JPH043409B2 - - Google Patents
Info
- Publication number
- JPH043409B2 JPH043409B2 JP18596884A JP18596884A JPH043409B2 JP H043409 B2 JPH043409 B2 JP H043409B2 JP 18596884 A JP18596884 A JP 18596884A JP 18596884 A JP18596884 A JP 18596884A JP H043409 B2 JPH043409 B2 JP H043409B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum
- porphyrin complex
- molecular weight
- polyester
- epoxide
- 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
- -1 aluminum porphyrin Chemical compound 0.000 claims description 19
- 229920000728 polyester Polymers 0.000 claims description 15
- 150000002118 epoxides Chemical class 0.000 claims description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 150000003839 salts Chemical group 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- JHYNXXDQQHTCHJ-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 JHYNXXDQQHTCHJ-UHFFFAOYSA-M 0.000 claims description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical group O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 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
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 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 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 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
- 238000001816 cooling Methods 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound 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
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- SLAFUPJSGFVWPP-UHFFFAOYSA-M ethyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC)C1=CC=CC=C1 SLAFUPJSGFVWPP-UHFFFAOYSA-M 0.000 description 1
- 238000001914 filtration 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003233 pyrroles Chemical group 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
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- GTCDARUMAMVCRO-UHFFFAOYSA-M tetraethylazanium;acetate Chemical compound CC([O-])=O.CC[N+](CC)(CC)CC GTCDARUMAMVCRO-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
（産業上の利用分野）
本発明は、分子量分布の狭いポリエステルの製
造法に関する。
（従来技術）
一般にポリエステルは、多塩基酸と多価アルコ
ールの重縮合反応により製造されるが、この反応
は逐次反応である為、分子量分布の狭いポリマー
を製造することは困難である。
また、ポリエステルは、酸無水物とエポキシド
の開環重合により製造することも可能であるが、
分子量分布の狭いポリエステルを製造することは
同様に、困難である。
本発明者らは、分子量分布の狭いポリエステル
を製造することを目的に種々検討を重ねた結果、
本発明者らが、エポキシドのホモポリマーの製造
触媒として発見した（Die Makromolekulare
Chemie.，182(4)、1073−９（1981）アルミニウム
ポルフイリン錯体に加えて有機第四級塩を触媒と
して組み合わせ用いることが、前記目的のために
好適であることを見出し、本発明に到達したもの
である。
（発明の目的）
本発明は、分子量分布の狭いポリエステルの製
造法を提供することを目的とする。
（発明の構成）
本発明は、アルミニウムポルフイリン錯体及び
有機第四級塩を触媒として、酸無水物とエポキシ
ドとを反応させるポリエステルの製造法に関す
る。
本発明において用いられるアルミニウムポルフ
イリン錯体は、有機アルミニウム化合物と、ポル
フインとを反応させて得られるもので、下記の構
造で示される。
ここで、Ｘはハロゲン、アルキル基またはアル
コキシ基、R1は水素または
(Industrial Application Field) The present invention relates to a method for producing polyester having a narrow molecular weight distribution. (Prior Art) Polyester is generally produced by a polycondensation reaction of a polybasic acid and a polyhydric alcohol, but since this reaction is a sequential reaction, it is difficult to produce a polymer with a narrow molecular weight distribution. Polyesters can also be produced by ring-opening polymerization of acid anhydrides and epoxides, but
It is likewise difficult to produce polyesters with narrow molecular weight distributions. As a result of various studies aimed at producing polyester with a narrow molecular weight distribution, the present inventors found that
Discovered by the present inventors as a catalyst for the production of epoxide homopolymers (Die Makromolekulare
