JPH05247184A - Production of lactone polymer - Google Patents
Production of lactone polymerInfo
- Publication number
- JPH05247184A JPH05247184A JP8169792A JP8169792A JPH05247184A JP H05247184 A JPH05247184 A JP H05247184A JP 8169792 A JP8169792 A JP 8169792A JP 8169792 A JP8169792 A JP 8169792A JP H05247184 A JPH05247184 A JP H05247184A
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- Prior art keywords
- polymer
- lactone
- polymerization
- catalyst
- molecular weight
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ラクトン類の高重合体
の新規なる製造方法に関する。さらに詳しく言えば、ハ
ロゲン化希土類メタロセン錯体であるシクロペンタジエ
ニル系希土類金属錯体を触媒に用いるリビングアニオン
重合反応により、低温にてラクトン類の高重合体を製造
する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing high polymers of lactones. More specifically, it relates to a method for producing a high polymer of lactone at a low temperature by a living anion polymerization reaction using a cyclopentadienyl rare earth metal complex which is a halogenated rare earth metallocene complex as a catalyst.
【０００２】[0002]
【従来の技術】εーカプロラクトンをはじめとするラク
トン類の重合体は、工業的にはポリウレタン、塗料用樹
脂、さらにはプラスチックスに柔軟性を付与する改質材
として広く用いられている。重合体の中でも特に分子量
数万以上のポリカプロラクトン高重合体は、生分解性プ
ラスチックスとして最近注目されている。BACKGROUND OF THE INVENTION Polymers of lactones such as ε-caprolactone are industrially widely used as modifiers for imparting flexibility to polyurethanes, paint resins, and plastics. Among the polymers, a polycaprolactone high polymer having a molecular weight of tens of thousands or more has recently attracted attention as a biodegradable plastic.
【０００３】ラクトン高重合体は、従来種々の方法によ
って製造されている。最も一般的な方法は、オクチル酸
スズ、ジブチルスズオキシド等の有機スズ化合物、塩化
第１スズの如きハロゲン化第１スズ化合物、テトラアル
コキシチタンのようなチタン化合物、モリブデンやバナ
ジウムの如き遷移金属の有機キレート化合物等を触媒に
用い、水やアルコールの如き活性水素を有する物質を開
始剤として、ラクトンを開環重合する方法が良く知られ
ている。High lactone polymers are conventionally produced by various methods. The most common methods are organotin compounds such as tin octylate and dibutyltin oxide, stannous halide compounds such as stannous chloride, titanium compounds such as tetraalkoxytitanium, and organic compounds of transition metals such as molybdenum and vanadium. A method of ring-opening polymerization of a lactone using a chelate compound or the like as a catalyst and a substance having active hydrogen such as water or alcohol as an initiator is well known.
【０００４】しかしながら、これらの方法は開環重合反
応に１００℃〜２３０℃の高温かつ長時間が必要とされ
る。そのため解重合反応によるモノマーやダイマー、さ
らにはトリマー等の不純物の生成、熱による酸化分解等
々が起こりやすいため、得られる高重合体の分子量コン
トロールが困難であるばかりでなく、重合体の臭気、色
相等工業製品としての品質の上でも必ずしも十分とは言
えなかった。However, these methods require a high temperature of 100 ° C. to 230 ° C. and a long time for the ring-opening polymerization reaction. Therefore, the production of impurities such as monomers and dimers by depolymerization, further trimers, and oxidative decomposition due to heat are likely to occur, so that not only is it difficult to control the molecular weight of the resulting high polymer, but the odor and hue of the polymer It was not always sufficient in terms of quality as an industrial product.
【０００５】ラクトンを重合する方法としてはＢＦ3・
エーテル錯体、四塩化スズ、硫酸等の強い酸及びルイス
酸を触媒として用いるカチオン重合による方法も知られ
ている。 しかしながらカチオン重合では低温で重合が
進行するにもかかわらず、オリゴマーのような低分子量
の重合体しか得られないことは周知のことである。As a method for polymerizing lactone, BF 3
A method by cationic polymerization using a strong acid such as an ether complex, tin tetrachloride, sulfuric acid and a Lewis acid as a catalyst is also known. However, it is well known that in cationic polymerization, although the polymerization proceeds at a low temperature, only a low molecular weight polymer such as an oligomer can be obtained.
