
フイリンはベンズアルデヒドとピロールとから常
法により製造される。
本発明は触媒として前記のような特定の錯体触
媒を用いる結果ブロツク共重合の活性が高く、ブ
ロツクコポリマーの分子量調節が容易であるばか
りでなく、得られたブロツクコポリマーの分子量
分布が狭く、かつブロツクコポリマーは規則正し
い頭尾結合のみからなるという特徴も有してい
る。
本発明で得られた分子量分布の狭いアルキレン
オキシドのブロツクコポリマーは非イオン界面活
性剤、分散染料、ポリウレタンなどの原料とし
て、また、粘結剤などとして使用可能である。ま
た他の化合物の分子量および分子量分布測定のた
めの標準試料として使用される。
参考例１ （錯体触媒の製造）
ベンズアルデヒド80ml（84.8ｇ）とピロール56
ml（53.6ｇ）をプロピオン酸３に入れ、30分間
還流下に反応させた後、１昼夜放置した。混合物
を過した後、メタノール―クロロホルム混合溶
媒で再結晶精製してα，β，γ，δ―テトラフエ
ニルポルフイリンを収率20％で取得した。
ジエチルアルミニウムクロリド0.12ｇとα，
β，γ，δ―テトラフエニルポルフイリン0.61ｇ
とを窒素雰囲気下、塩化メチレン溶媒20mlの存在
下室温で反応させて、前記構造式（）を有する
と推定される錯体触媒0.68ｇを含有する触媒溶液
20mlを取得した。
実施例 １〜４
塩化メチレン20mlに、錯体触媒〔〕を含有す
る触媒溶液20mlと第１表記載量のプロピレンオキ
シドを入れ、窒素雰囲気下室温で３日間重合し、
ついで第１表記載量のエチレンオキシドを加え、
３日間ブロツク共重合を行つた。ブロツク共重合
終了後、重合生成物を水に溶解し、遠心分離によ
り水可溶分と不溶分とに分離した。水可溶分は濃
縮後ベンゼンにより凍結乾燥し、第１表記載量の
プロピレンオキシド．エチレンオキシドブロツク
コポリマーを得た。水不溶分はメタノールに溶か
し、シリカゲルカラムを通して精製したが触媒の
みであつた。
プロピレンオキシドプレポリマーの平均分子量
と分子量分布およびプロピレンオキシド―エチレ
ンオキシドブロツクコポリマーの平均分子量、分
子量分布およびブロツク組成を第１表に示した。
The present invention relates to a method for producing alkylene oxide block copolymers having a narrow molecular weight distribution. It is generally difficult to efficiently produce alkylene oxide block copolymers by anionic polymerization, and even if block copolymers can be obtained, they have drawbacks such as a wide molecular weight distribution, low yield, and difficulty in controlling the molecular weight. . As a result of various studies aimed at producing a block copolymer of alkylene oxide with a narrow molecular weight distribution by anionic polymerization, the present inventor discovered it as a catalyst for producing a homopolymer of alkylene oxide. The Society of Polymer Science and Technology (November 1972)
It was discovered that the complex catalyst announced in 2006 (January 1st to 3rd) is suitable for the above purpose, and the present invention was achieved. That is, the present invention is a method for producing a block copolymer, which comprises carrying out block copolymerization of alkylene oxide using a complex catalyst obtained by reacting an organoaluminum compound and tetraphenylporphyrin. In the block copolymerization of the present invention, alkylene oxide is polymerized using a complex catalyst in an inert gas atmosphere or in the presence of a solvent to obtain a prepolymer, and then a second alkylene oxide is added to polymerize. This will be implemented by continuing. When increasing the number of blocks, it is sufficient to repeat the method described above. After polymerizing the first alkylene oxide, it is preferable to polymerize the second alkylene oxide as soon as possible. At this time, it is particularly preferable to add a new solvent depending on the degree of increase in the viscosity of the polymerization system. Generally, after the polymerization is completed, methanol is added to the product mixture to separate it into methanol-soluble and methanol-insoluble components. The methanol-soluble fraction is purified through a silica gel column to recover the low molecular weight block copolymer, while the methanol-insoluble fraction is purified through a silica gel column.