Chemie., 182 (4), 1073-9 (1981) It was discovered that the combination of an organic quaternary salt as a catalyst in addition to an aluminum porphyrin complex is suitable for the above purpose, and the present invention was achieved. This is what I did. (Objective of the Invention) An object of the present invention is to provide a method for producing polyester having a narrow molecular weight distribution. (Structure of the Invention) The present invention relates to a method for producing polyester in which an acid anhydride and an epoxide are reacted using an aluminum porphyrin complex and an organic quaternary salt as a catalyst. The aluminum porphyrin complex used in the present invention is obtained by reacting an organoaluminum compound and porphyrin, and is shown by the structure below. Here, X is halogen, alkyl group or alkoxy group, R 1 is hydrogen or
【式】R2は
水素ハロゲン、アルキル基またはアルコキシ基で
ある。
例えば、テトラフエニルポルフイナートアルミ
ニウムクロライド、テトラフエニルポルフイナー
トアルミニウムメトキシド、テトラフエニルポル
フイナートアルミニウムメチルなどがある。
このアルミニウムポルフイリン錯体は、例えば
不活性気体の雰囲気で、溶媒の存在下に、ポルフ
イ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得られる公知の
化合物である。
アルミニウムポルフイリン錯体の製造には、ポ
ルフインまたはフエニル基が置換のもしくは、非
置換のテトラフエニルポルフインを用いることが
出来る。
置換基としては、
クロライド、ブロマイドなどのハロゲン、
メチル基、エチル基などのアルキル基、
メトキシ基、エトキシ基などのアルコキシ基を
用いることが出来る。
ポルフインまたはフエニル基が置換のもしくは
非置換のテトラフエニルポルフインはそれぞれ例
えばベンズアルデヒドとピロールまたは対応する
置換基で置換されたベンズアルデヒドとピロール
から常法により、製造される。
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ライド、ジエチルア
ルミニウムブロマイド等の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等のジアルキルアルミニウ
ムアルコキシド
などがあげられる。
溶媒としては、
ベンゼン、トルエン、キシレン等の炭化水素、
塩化メチレン、クロロホルム、ジクロロエタン
等のハロゲン化炭化水素
などが使用出来る。
溶媒の使用量は任意に選択できる。
またアルミニウムポルフイリン錯体と組み合わ
せて用いる有機第四級塩としては、
エチルトリフエニルホスホニウムブロマイド、
エチルトリフエニルホスホニウムヨージド等のホ
スホニウム塩、
テトラエチルアンモニウムクロライド、テトラ
エチルアンモニウムブロマイド、テトラエチルア
ンモニウムアセテート等のアンモニウム塩などを
用いることが出来る。
特にエチルトリフエニルホスホニウムブロマイ
ドを用いることが好ましい。
本発明に用いられる酸無水物としては、
無水フタル酸、テトラヒドロ無水フタル酸、
テトラブロモ無水フタル酸、無水マレイン酸な
どがある。
これらは単独であるいは２種以上組み合わせて
エポキシドとの共重合に用いることが出来る。
本発明に用いられるエポキシドとしては、
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等の末端
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
シド等の三員環エポキシ基を有する脂環式アルキ
レンオキシド、
スチレンオキシド、フエニルグリシジルエーテ
ル等の三員環エポキシ基を有する芳香族アルキレ
ンオキシド
などがある。
これらは単独であるいは２種以上組み合わせ
て、酸無水物との共重合に用いることが出来る。
本発明のポリエステルの製造法は、無溶媒もし
くは、溶媒の存在下に、酸無水物とエポキシドの
混合物にアルミニウムポルフイリン錯体及び有機
第四級塩を加えて行われる。
不活性気体として窒素を用いることが好まし
い。
溶媒としては、塩化メチレン、クロロホルム、
ジクロロエタン、ベンゼン、トルエン、ジオキサ
ン、テトラヒドロフランなどを用いることが出来
るが、ハロゲン化炭化水素が好ましい。
反応は室温で十分進行するが加熱することも出
来る。
酸無水物とエポキシドの使用割合は、特に制限
はないが、酸無水物とエポキシドが等モルである
ことが好ましい。
アルミニウムポルフイリン錯体と有機第四級塩
の使用割合には特に制限はないが、通常アルミニ
ウムポルフイリン錯体１モルに対して有機第四級
塩は1/10倍モルから10倍モルの範囲で用いられ、
ほぼ等モルであることが好ましい。
またアルミニウムポルフイリン錯体に対するエ
ポキシドの割合には特に制限はないが、アルミニ
ウムポルフイリン錯体１モルに対してエポキシド
を10倍モルから、1000倍モルの範囲で用いるのが
好ましい。
（実施例）
実施例により本発明を説明する。
参考例 １
（アルミニウムポリフイリン錯体の製造）
冷却管を付けた４のフラスコにベンズアルデ
ヒド80ml（84.8ｇ）とピロール56ml（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。混合物をろ過した後、
メタノール−クロロホルム混合溶媒（重量で１対
１）で再結晶を行い、精製した。このようにして
得た、α、β、γ、δ−テトラフエニルポルフイ
ンは収率20％であつた。
このα、β、γ、δ−テトラフエニルポルフイ
ン0.61ｇと、ジエチルアルミニウムクロライド
0.12ｇを窒素雰囲気で、塩化メチレン溶媒20mlの
存在下に室温で反応させ、アルミニウムポルフイ
リン錯体触媒（）〔α、β、γ、δ−テトラフ
エニルポルフイナートアルミニウムクロライド〕
0.68ｇを含有する触媒溶液20mlを得た。
実施例 １〜８
酸無水物として無水フタル酸を用い、表１に示
す、各種エポキシドを酸無水物に対し、等モル混
合したのち、参考例１で得たアルミニウムポルフ
イリン錯体触媒〔〕およびエチルトリフエニル
ホスホニウムブロマイド〔〕の塩化メチレン溶
液（〔〕と〔〕の混合比は等モル、また錯体
触媒〔〕量は、酸無水物に対し、４モル％とな
るようにした）を加え、窒素雰囲気下、撹拌して
室温で反応を行つた。
重合終了後、重合生成物をクロロホルムに溶解
し、さらに、多量のメタノール中へ滴下し、ポリ
エステルを得た。得られたポリエステルの平均分
子量、分子量分布を表１に示した。
分子量分布は1.08〜1.17と１に近く、分子量の
揃つたポリエステルが得られていることが示され
る。
分子量の測定は、ポリスチレンゲルを充填した
４本のカラム（東洋曹達製カラムmix−mix−
3000−2000）に、テトラヒドロフラン溶媒を用い
て、カラム温度38℃で行つた。分子量の算出は、
得られたGPCスペクトルを、標準ポリスチレン
のGPCスペクトルで検量し、行つた。[Formula] R 2 is hydrogen halogen, an alkyl group or an alkoxy group. Examples include tetraphenylporphinate aluminum chloride, tetraphenylporphinate aluminum methoxide, and tetraphenylporphinate aluminum methyl. This aluminum porphyrin complex is a known compound that can be obtained, for example, by adding approximately equimolar amounts of an organoaluminum compound to porphyrin in an inert gas atmosphere in the presence of a solvent and reacting the mixture at room temperature. In the production of the aluminum porphyrin complex, porphin or tetraphenylporphin with a substituted or unsubstituted phenyl group can be used. As the substituent, halogens such as chloride and bromide, alkyl groups such as methyl and ethyl groups, and alkoxy groups