【０００６】また、アルミニウムアルコキシドやアルカ
リ金属アルコキシドでもラクトン類の重合が比較的低温
で進行することが知られているが、高重合体が得られな
いという問題がある。It is also known that lactones can be polymerized at a relatively low temperature even with aluminum alkoxides and alkali metal alkoxides, but there is a problem that a high polymer cannot be obtained.
【０００７】低温でラクトン重合体を得る方法としては
アルキルリチウム等を用いるリビングアニオン重合によ
る方法が知られている。この方法によれば０〜４０℃と
いった室温付近で、あるいは０℃以下のさらに低温でも
重合が可能である。しかしながら、これらのリビングア
ニオン重合触媒でも、分子量が十分大きくならないとい
う問題がある。As a method for obtaining a lactone polymer at low temperature, a method by living anion polymerization using alkyllithium or the like is known. According to this method, the polymerization can be carried out near room temperature such as 0 to 40 ° C. or even at a lower temperature of 0 ° C. or lower. However, even these living anionic polymerization catalysts have a problem that the molecular weight does not become sufficiently large.
【０００８】[0008]
【発明が解決しようとする課題】以上のような問題点に
鑑み、解重合や熱分解反応を起こすことのない比較的低
温で容易にラクトン類の高重合体を得んと鋭意研究を行
った結果、電気陰性度がリチウムやマグネシウムに近い
希土類金属のシクロペンタジニエル錯体がラクトン類の
極めてすぐれた高重合触媒作用があることを見いだし、
本発明に至った。In view of the above problems, the inventors have earnestly studied to obtain a high polymer of lactones easily at a relatively low temperature without depolymerization or thermal decomposition reaction. As a result, they found that cyclopentadiene complexes of rare earth metals, whose electronegativity is close to that of lithium and magnesium, have a very high polymerization catalytic action of lactones,
The present invention has been reached.
【０００９】すなわち本発明は、一般式（Ｃ5Ｒ5）aＬ
ｎＸbで表されるシクロペンタジエニル系希土類金属錯
体を触媒とし、ラクトン類を開環重合させることを特徴
とするラクトン類の高重合体の製造方法に関する。（但
し、上記一般式中のＲはＨ、アルキル基またはＳｉ（Ｃ
Ｈ3）3を表わし、これらが各単独または任意に混合され
て構成されていてもよく、ＬｎはＳｃ、Ｙ、またはラン
タノイド（Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅ
ｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌ
ｕ）を表わし、Ｘはフッ素を除くハロゲンを表わし、
ａ、ｂは共に０でない正の整数値を表し、ａ＋ｂ＝３で
ある。）That is, the present invention has the general formula (C 5 R 5 ) aL
The present invention relates to a method for producing a high polymer of lactones, which comprises subjecting a lactone to ring-opening polymerization using a cyclopentadienyl rare earth metal complex represented by nXb as a catalyst. (However, R in the above general formula is H, an alkyl group or Si (C
H 3 ) 3 , each of which may be used alone or in any mixture thereof, and Ln is Sc, Y, or a lanthanoid (La, Ce, Pr, Nd, Pm, Sm, E).