A high molecular weight block copolymer is recovered by recrystallization and purification using a methanol mixed solvent. Nitrogen is suitable as the inert gas. Hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane are used as solvents. The amount of solvent used can be selected arbitrarily. Polymerization proceeds satisfactorily at room temperature, but polymerization can also be carried out by heating. The alkylene oxides to which the present invention is applied include ethylene oxide, propylene oxide, 1-butylene oxide, aliphatic alkylene oxides having an unterminated three-membered ring epoxy group such as epichlorohydrin, and three-membered ring epoxy groups such as cyclohexene oxide and cyclopentene oxide. and aromatic alkylene oxides having a three-membered ring epoxy group such as styrene oxide, aliphatic alkylene oxides are preferred, and ethylene oxide and propylene oxide are particularly preferred. A typical combination is ethylene oxide and propylene oxide. The molecular weight and block composition ratio of the block copolymer are almost automatically determined by the total amount of alkylene oxide used in block copolymerization and the ratio of each alkylene oxide. Usually, the amount of alkylene oxide used can be arbitrarily selected, but is, for example, 100 to 1000 times the mole of the complex catalyst. The ratio of the primary alkylene oxide and the secondary alkylene oxide can be selected arbitrarily, but for example,
It is in the range of 10:1 to 1:10. The complex catalyst is obtained by reacting an organoaluminium compound and tetraphenylporphyrin, but it also includes complex catalysts obtained by further modifying the reaction product. The structure of the complex catalyst is estimated as follows when, for example, diethylaluminum chloride is used as the organoaluminum compound. The complex catalyst is prepared by adding approximately equimolar amounts of an organoaluminum compound to tetraphenylporphyrin in the presence of a solvent under an inert gas atmosphere and reacting at room temperature. Modification of the complex catalyst is carried out using an alcohol such as methanol or water for the complex catalyst prepared as described above. Examples of the organic aluminum compound include dialkylaluminum halides such as diethylaluminum chloride and diethylaluminum bromide, dialkylaluminum alkoxides such as diethylaluminium methoxide and diethylaluminum ethoxide, and diethylaluminium hydroxide. The solvent used for catalyst preparation is the same as the solvent used as the polymerization solvent of the present invention, but
It is not necessary to match the solvent type during catalyst preparation and during polymerization. Nitrogen is suitable as the inert gas. Tetraphenylporphyrin, which is a raw material for preparing the complex catalyst, is produced from benzaldehyde and pyrrole by a conventional method. As a result of using the above-mentioned specific complex catalyst as a catalyst, the present invention not only has high block copolymerization activity and can easily control the molecular weight of the block copolymer, but also has a narrow molecular weight distribution of the obtained block copolymer. Copolymers are also characterized by consisting only of regular head-to-tail bonds. The alkylene oxide block copolymer with a narrow molecular weight distribution obtained in the present invention can be used as a raw material for nonionic surfactants, disperse dyes, polyurethanes, etc., and as a binder. It is also used as a standard sample for measuring the molecular weight and molecular weight distribution of other compounds. Reference example 1 (Production of complex catalyst) Benzaldehyde 80ml (84.8g) and pyrrole 56
ml (53.6 g) was added to propionic acid 3, reacted under reflux for 30 minutes, and then left for one day and night. After the mixture was filtered, it was recrystallized and purified using a methanol-chloroform mixed solvent to obtain α,β,γ,δ-tetraphenylporphyrin in a yield of 20%. 0.12g of diethylaluminum chloride and α,
β, γ, δ-tetraphenylporphyrin 0.61g
A catalyst solution containing 0.68 g of a complex catalyst estimated to have the above structural formula () was prepared by reacting the above with the above in the presence of 20 ml of methylene chloride solvent at room temperature under a nitrogen atmosphere.
Obtained 20ml. Examples 1 to 4 20 ml of a catalyst solution containing the complex catalyst [ ] and propylene oxide in the amounts listed in Table 1 were added to 20 ml of methylene chloride, and polymerized for 3 days at room temperature under a nitrogen atmosphere.
Next, add ethylene oxide in the amount listed in Table 1,
Block copolymerization was carried out for 3 days. After the block copolymerization was completed, the polymerized product was dissolved in water and separated into water-soluble and insoluble components by centrifugation. The water-soluble portion was concentrated and freeze-dried with benzene, and the amount of propylene oxide listed in Table 1 was added. An ethylene oxide block copolymer was obtained. The water-insoluble matter was dissolved in methanol and purified through a silica gel column, but only the catalyst was found. Table 1 shows the average molecular weight and molecular weight distribution of the propylene oxide prepolymer and the average molecular weight, molecular weight distribution, and block composition of the propylene oxide-ethylene oxide block copolymer.
