JP3079717B2 - Method for producing high molecular weight aliphatic polyester - Google Patents
Method for producing high molecular weight aliphatic polyesterInfo
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- JP3079717B2 JP3079717B2 JP03338501A JP33850191A JP3079717B2 JP 3079717 B2 JP3079717 B2 JP 3079717B2 JP 03338501 A JP03338501 A JP 03338501A JP 33850191 A JP33850191 A JP 33850191A JP 3079717 B2 JP3079717 B2 JP 3079717B2
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- molecular weight
- acid
- component
- polyester
- aliphatic polyester
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、成形品を始め各種用途
に利用可能な、高分子量脂肪族ポリエステルの製造方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a high molecular weight aliphatic polyester, which can be used for various uses including molded articles.
【０００２】従来、脂肪族ポリエステルは、その熱安定
性が不十分であることから、分子量(数平均、以下同様)
は約１５，０００程度が限界で、それ以上に高めること
は、分子量を高めるエステル化、脱グリコールの諸反応
よりも熱分解による分子量低下反応が優先して、かえっ
て分子量の低下が起ることが知られており、頗る困難で
あると思われていた。また、従来の方法で得られる前記
した程度の分子量を有する脂肪族ポリエステルでは、実
用性のある物性を示さず、例えば強度面一つをとってみ
ても、実用に耐え得るものはまったく得られない。[0002] Conventionally, aliphatic polyesters have a low molecular weight (number average, hereinafter the same) because of insufficient heat stability.
The limit is about 15,000. If the molecular weight is increased further, the molecular weight reduction reaction due to thermal decomposition takes precedence over the esterification and deglycolization reactions that increase the molecular weight, and the molecular weight may rather decrease. Known and thought to be very difficult. In addition, aliphatic polyesters having a molecular weight of the above-described degree obtained by a conventional method do not exhibit practical physical properties. .
【０００３】[0003]
【発明が解決しようとする課題】本発明は、脂肪族ポリ
エステルの分子量を増大させて実用上十分な物性を有す
る高分子量脂肪族ポリエステルの製造方法を提供するこ
とを目的とする。An object of the present invention is to provide a method for producing a high molecular weight aliphatic polyester having practically sufficient physical properties by increasing the molecular weight of the aliphatic polyester.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、分子量を
極力高めて、脂肪族ポリエステルに実用性のある性質を
与えるべく研究を重ねた結果、グリコール成分とジカル
ボン酸（またはその酸無水物）成分だけからでは、触媒
として有機チタン化合物または他の金属化合物、または
これらを併用しても目的を達成することは頗る困難であ
ることを再確認した。結局、本発明者らが見出した従来
の方法では達成困難な分子量２０，０００以上のポリエ
ステルを得る方法は、３官能のオキシカルボン酸成分を
反応系に加えることが有効であり、上記目的を達成でき
ることを見出した。この３官能のオキシカルボン酸成分
を有機チタン化合物触媒と共に、グリコール成分並びに
脂肪族(環状脂肪族を含む)ジカルボン酸(またはその酸
無水物)との反応系に併用すると、エステル化、脱グリ
コール反応により、ゲル化をみることなく、容易に分子
量２０，０００以上、３０，０００程度に迄高めること
が可能であることを見出し、本発明を完成するに至っ
た。Means for Solving the Problems The inventors of the present invention have conducted studies to increase the molecular weight as much as possible and to give practical properties to aliphatic polyesters. As a result, the glycol component and the dicarboxylic acid (or an acid anhydride thereof) are obtained. It has been reconfirmed that it is extremely difficult to achieve the object by using the organotitanium compound or other metal compound as a catalyst, or a combination thereof, only from the component (1). As a result, the method of obtaining a polyester having a molecular weight of 20,000 or more, which is difficult to achieve by the conventional method found by the present inventors, is effective by adding a trifunctional oxycarboxylic acid component to the reaction system, and achieves the above object. I found what I could do. When this trifunctional oxycarboxylic acid component is used together with an organic titanium compound catalyst in a reaction system with a glycol component and an aliphatic (including cycloaliphatic) dicarboxylic acid (or an acid anhydride thereof), an esterification and a deglycolization reaction are caused. As a result, the inventors have found that the molecular weight can be easily increased to 20,000 or more and about 30,000 without gelation, and the present invention has been completed.