u, Gd, Tb, Dy, Ho, Er, Tm, Yb, L
u), X represents halogen other than fluorine,
Both a and b represent a positive integer value which is not 0, and a + b = 3. )
【００１０】本発明のラクトン類としてはβープロピオ
ラクトン、γーブチロラクトン、δーバレロラクトン、
εーカプロラクトン等が挙げられるが、βーメチルプロ
ピオラクトン、３，３，５ートリメチルーεーカプロラ
クトン等の置換基をもつラクトン類も用いることができ
る。しかし、一般的に置換基を有するラクトン類は高重
合体が得られにくい。最も工業的に安価に製造され、か
つ重合が容易に進行するラクトン類はεーカプロラクト
ンである。εーカプロラクトンは、シクロヘキサノンを
過酢酸のような過酸によるバイヤービリガー反応によっ
て、工業的に大量生産されている。例えば、ダイセル化
学工業株式会社によって製造販売されている商品名「プ
ラクセルーＭ」を用いることができる。The lactones of the present invention include β-propiolactone, γ-butyrolactone, δ-valerolactone,
Examples thereof include ε-caprolactone and the like, but lactones having a substituent such as β-methylpropiolactone and 3,3,5-trimethyl-ε-caprolactone can also be used. However, it is generally difficult to obtain a high polymer with a lactone having a substituent. The lactone which is most industrially manufactured at a low cost and whose polymerization proceeds easily is ε-caprolactone. ε-caprolactone is industrially mass-produced by the Bayer-Villiger reaction of cyclohexanone with a peracid such as peracetic acid. For example, the trade name “Placcel M” manufactured and sold by Daicel Chemical Industries, Ltd. can be used.
【００１１】これらのラクトン類は単独で重合させるこ
ともできるが、２種類以上のラクトンモノマーを共重合
させることもできる。さらに、ラクトン以外のモノマー
をラクトンと共に加えて共重合させることも可能であ
る。そのようなモノマーの例としては環状モノカーボネ
ートが挙げられる。例えばネオペンチルグリコールの環
状モノカーボネート化合物もラクトンとの共重合が可能
である。These lactones can be polymerized alone, or two or more kinds of lactone monomers can be copolymerized. Furthermore, it is also possible to add a monomer other than the lactone together with the lactone for copolymerization. Examples of such monomers include cyclic monocarbonates. For example, a cyclic monocarbonate compound of neopentyl glycol can also be copolymerized with a lactone.
【００１２】本発明で使用するラクトン類の高重合触媒
は一般式（Ｃ5Ｒ5）aＬｎＸbで表されるシクロペンタジ
エニル系希土類金属錯体であり、式中のＲが表す好まし
いアルキル基としてはメチル基、エチル基、プロピル基
等の低級アルキル基を例示することが出来、またＸはフ
ッ素を除くハロゲンとして塩素、臭素、ヨウ素を示し、
触媒としては例えば（Ｃ5Ｈ5）2ＹＣｌ、〔Ｃ5Ｈ4Ｓｉ
（ＣＨ3）3〕2ＹＣｌ、（Ｃ5Ｈ4ｔーＢｕ）2ＹＣｌ、
〔Ｃ5（ＣＨ3）5〕2ＳｍＣｌ、〔Ｃ5（ＣＨ3）5〕2Ｓｍ
Ｉ、〔Ｃ5（ＣＨ3）5〕2ＬｕＣｌ、（Ｃ5Ｈ5）ＹＣ
ｌ2、（Ｃ5Ｈ5）ＳｍＣｌ2、（Ｃ5Ｈ5）2ＹＢｒ、（Ｃ5
Ｈ5）2ＳｍＢｒ等が挙げられる。これらの金属錯体はい
ずれも「第４版実験化学講座有機金属化合物」（日本化
学会編），丸善（１９９０）にその合成法が記載されて
おり、ＴＨＦ（テトラハイドロフラン）が１分子配位し
た形で容易に得ることができる。なお、これらの触媒は
２量体であっても良い。The lactone high polymerization catalyst used in the present invention is a cyclopentadienyl rare earth metal complex represented by the general formula (C 5 R 5 ) aLnXb, and a preferable alkyl group represented by R in the formula is Examples thereof include lower alkyl groups such as a methyl group, an ethyl group, and a propyl group, and X represents chlorine, bromine, or iodine as halogen other than fluorine,
Examples of the catalyst include (C 5 H 5 ) 2 YCl and [C 5 H 4 Si
(CH 3) 3] 2 YCl, (C 5 H 4 t chromatography Bu) 2 YCl,
[C 5 (CH 3 ) 5 ] 2 SmCl, [C 5 (CH 3 ) 5 ] 2 Sm
I, [C 5 (CH 3 ) 5 ] 2 LuCl, (C 5 H 5 ) YC
l 2 , (C 5 H 5 ) SmCl 2, (C 5 H 5 ) 2 YBr, (C 5
H 5) 2 SmBr the like. The synthesis method of each of these metal complexes is described in "4th Edition Experimental Chemistry Course Organometallic Compounds" (edited by the Chemical Society of Japan), Maruzen (1990), and one molecule of THF (tetrahydrofuran) is coordinated. It can be easily obtained in the form Note that these catalysts may be dimers.