such as methoxy and ethoxy groups can be used. Porphine or tetraphenylporphine with a substituted or unsubstituted phenyl group is produced by a conventional method from, for example, benzaldehyde and pyrrole or benzaldehyde and pyrrole substituted with the corresponding substituents, respectively. Examples of the organic aluminum compound include dialkyl aluminum halides such as diethylaluminum chloride and diethylaluminum bromide, and dialkyl aluminum alkoxides such as diethylaluminum methoxide and diethylaluminum ethoxide. As the solvent, hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane can be used. The amount of solvent used can be selected arbitrarily. In addition, organic quaternary salts used in combination with the aluminum porphyrin complex include ethyltriphenylphosphonium bromide,
Phosphonium salts such as ethyl triphenylphosphonium iodide, ammonium salts such as tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium acetate, etc. can be used. In particular, it is preferable to use ethyltriphenylphosphonium bromide. Examples of acid anhydrides used in the present invention include phthalic anhydride, tetrahydrophthalic anhydride, tetrabromophthalic anhydride, and maleic anhydride. These can be used alone or in combination of two or more for copolymerization with epoxide. Epoxides used in the present invention include ethylene oxide, propylene oxide, 1-
Aliphatic alkylene oxides having a terminal three-membered epoxy group such as butylene oxide and epichlorohydrin, alicyclic alkylene oxides having a three-membered ring epoxy group such as cyclohexene oxide and cyclopentene oxide, three-membered styrene oxide, phenyl glycidyl ether, etc. Examples include aromatic alkylene oxides having a ring epoxy group. These can be used alone or in combination of two or more for copolymerization with an acid anhydride. The method for producing polyester of the present invention is carried out by adding an aluminum porphyrin complex and an organic quaternary salt to a mixture of an acid anhydride and an epoxide without a solvent or in the presence of a solvent. Preferably, nitrogen is used as the inert gas. As a solvent, methylene chloride, chloroform,
Although dichloroethane, benzene, toluene, dioxane, tetrahydrofuran, etc. can be used, halogenated hydrocarbons are preferred. The reaction proceeds satisfactorily at room temperature, but can also be heated. The ratio of acid anhydride and epoxide used is not particularly limited, but it is preferable that the acid anhydride and epoxide be equimolar. There is no particular restriction on the ratio of the aluminum porphyrin complex and the organic quaternary salt used, but the organic quaternary salt is usually used in a range of 1/10 to 10 times the mole of the aluminum porphyrin complex. is,
Preferably, the moles are approximately equimolar. Although there is no particular restriction on the ratio of epoxide to aluminum porphyrin complex, it is preferable to use the epoxide in a range of 10 to 1000 times by mole per mole of aluminum porphyrin complex. (Example) The present invention will be explained with reference to an example. Reference Example 1 (Production of aluminum polyphylline complex) 80 ml (84.8 g) of benzaldehyde and 56 ml (53.6 g) of pyrrole were added to propionic acid 3 in a No. 4 flask equipped with a cooling tube, and after reacting under reflux for 30 minutes, I left it for a day and night. After filtering the mixture,
The product was purified by recrystallization using a methanol-chloroform mixed solvent (1:1 by weight). The yield of α, β, γ, δ-tetraphenylporphin thus obtained was 20%. This α, β, γ, δ-tetraphenylporphin 0.61g and diethylaluminum chloride
0.12 g was reacted at room temperature in the presence of 20 ml of methylene chloride solvent in a nitrogen atmosphere to prepare aluminum porphyrin complex catalyst () [α, β, γ, δ-tetraphenylporphynate aluminum chloride].