【０００５】即ち、本発明は、(１)グリコール成分、
(２)脂肪族(環状脂肪族を含む)ジカルボン酸(またはそ
の酸無水物)成分、(３)３官能のオキシカルボン酸成分
および(４)有機チタン化合物 を併用することよりなる高分子量脂肪族ポリエステルの
製造方法に関する。That is, the present invention provides (1) a glycol component,
(2) aliphatic (including cycloaliphatic) dicarboxylic acid (or anhydride thereof) component, (3) trifunctional oxycarboxylic acid component and (4) high molecular weight aliphatic obtained by using an organic titanium compound in combination The present invention relates to a method for producing a polyester.
【０００６】本発明を特徴づける３官能のオキシカルボ
ン酸成分は、（ｉ）カルボキシル基が２個とヒドロキシ
ル基が１個、（ii）カルボキシル基が１個とヒドロキシ
ル基が２個、を各々分子中に有するタイプとに分れる
が、実用的には、市販品が容易に、且つ低コストで入手
可能といった点から、（ｉ）の同一分子中に２個のカル
ボキシル基と１個のヒドロキシル基とを共有する下式の
リンゴ酸The trifunctional oxycarboxylic acid component characterizing the present invention comprises (i) two carboxyl groups and one hydroxyl group, and (ii) one carboxyl group and two hydroxyl groups, respectively. In practical terms, two carboxyl groups and one hydroxyl group in the same molecule of (i) are practically commercially available because they are easily available at low cost. And share the following formula malic acid
【化１】 が有利であり、本発明の目的には十分である。Embedded image Is advantageous and sufficient for the purposes of the present invention.
【０００７】３官能のオキシカルボン酸成分の使用割合
はグリコール成分または脂肪族（環状脂肪族を含む）ジ
カルボン酸（またはその酸無水物）成分１００モル％に
対して、０．５〜５モル％、望ましくは０．８〜３モル
％が好ましい。３官能のオキシカルボン酸成分の使用割
合が５モル％より多い場合には、反応中にゲル化する危
険性が著しく増大する。また、０．５モル％未満では、
実際問題として併用の効果が現れない。但し、例として
リンゴ酸の併用のみでは、分子量を目的迄高めることは
できない。有機チタン化合物を脱グリコール反応の触媒
に併用しなければ、２０，０００以上の分子量をもつ高
分子量脂肪族ポリエステルを安全に合成することは不可
能である。The proportion of the trifunctional oxycarboxylic acid component used is 0.5 to 5 mol% with respect to 100 mol% of the glycol component or the aliphatic (including cycloaliphatic) dicarboxylic acid (or acid anhydride) component. And desirably 0.8 to 3 mol%. When the use ratio of the trifunctional oxycarboxylic acid component is more than 5 mol%, the risk of gelling during the reaction is significantly increased. Also, if it is less than 0.5 mol%,
As a practical matter, the effect of the combination is not exhibited. However, the molecular weight cannot be increased to the intended purpose only by using malic acid alone. Unless an organic titanium compound is used in combination with a catalyst for the deglycolization reaction, it is impossible to safely synthesize a high-molecular-weight aliphatic polyester having a molecular weight of 20,000 or more.
【０００８】触媒として有用な有機チタン化合物は、テ
トラアルコキシチタン化合物、並びにチタンのオキシア
セチルアセトネートである。一般式で示せば テトラアルコキシチタン化合物[0008] Organotitanium compounds useful as catalysts are tetraalkoxytitanium compounds, as well as titanium oxyacetylacetonates. In general formula, tetraalkoxy titanium compound
【化２】Ｔｉ（ＯＲ）4 （但し、式中、Ｒはアルキル基またはアリル基であ
る。）上記一般式において、Ｒはイソプロピル基、ブチ
ル基の場合が最も一般的である。チタンのオキシアセチ
ルアセトネートは下式## STR2 ## Ti (OR) 4 (In the formula, R is an alkyl group or an allyl group.) In the general formulas, R is an isopropyl group, is the case of the butyl group is the most common. The oxyacetylacetonate of titanium is
【化３】 で示される。Embedded image Indicated by
【０００９】有機チタン化合物の使用量は、ポリエステ
ル１００重量部当り金属チタン量として１ppm以上２，
０００ppm以下、望ましくは１０ppm以上１，０００ppm
以下であることが好ましい。有機チタン化合物の使用量
が１ppm未満では、触媒効果が著しく低減し、２,０００
ppm を超える使用量では触媒作用に変化は認められない
が、着色の原因ともなりかえって不利となる。有機チタ
ン化合物の添加は、エステル化の当初からか、または脱
グリコール反応前に加えても良い。The amount of the organic titanium compound to be used is 1 ppm or more in terms of the amount of metallic titanium per 100 parts by weight of the polyester.