【００１３】これらのシクロペンタジエニル系希土類金
属錯体触媒はラクトン類モノマーに対し１×１０-4〜１
０モル％、好ましくは１×１０-3〜１モル％用いること
が出来る。触媒濃度が低いほど、重合体の分子量は大き
くなる。These cyclopentadienyl rare earth metal complex catalysts are used in an amount of 1 × 10 -4 to 1 with respect to the lactone monomer.
0 mol%, preferably 1 × 10 −3 to 1 mol% can be used. The lower the catalyst concentration, the higher the molecular weight of the polymer.
【００１４】重合反応は−７０℃〜１５０℃、好ましく
は−３０℃〜１００℃の温度範囲で行う。重合温度が高
い程、重合速度は大きいが、得られる重合体の分子量分
布は広くなる。逆に重合温度が低い程、重合速度は小さ
いが、極めて分子量分布の狭い重合体が得られる。The polymerization reaction is carried out in the temperature range of -70 ° C to 150 ° C, preferably -30 ° C to 100 ° C. The higher the polymerization temperature, the higher the polymerization rate, but the broader the molecular weight distribution of the polymer obtained. Conversely, the lower the polymerization temperature, the lower the polymerization rate, but a polymer having a very narrow molecular weight distribution can be obtained.
【００１５】重合反応は溶媒を用いないで行うこともで
きるが、トルエン、キシレンのような芳香族系溶媒、テ
ロラハイドロフラン、ジオキサン、ジエチルエーテル等
のエーテル系溶媒、塩化メチレンのような塩素系溶媒等
を重合反応を阻害しない範囲で用いることが出来る。Although the polymerization reaction can be carried out without using a solvent, an aromatic solvent such as toluene or xylene, an ether solvent such as terorahydrofuran, dioxane or diethyl ether, or a chlorine solvent such as methylene chloride. And the like can be used within a range that does not hinder the polymerization reaction.
【００１６】重合反応にはバッチ式の反応器、あるいは
連続式の反応器のいずれでも採用可能であるが、重合熱
を効率よく除去し、重合温度を一定に保つことのできる
冷却装置を備えた強力な撹拌が可能な重合装置が好まし
い。あるいはモノマーのラクトンと触媒を溶解し、重合
体を溶解しないような不活性溶媒の中で重合を行ない、
生成した重合体を溶媒の中に沈澱せしめる沈澱重合も、
実際の工業的な製造プロセスとしては有効な手段であ
る。Either a batch type reactor or a continuous type reactor can be used for the polymerization reaction, and a cooling device capable of efficiently removing the heat of polymerization and keeping the polymerization temperature constant is provided. A polymerization apparatus capable of vigorous stirring is preferable. Alternatively, the monomer lactone and the catalyst are dissolved, and the polymerization is performed in an inert solvent that does not dissolve the polymer,
Precipitation polymerization, in which the produced polymer is precipitated in a solvent,
This is an effective means for an actual industrial manufacturing process.
【００１７】重合反応は窒素のような不活性ガスの奮囲
気下で行うことが好ましい。また、不活性ガスやモノマ
ーは十分に乾燥し、水分を含まぬことが重要である。何
故ならば水分は有機金属錯体触媒と反応し、触媒活性を
損なうからである。The polymerization reaction is preferably carried out under an atmosphere of an inert gas such as nitrogen. Further, it is important that the inert gas and the monomer are sufficiently dried and do not contain water. This is because water reacts with the organometallic complex catalyst and impairs the catalytic activity.