20 ml of catalyst solution containing 0.68 g was obtained. Examples 1 to 8 Using phthalic anhydride as the acid anhydride, various epoxides shown in Table 1 were mixed in equimolar amounts with the acid anhydride, and then the aluminum porphyrin complex catalyst [] obtained in Reference Example 1 and ethyl A methylene chloride solution of triphenylphosphonium bromide [] was added (the mixing ratio of [] and [] was equimolar, and the amount of complex catalyst [] was 4 mol% relative to the acid anhydride), and nitrogen was added. The reaction was carried out at room temperature under an atmosphere of stirring. After the polymerization was completed, the polymerization product was dissolved in chloroform and further added dropwise into a large amount of methanol to obtain a polyester. Table 1 shows the average molecular weight and molecular weight distribution of the obtained polyester. The molecular weight distribution was 1.08 to 1.17, close to 1, indicating that a polyester with uniform molecular weight was obtained. The molecular weight was measured using four columns packed with polystyrene gel (Column mix-mix- manufactured by Toyo Soda).
3000-2000) using tetrahydrofuran solvent at a column temperature of 38°C. Calculation of molecular weight is
The obtained GPC spectrum was calibrated with the GPC spectrum of standard polystyrene.
【表】【table】
【表】
（発明の効果）
本発明の製造法により、分子量分布の狭いポリ
エステルを、室温下の温和な条件の下で得ること
が出来る。[Table] (Effects of the Invention) According to the production method of the present invention, polyester with a narrow molecular weight distribution can be obtained under mild conditions at room temperature.
Claims (1)
級塩を触媒として酸無水物とエポキシドとを反応
させることを特徴とするポリエステルの製造法。 ２ アルミニウムポルフイリン錯体が、テトラフ
エニルポルフイナートアルミニウムクロライドで
ある特許請求の範囲第１項記載のポリエステルの
製造法。 ３ 有機第四級塩がエチルトリフエニルホスホニ
ウムブロマイドである特許請求の範囲第１項また
は第２項記載のポリエステルの製造法。[Claims] 1. A method for producing polyester, which comprises reacting an acid anhydride and an epoxide using an aluminum porphyrin complex and an organic quaternary salt as catalysts. 2. The method for producing a polyester according to claim 1, wherein the aluminum porphyrin complex is tetraphenylporphynate aluminum chloride. 3. The method for producing a polyester according to claim 1 or 2, wherein the organic quaternary salt is ethyltriphenylphosphonium bromide.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18596884A JPS6164722A (en) | 1984-09-05 | 1984-09-05 | Production of polyester |
| US06/706,181 US4565845A (en) | 1984-09-05 | 1985-02-27 | Process for producing polyester and block copolymer thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18596884A JPS6164722A (en) | 1984-09-05 | 1984-09-05 | Production of polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6164722A JPS6164722A (en) | 1986-04-03 |
| JPH043409B2 true JPH043409B2 (en) | 1992-01-23 |
Family
ID=16180024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18596884A Granted JPS6164722A (en) | 1984-09-05 | 1984-09-05 | Production of polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6164722A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998042769A1 (en) * | 1997-03-25 | 1998-10-01 | Toray Industries, Inc. | Catalyst for producing polyester, process for producing the same, and process for producing polyester by using the same |
-
1984
- 1984-09-05 JP JP18596884A patent/JPS6164722A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998042769A1 (en) * | 1997-03-25 | 1998-10-01 | Toray Industries, Inc. | Catalyst for producing polyester, process for producing the same, and process for producing polyester by using the same |
| CN1109057C (en) * | 1997-03-25 | 2003-05-21 | 东丽株式会社 | Catalyst for producing polyester, process for producing the same, and process for producing polyester by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6164722A (en) | 1986-04-03 |
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