000 ppm or less, desirably 10 ppm or more and 1,000 ppm
The following is preferred. When the amount of the organic titanium compound is less than 1 ppm, the catalytic effect is remarkably reduced, and 2,000
If the amount used exceeds ppm, no change in the catalytic action is observed, but it is disadvantageous because it causes coloring. The organic titanium compound may be added from the beginning of the esterification or before the deglycolization reaction.
【００１０】本発明に用いられるグリコール成分は特に
制限を加える必要はなく、例えば次の種類があげられ
る。エチレングリコール、プロピレングリコール、ブタ
ンジオール１，３、ブタンジオール１,４、３−メチル
プロパンジオール１,３、ネオペンチルグリコール、ジ
エチレングリコール、ジプロピレングリコール、３−メ
チルペンタンジオール１，５、ヘキサンジオール１，
６、１，４−シクロヘキサンジメタノール、水素化ビス
フェノールＡ、ビスフェノールＡエチレンオキシド付加
物（各１モル付加体）。The glycol component used in the present invention does not need to be particularly limited, and examples thereof include the following types. Ethylene glycol, propylene glycol, butanediol 1,3, butanediol 1,4, 3-methylpropanediol 1,3, neopentyl glycol, diethylene glycol, dipropylene glycol, 3-methylpentanediol 1,5, hexanediol 1,
6,1,4-cyclohexanedimethanol, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct (each 1 mol adduct).
【００１１】これらグリコール成分と反応してポリエス
テルを形成させるための脂肪族（環状脂肪族を含む）ジ
カルボン酸(またはその酸無水物)成分としては、例えば
コハク酸(または無水コハク酸、以下酸無水物は省略)、
アジピン酸、スベリン酸、アゼライン酸、セバシン酸、
ドデカン酸、テトラヒドロ無水フタル酸、ヘキサヒドロ
無水フタル酸があげられる。用途、例えば生分解性成形
品を妨げない範囲で、テレフタル酸、イソフタル酸など
の芳香族ジカルボン酸を併用することは妨げない。また
エチレンオキシド、プロピレンオキシドのようなモノア
ルキレンエポキシドをグリコール成分に替えて用いるこ
ともできる。The aliphatic (including cycloaliphatic) dicarboxylic acid (or acid anhydride) component for reacting with the glycol component to form a polyester includes, for example, succinic acid (or succinic anhydride, hereinafter referred to as acid anhydride). Things are omitted),
Adipic acid, suberic acid, azelaic acid, sebacic acid,
Dodecanoic acid, tetrahydrophthalic anhydride and hexahydrophthalic anhydride. Use of aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid will not be hindered as long as they do not hinder applications, for example, biodegradable molded articles. Further, a monoalkylene epoxide such as ethylene oxide or propylene oxide can be used instead of the glycol component.
【００１２】本発明の高分子量脂肪族ポリエステルは、
実用に当って、補強材、フィラー、着色剤、離型剤など
を必要に応じ併用可能なことは勿論である。The high molecular weight aliphatic polyester of the present invention comprises
In practical use, a reinforcing material, a filler, a coloring agent, a release agent, and the like can be used in combination as needed.
【００１３】[0013]
【実施例】次に本発明の理解を助けるために、以下に実
施例を示す。なお、実施例および比較例中の分子量の測
定は、Ｓｈｏｄｅｘ ＧＰＣ ＳＹＳＴＥＭ−１１，溶
離液ＣＦ3ＣＯＯＮａ，５mmol/ＨＦＩＰ（１ｌ），カラ
ム温度４０℃，流量１．０ml/min，検出器Ｓｈｏｄｅｘ
ＲＩで行った。EXAMPLES Next, examples will be shown below to facilitate understanding of the present invention. The molecular weights in Examples and Comparative Examples were measured by using Shodex GPC SYSTEM-11, eluent CF 3 COONa, 5 mmol / HFIP (1 liter), column temperature 40 ° C., flow rate 1.0 ml / min, and detector Shodex.
Performed at RI.
【００１４】実施例１ 撹拌機、分溜コンデンサー、温度計、ガス導入管を付し
た１ｌのセパラブルフラスコに、エチレングリコール２
０５g、コハク酸３５４g、リンゴ酸８g(２モル％)、テ
トライソプロピルチタネート０．０６ｇ(金属チタンと
して約３０ppm)を仕込み、窒素ガス気流中、２００〜２
０５℃でエステル化して酸価５．６、分子量５，６００
のポリエステルを合成した後、０．７〜０．５Torrの減
圧下、２００℃で脱グリコール反応を３時間行った所、
分子量２９，２００のポリエステル（Ａ）が、白色ワッ
クス状、融点９７℃で得られた。Example 1 A 1-liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer and a gas inlet tube was charged with ethylene glycol 2
05 g, succinic acid 354 g, malic acid 8 g (2 mol%), tetraisopropyl titanate 0.06 g (about 30 ppm as titanium metal) were charged, and 200 to 2 g in a nitrogen gas stream.