【００１８】本発明で得られたラクトン重合体は、高重
合体の場合はその中に含まれる金属触媒の含有量が極め
て少ないため、触媒を除去しなくても良い。もし除去す
る必要のあるときは、水あるいは薄い塩酸などによって
洗滌して触媒を除去し、よく水洗の後、重合体を乾燥す
る。When the lactone polymer obtained by the present invention is a high polymer, the content of the metal catalyst contained therein is extremely small, and therefore the catalyst need not be removed. If it is necessary to remove it, the catalyst is removed by washing with water or dilute hydrochloric acid, and after thoroughly washing with water, the polymer is dried.
【００１９】本発明によるラクトン類の高重合体は比較
的低い温度で製造可能なため、解重合や熱分解によって
生成する不純物が極めて少なく、従って色調にすぐれ、
また臭気も少ない。またこれらの重合体は従来の方法で
得られるものに比べ、分子量分布も狭い。Since the high polymer of lactones according to the present invention can be produced at a relatively low temperature, impurities produced by depolymerization or thermal decomposition are extremely small, and therefore the color tone is excellent.
It also has little odor. Further, these polymers have a narrower molecular weight distribution than those obtained by conventional methods.
【００２０】またこうして得られた重合体は、押出機に
て溶融下にペレット化し、さらにフィルム、繊維、発砲
体シート及び各種成形物として用いることが出来る。The polymer thus obtained can be pelletized while being melted by an extruder and used as a film, a fiber, a foam sheet or various molded products.
【００２１】[0021]
【実施例】以下、実施例をもって本発明をさらに具体的
に説明する。なお本実施例をもって本発明の範囲が限定
されるものではない。EXAMPLES The present invention will be described in more detail with reference to examples. The scope of the present invention is not limited by the present embodiment.
【００２２】（実施例１）（Ｃ5Ｈ5）2ＹＣｌ（ＴＨ
Ｆ）０．１ｍｍｏｌ（３３ｍｇ）をトルエン１００ｍｌ
に溶解し、δーバレロラクトン５０ｍｍｏｌ（４．６ｍ
ｌ）を加え、２０℃で窒素下に３時間反応させた。反応
物をメタノール１００ｍｌに注ぎ、ポリマーを析出させ
た。ポリマー沈澱をメタノールと分離し、乾燥し、ポリ
δーバレロラクトンを得た。収率は８５％、数平均分子
量Ｍｎ＝８４，０００、分子量分布はＭｗ（重量平均分
子量）とＭｎとの比Ｍｗ／Ｍｎで表し、Ｍｗ／Ｍｎ＝
１．６６であった。Example 1 (C 5 H 5 ) 2 YCl (TH
F) 0.1 mmol (33 mg) of toluene 100 ml
Dissolved in 50 mmol of δ-valerolactone (4.6 m
1) was added, and the mixture was reacted at 20 ° C. under nitrogen for 3 hours. The reaction product was poured into 100 ml of methanol to precipitate a polymer. The polymer precipitate was separated from methanol and dried to obtain poly δ-valerolactone. The yield is 85%, the number average molecular weight Mn is 84,000, and the molecular weight distribution is represented by the ratio Mw / Mn of Mw (weight average molecular weight) and Mn, and Mw / Mn =
It was 1.66.