【表】
＊ 収量に相当する。
＊＊ ポリスチレンゲル(東洋曹達製)を充填したカラ
ムに、テトラヒドロフラン溶媒を用いてオー
ブン温度40℃で分析したGPCスペクトルより求め
た。
参考例２，３ （変性錯体触媒の製造）
トリエチルアルミニウム0.57ｇとαβγδ―テトラ
フエニルポルフイリン3.07ｇとを窒素雰囲気下、
塩化メチレン溶媒150mlの存在下室温で反応させ
て、後記構造式を有すると推定される錯体触媒
3.34ｇを含有する触媒溶液20mlを取
得した。つぎにメタノール50mlまたは水200mlを
加えて室温で反応させて、後記構造式を有すると
推定される変性錯体触媒３ｇをそれぞれ得た。
実施例 ５，６
参考例２，３の変性錯体触媒〔〕または
〔〕を用いて実施例１と同様にプロピレンオキ
シドとエチレンオキシドのブロツク共重合を行つ
たところ、実施例１と同様に分子量分布の狭いブ
ロツク共重合体が好収率で得られた。[Table] * Corresponds to yield.
** Determined from a GPC spectrum analyzed using a column packed with polystyrene gel (manufactured by Toyo Soda) and an oven temperature of 40°C using tetrahydrofuran solvent.
Reference Examples 2 and 3 (Production of modified complex catalyst) 0.57 g of triethylaluminum and 3.07 g of αβγδ-tetraphenylporphyrin were mixed in a nitrogen atmosphere.
A complex catalyst estimated to have the structural formula shown below by reacting at room temperature in the presence of 150 ml of methylene chloride solvent
Take 20 ml of catalyst solution containing 3.34 g. I got it. Next, 50 ml of methanol or 200 ml of water was added and reacted at room temperature to obtain 3 g of each modified complex catalyst estimated to have the structural formula shown below. Examples 5 and 6 When block copolymerization of propylene oxide and ethylene oxide was carried out in the same manner as in Example 1 using the modified complex catalysts [ ] or [ ] of Reference Examples 2 and 3, the molecular weight distribution was changed as in Example 1. A narrow block copolymer was obtained in good yield.
Claims (1)
ルフイリンとを反応して得られる錯体触媒を用い
てアルキレンオキシドのブロツク共重合を行うこ
とを特徴とするブロツクコポリマーの製造方法。 ２ 有機アルミニウム化合物がジエチルアルミニ
ウムクロリドであることを特徴とする特許請求の
範囲第１項記載の方法。 ３ アルキレンオキシドがエチレンオキシドおよ
びプロピレンオキシドであることを特徴とする特
許請求の範囲第１項記載の方法。[Scope of Claims] 1. A method for producing a block copolymer, which comprises carrying out block copolymerization of alkylene oxide using a complex catalyst obtained by reacting an organoaluminum compound and tetraphenylporphyrin. 2. The method according to claim 1, wherein the organoaluminum compound is diethylaluminum chloride. 3. The method according to claim 1, wherein the alkylene oxide is ethylene oxide and propylene oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216080A JPS578223A (en) | 1980-06-19 | 1980-06-19 | Production of alkylene oxide block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8216080A JPS578223A (en) | 1980-06-19 | 1980-06-19 | Production of alkylene oxide block copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS578223A JPS578223A (en) | 1982-01-16 |
| JPS6335659B2 true JPS6335659B2 (en) | 1988-07-15 |
Family
ID=13766671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8216080A Granted JPS578223A (en) | 1980-06-19 | 1980-06-19 | Production of alkylene oxide block copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS578223A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61197631A (en) * | 1985-02-28 | 1986-09-01 | Kanegafuchi Chem Ind Co Ltd | Production of polyalkylene oxide of narrow mw distribution |
| CA1255050A (en) * | 1985-03-22 | 1989-05-30 | Shohei Inoue | Polyalkylene oxide having unsaturated end group and narrow molecular weight distribution |
| US5674911A (en) * | 1987-02-20 | 1997-10-07 | Cytrx Corporation | Antiinfective polyoxypropylene/polyoxyethylene copolymers and methods of use |
| US5567859A (en) * | 1991-03-19 | 1996-10-22 | Cytrx Corporation | Polyoxypropylene/polyoxyethylene copolymers with improved biological activity |
| JPH03195729A (en) * | 1989-12-25 | 1991-08-27 | Tokuyama Soda Co Ltd | Block copolymer and production thereof |
| CA2106474C (en) | 1991-03-19 | 2004-02-10 | R. Martin Emanuele | Polyoxypropylene/polyoxyethylene copolymers with improved biological activity |
| USRE38558E1 (en) | 1991-03-19 | 2004-07-20 | Cytrx Corporation | Polyoxypropylene/polyoxyethylene copolymers with improved biological activity |
| US5696298A (en) * | 1991-03-19 | 1997-12-09 | Cytrx Corporation | Polyoxypropylene/polyoxyethylene copolymers with improved biological activity |
-
1980
- 1980-06-19 JP JP8216080A patent/JPS578223A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS578223A (en) | 1982-01-16 |
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