Esterified at 05 ° C, acid value 5.6, molecular weight 5,600
After synthesizing the polyester, a glycol removal reaction was performed at 200 ° C. for 3 hours under a reduced pressure of 0.7 to 0.5 Torr.
Polyester (A) having a molecular weight of 29,200 was obtained as a white wax having a melting point of 97 ° C.
【００１５】比較例１ チタン触媒を使用しない他は実施例１と同一配合、同一
製造条件で製造したポリエステル（Ｂ）は分子量が７，
８００であった。Comparative Example 1 A polyester (B) produced under the same composition and under the same production conditions as in Example 1 except that no titanium catalyst was used, had a molecular weight of 7,
800.
【００１６】比較例２ リンゴ酸を加えない他は実施例１と同一条件で製造した
ポリエステル（Ｃ）の分子量は１５，３００に止まっ
た。Comparative Example 2 The molecular weight of the polyester (C) produced under the same conditions as in Example 1 except that malic acid was not added was only 15,300.
【００１７】実施例２ 撹拌機、分溜コンデンサー、温度計、ガス導入管を付し
た１ｌのセパラブルフラスコに、ブタンジオール１，４
を２００g、コハク酸１８９g、アジピン酸５８g、リン
ゴ酸４．５g(１．５モル％)、チタンオキシアセチルア
セトネート０．０５g(金属チタンとして約１８ppm)を仕
込み、２０５〜２２０℃、窒素気流中エステル化して酸
価９．４、分子量６，９００とした後、２１５〜２２０
℃、０．５〜０．６Torrの減圧下、４時間脱グリコール
反応を行った所、分子量３２，０００のポリエステル
（Ｄ）が、白色ワックス状、融点約９０℃で得られた。Example 2 In a 1-liter separable flask equipped with a stirrer, a fractionating condenser, a thermometer and a gas inlet tube, butanediol 1,4 was added.
200 g, 189 g of succinic acid, 58 g of adipic acid, 4.5 g (1.5 mol%) of malic acid, 0.05 g of titanium oxyacetylacetonate (about 18 ppm as titanium metal), at 205 to 220 ° C. in a nitrogen stream. After esterification to an acid value of 9.4 and a molecular weight of 6,900, 215 to 220
A deglycol reaction was performed for 4 hours under a reduced pressure of 0.5 to 0.6 Torr at a temperature of 0 ° C., and a polyester (D) having a molecular weight of 32,000 was obtained as a white wax having a melting point of about 90 ° C.
【００１８】比較例３ チタン触媒を使用しない他は実施例２と同一配合、製造
条件で合成したポリエステル（Ｅ）は、分子量７，９０
０に止まった。Comparative Example 3 A polyester (E) synthesized under the same blending and production conditions as in Example 2 except that no titanium catalyst was used, had a molecular weight of 7,90.
Stopped at zero.
【００１９】比較例４ リンゴ酸を加えない他は実施例２と同一条件で製造した
ポリエステル（Ｆ）の分子量は１３，９００に止まっ
た。Comparative Example 4 The molecular weight of the polyester (F) produced under the same conditions as in Example 2 except that malic acid was not added was only 13,900.
【００２０】実施例３ 撹拌機、分溜コンデンサー、温度計、ガス導入管を付し
た１ｌのセパラブルフラスコに、１，４−シクロヘキサ
ンジメタノール（米国イーストマンケミカル社製）を３
００g、ドデカン酸４６０g、リンゴ酸９g(約３モル
％）、テトラブチルチタン０．０７g(金属チタンとして
約１５ppm)を仕込み、２１０〜２１５℃、窒素気流中で
エステル化して酸価７.８、分子量７,９００とした後、
０.５〜０.６Torrの減圧下、２２０〜２２５℃で脱グリ
コール反応を６時間行った。分子量２８，８００のポリ
エステル（Ｇ）が淡アイボリー色ワックス状、融点約７
２℃で得られた。Example 3 In a 1-liter separable flask equipped with a stirrer, a distillation condenser, a thermometer and a gas inlet tube, 1,4-cyclohexanedimethanol (manufactured by Eastman Chemical Co., USA) was charged.