【００２３】（実施例２）（Ｃ5Ｈ5）2ＹＣｌ（ＴＨ
Ｆ）０．１ｍｍｏｌ（３３ｍｇ）をトルエン１００ｍｌ
に溶解し、εーカプロラクトン５０ｍｍｏｌ（５．７
ｇ）を加え２０℃、３時間かかって重合させた。反応生
成物をメタノール１００ｍｍｌに注ぎ、白色沈澱として
ポリカプロラクトンを得た。乾燥後得られたポリマーの
収率を測定すると、９８％であった。数平均分子量はＭ
ｎ＝１２５，０００、分子量分布Ｍｗ／Ｍｎ＝１．７８
であった。Example 2 (C 5 H 5 ) 2 YCl (TH
F) 0.1 mmol (33 mg) of toluene 100 ml
Dissolved in 50 mmol of ε-caprolactone (5.7
g) was added and polymerization was carried out at 20 ° C. for 3 hours. The reaction product was poured into 100 ml of methanol to obtain polycaprolactone as a white precipitate. The yield of the polymer obtained after drying was 98%. Number average molecular weight is M
n = 125,000, molecular weight distribution Mw / Mn = 1.78
Met.
【００２４】（実施例３）〔Ｃ5（ＣＨ3）5〕2ＬｕＣｌ
（ＴＨＦ）０．１ｍｍｏｌ（５５ｍｇ）をトルエン１０
ｍｌに溶解し、δーバレロラクトン１０ｍｍｏｌ（１．
５ｍｌ）を加え２０℃で３時間反応させ、反応物をメタ
ノール１００ｍｌに注ぎポリマーを得た。収率８５％、
数平均分子量Ｍｎ＝８２，６００、分子量分布Ｍｗ／Ｍ
ｎ＝１．２２であった。Example 3 [C 5 (CH 3 ) 5 ] 2 LuCl
(THF) 0.1 mmol (55 mg) with toluene 10
10 ml of δ-valerolactone (1.
5 ml) was added and reacted at 20 ° C. for 3 hours, and the reaction product was poured into 100 ml of methanol to obtain a polymer. Yield 85%,
Number average molecular weight Mn = 82,600, molecular weight distribution Mw / M
It was n = 1.22.
【００２５】（実施例４）〔（Ｃ5Ｈ5）2ＹｂＣｌ〕
2０．１ｍｍｏｌ（３４ｍｇ）をトルエン２０ｍｌに溶
解し、δーバレロラクトン１０ｍｍｏｌ（１．５ｍｌ）
を加え、４０℃で１時間反応させた後、メタノールに注
ぎポリマーを沈澱させた。乾燥後の重量を測定したとこ
ろ、収率７５％であった。また数平均分子量Ｍｎ＝４
５，０００、分子量分布Ｍｗ／Ｍｎ＝１．３７であっ
た。(Example 4) [(C 5 H 5 ) 2 YbCl]
2 0.1 mmol (34 mg) was dissolved in 20 ml of toluene, and 10 mmol (1.5 ml) of δ-valerolactone was dissolved.
Was added, and the mixture was reacted at 40 ° C. for 1 hour and then poured into methanol to precipitate a polymer. When the weight after drying was measured, the yield was 75%. The number average molecular weight Mn = 4
The molecular weight distribution was 5,000 and Mw / Mn = 1.37.
【００２６】（実施例５）〔（Ｃ5Ｈ5）2ＹｂＣｌ〕
2０．１ｍｍｏｌ（３４ｍｇ）をトルエン２０ｍｌに溶
解し、εーカプロラクトン１０ｍｍｏｌ（１．１４ｇ）
を加え、３０℃で２時間反応させ、反応液をメタノール
に注いだ。析出したポリマーの収率は９２％、数平均分
子量Ｍｎ＝５６，０００、分子量分布Ｍｗ／Ｍｎ＝１．
３１であった。Example 5 [(C 5 H 5 ) 2 YbCl]
2 0.1 mmol (34 mg) was dissolved in 20 ml of toluene, and 10 mmol (1.14 g) of ε-caprolactone was dissolved.
Was added and reacted at 30 ° C. for 2 hours, and the reaction solution was poured into methanol. The yield of the precipitated polymer was 92%, the number average molecular weight was Mn = 56,000, and the molecular weight distribution was Mw / Mn = 1.
It was 31.