00g, 460 g of dodecanoic acid, 9 g of malic acid (about 3 mol%), and 0.07 g of tetrabutyl titanium (about 15 ppm as metal titanium) were esterified in a nitrogen stream at 210 to 215 ° C. to give an acid value of 7.8. After having a molecular weight of 7,900,
The glycol removal reaction was performed at 220 to 225 ° C. for 6 hours under a reduced pressure of 0.5 to 0.6 Torr. Polyester (G) having a molecular weight of 28,800 is a pale ivory wax, melting point of about 7
Obtained at 2 ° C.
【００２１】比較例５ チタン触媒を使用しない他は実施例３と同一条件で反応
した場合に得られるポリエステル（Ｈ）の分子量は約
８，４００であった。Comparative Example 5 The molecular weight of the polyester (H) obtained when reacted under the same conditions as in Example 3 except that no titanium catalyst was used was about 8,400.
【００２２】比較例６ リンゴ酸を加えない他は実施例３と同一条件での反応条
件で得られたポリエステル（Ｉ）の分子量は１４，４０
０に止まった。Comparative Example 6 The molecular weight of the polyester (I) obtained under the same reaction conditions as in Example 3 except that malic acid was not added was 14,40.
Stopped at zero.
【００２３】[0023]
【発明の効果】本発明の製造方法によれば、成形品を始
め、各種の用途に有用な、高分子量脂肪族ポリエステル
が得られる。According to the production method of the present invention, a high molecular weight aliphatic polyester useful for various uses including a molded article can be obtained.
フロントページの続き (56)参考文献 特開 昭62−27424（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 63/00 - 63/91 Continuation of front page (56) References JP-A-62-27424 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08G 63/00-63/91
Claims (3)
の酸無水物)成分、 (３)３官能のオキシカルボン酸成分および (４)有機チタン化合物 を併用することよりなる高分子量脂肪族ポリエステルの
製造方法。1. A glycol component, (2) an aliphatic (including cycloaliphatic) dicarboxylic acid (or acid anhydride) component, (3) a trifunctional oxycarboxylic acid component, and (4) an organic titanium A method for producing a high molecular weight aliphatic polyester, which comprises using a compound in combination.
合が、グリコール成分または脂肪族（環状脂肪族を含
む）ジカルボン酸（またはその酸無水物）成分１００モ
ル％に対して、５モル％以下、０．５モル％以上であ
る、請求項１記載の高分子量脂肪族ポリエステルの製造
方法。2. The use ratio of the trifunctional oxycarboxylic acid component is 5 mol% or less based on 100 mol% of the glycol component or the aliphatic (including cycloaliphatic) dicarboxylic acid (or acid anhydride) component. The method for producing a high-molecular-weight aliphatic polyester according to claim 1, which is at least 0.5 mol%.
テル１００重量部当り金属チタンとして１ppm以上、
２，０００ppm以下である、請求項１または請求項２記
載の高分子量脂肪族ポリエステルの製造方法。3. The amount of the organic titanium compound used is 1 ppm or more as metallic titanium per 100 parts by weight of polyester,
The method for producing a high-molecular-weight aliphatic polyester according to claim 1 or 2, which is 2,000 ppm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03338501A JP3079717B2 (en) | 1991-12-20 | 1991-12-20 | Method for producing high molecular weight aliphatic polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03338501A JP3079717B2 (en) | 1991-12-20 | 1991-12-20 | Method for producing high molecular weight aliphatic polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05170885A JPH05170885A (en) | 1993-07-09 |
| JP3079717B2 true JP3079717B2 (en) | 2000-08-21 |
Family
ID=18318753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03338501A Expired - Fee Related JP3079717B2 (en) | 1991-12-20 | 1991-12-20 | Method for producing high molecular weight aliphatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3079717B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009075303A1 (en) | 2007-12-12 | 2009-06-18 | Mitsubishi Chemical Corporation | Aliphatic polyester resin and method for producing the same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105186A (en) * | 2000-10-03 | 2002-04-10 | Agency Of Ind Science & Technol | Method for producing high-molecular weight polybutylene succinate |
| EP1640397B1 (en) | 2003-05-21 | 2016-04-13 | Mitsubishi Chemical Corporation | Aliphatic polyester and process for production thereof |
| JP4635475B2 (en) * | 2003-05-21 | 2011-02-23 | 三菱化学株式会社 | Aliphatic polyester and method for producing the same |
| US7345137B2 (en) | 2004-10-18 | 2008-03-18 | 3M Innovative Properties Company | Modified copolyesters and optical films including modified copolyesters |
-
1991
- 1991-12-20 JP JP03338501A patent/JP3079717B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009075303A1 (en) | 2007-12-12 | 2009-06-18 | Mitsubishi Chemical Corporation | Aliphatic polyester resin and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05170885A (en) | 1993-07-09 |
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