【００２７】（実施例６）〔Ｃ5Ｈ5〕2ＹＣｌ（ＴＨ
Ｆ）０．１ｍｍｏｌ（３３ｍｇ）を溶媒を用いずに直接
εーカプロラクトン４．６ｍｌと０℃で混合し、３０℃
で２時間反応を行った。反応系は重合の進行と共に、ポ
リマーの結晶化のため系全体が白く固化した。メタノー
ルに浸漬し、残留モノマーを洗い、乾燥してポリマーを
得た。収率は７５％、数平均分子量Ｍｎ＝１２５，００
０、分子量分布Ｍｗ／Ｍｎ＝１．８２であった。Example 6 [C 5 H 5 ] 2 YCl (TH
F) 0.1 mmol (33 mg) was directly mixed with 4.6 ml of ε-caprolactone at 0 ° C. without using a solvent, and 30 ° C.
The reaction was carried out for 2 hours. As the reaction system proceeded with the polymerization, the entire system solidified white due to the crystallization of the polymer. It was immersed in methanol, the residual monomer was washed, and dried to obtain a polymer. Yield 75%, number average molecular weight Mn = 125,000
0, the molecular weight distribution was Mw / Mn = 1.82.
【００２８】（実施例７）〔Ｃ5（ＣＨ3）5〕ＬａＩ
2（ＴＨＦ）3０．１ｍｍｏｌ（７４ｍｇ）をトルエン５
０ｍｌに溶解し、εーカプロラクトン２０ｍｍｏｌ（３
ｍｌ）を加え４０℃で２時間反応させた。メタノール１
００ｍｌに反応液を注ぎ、白色ポリマーを得た。収率２
５％、数平均分子量Ｍｎ＝１５，０００、分子量分布Ｍ
ｗ／Ｍｎ＝１．８２であった。Example 7 [C 5 (CH 3 ) 5 ] LaI
2 (THF) 3 0.1 mmol (74 mg) was added to toluene 5
It is dissolved in 0 ml and 20 mmol of ε-caprolactone (3
(ml) was added and the mixture was reacted at 40 ° C. for 2 hours. Methanol 1
The reaction solution was poured into 00 ml to obtain a white polymer. Yield 2
5%, number average molecular weight Mn = 15,000, molecular weight distribution M
It was w / Mn = 1.82.
【００２９】（比較例１）ブチルリチウム（０．１ｍｍ
ｏｌ）をトルエン２０ｍｌに溶解し、δーバレロラクト
ン１０ｍｍｏｌ（１．５ｍｌ）を加え、４０℃で１時間
反応させポリマーを得た。収率は３５％であった。また
数平均分子量Ｍｎ＝２７，０００、分子量分布Ｍｗ／Ｍ
ｎ＝１．９１であった。Comparative Example 1 Butyllithium (0.1 mm
was dissolved in 20 ml of toluene, 10 mmol (1.5 ml) of δ-valerolactone was added, and the mixture was reacted at 40 ° C. for 1 hour to obtain a polymer. The yield was 35%. Further, the number average molecular weight Mn = 27,000, the molecular weight distribution Mw / M
It was n = 1.91.
【００３０】（参考例２）塩化第１スズ（０．１ｍｍｏ
ｌ）をトルエン２０ｍｌに溶解し、εーカプロラクトン
（１０ｍｍｏｌ）を加え、４０℃で１時間反応させてポ
リマーを得た。収率は３％であった。Reference Example 2 Stannous chloride (0.1 mmo)
l) was dissolved in 20 ml of toluene, ε-caprolactone (10 mmol) was added, and the mixture was reacted at 40 ° C. for 1 hour to obtain a polymer. The yield was 3%.
【００３１】[0031]
【発明の効果】以上詳しく説明したように、本発明の製
造方法を採用することにより、解重合や熱分解反応を起
こすことのない比較的低温で、容易にラクトン類の高重
合体を得ることが出来るようになった。As described in detail above, by adopting the production method of the present invention, a high polymer of lactones can be easily obtained at a relatively low temperature without depolymerization or thermal decomposition reaction. Is now possible.
Claims (1)
ニル系希土類金属錯体を触媒とし、ラクトン類を開環重
合させることを特徴とするラクトン類の高重合体の製造
方法。（但し、一般式中のＲはＨ、アルキル基またはＳ
ｉ（ＣＨ3）3を表わし、これらが各単独または任意に混
合されて構成されていてもよく、ＬｎはＳｃ、Ｙ、また
はランタノイド（Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓ
ｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙ
ｂ、Ｌｕ）を表わし、Ｘはフッ素を除くハロゲンを表わ
し、ａ、ｂは共に０でない正の整数値を表し、ａ＋ｂ＝
３である。）A method for producing a high polymer of lactones, which comprises subjecting a lactone to ring-opening polymerization using a cyclopentadienyl rare earth metal complex represented by the general formula (C 5 R 5 ) aLnXb as a catalyst. (However, R in the general formula is H, an alkyl group or S
i (CH 3 ) 3 and each of them may be formed alone or in an arbitrary mixture, and Ln is Sc, Y, or a lanthanoid (La, Ce, Pr, Nd, Pm, S).
m, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
b, Lu), X represents a halogen other than fluorine, a and b each represent a positive integer other than 0, and a + b =
It is 3. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04081697A JP3131493B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing lactone polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04081697A JP3131493B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing lactone polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05247184A true JPH05247184A (en) | 1993-09-24 |
| JP3131493B2 JP3131493B2 (en) | 2001-01-31 |
Family
ID=13753570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04081697A Expired - Fee Related JP3131493B2 (en) | 1992-03-03 | 1992-03-03 | Method for producing lactone polymer |
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| Country | Link |
|---|---|
| JP (1) | JP3131493B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019379A1 (en) * | 1997-10-15 | 1999-04-22 | Daicel Chemical Industries, Ltd. | Processes for the preparation of monodisperse polymers, processes for the continuous polymerization of cyclic monomers, and polymers prepared thereby |
| JP2003064174A (en) * | 2001-08-24 | 2003-03-05 | Nagoya Industrial Science Research Inst | Lactone ring-opening polymerization catalyst, method for producing polyester, and method for producing block copolymer |
| WO2008004628A1 (en) | 2006-07-07 | 2008-01-10 | Sumitomo Chemical Company, Limited | Rare earth metal complex, polymerization catalyst and method for producing polymer |
-
1992
- 1992-03-03 JP JP04081697A patent/JP3131493B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999019379A1 (en) * | 1997-10-15 | 1999-04-22 | Daicel Chemical Industries, Ltd. | Processes for the preparation of monodisperse polymers, processes for the continuous polymerization of cyclic monomers, and polymers prepared thereby |
| US6191250B1 (en) * | 1997-10-15 | 2001-02-20 | Daicel Chemical Industries, Ltd. | Processes for the preparation of a monodisperse polymers, processes for the continuous polymerization of cyclic monomers, and polymers prepared thereby |
| JP4311768B2 (en) * | 1997-10-15 | 2009-08-12 | ダイセル化学工業株式会社 | Monodispersed polymer production method, cyclic monomer continuous polymerization method, and polymer thereby |
| JP2003064174A (en) * | 2001-08-24 | 2003-03-05 | Nagoya Industrial Science Research Inst | Lactone ring-opening polymerization catalyst, method for producing polyester, and method for producing block copolymer |
| WO2008004628A1 (en) | 2006-07-07 | 2008-01-10 | Sumitomo Chemical Company, Limited | Rare earth metal complex, polymerization catalyst and method for producing polymer |
| JP2008231084A (en) * | 2006-07-07 | 2008-10-02 | Sumitomo Chemical Co Ltd | Rare earth metal complex, polymerization catalyst, and method for producing polymer |
| US7851569B2 (en) | 2006-07-07 | 2010-12-14 | Sumitomo Chemical Company, Limited | Rare earth metal complex, polymerization catalyst, and process for producing polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3131493B2 (en) | 2001-01-31 |
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