JP4734626B2 - Catalyst for polyester synthesis - Google Patents
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- JP4734626B2 JP4734626B2 JP2005017437A JP2005017437A JP4734626B2 JP 4734626 B2 JP4734626 B2 JP 4734626B2 JP 2005017437 A JP2005017437 A JP 2005017437A JP 2005017437 A JP2005017437 A JP 2005017437A JP 4734626 B2 JP4734626 B2 JP 4734626B2
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本発明は、アルコールとカルボン酸からエステル化合物を、ジオールとジカルボン酸またはヒドロキシカルボン酸からポリエステルを合成するための触媒およびポリエステルの製法に関する。 The present invention relates to a catalyst for synthesizing an ester compound from an alcohol and a carboxylic acid, and a polyester for synthesizing a polyester from a diol and a dicarboxylic acid or a hydroxycarboxylic acid, and a method for producing the polyester.
一般にポリエステルの合成にはジカルボン酸とジオールまたはヒドロキシカルボン酸の直接重合法が採用されているが、非常に高温でエステル化をさせるのが一般的である。また、脂肪族のポリエステルは、耐熱性に劣り、熱分解してしまうこともある。より低温（２００℃以下）で反応させるためにはこの反応を効率よく触媒する触媒の検索が必須となるが、ほとんどのルイス酸触媒は、水をはじめとするプロトン性の化合物に対する安定性が非常に低く困難であった。 In general, a direct polymerization method of a dicarboxylic acid and a diol or a hydroxycarboxylic acid is employed for the synthesis of the polyester, but the esterification is generally performed at a very high temperature. In addition, aliphatic polyester is inferior in heat resistance and may be thermally decomposed. In order to react at a lower temperature (200 ° C or lower), it is essential to search for a catalyst that efficiently catalyzes this reaction. However, most Lewis acid catalysts are very stable against protic compounds such as water. It was difficult to lower.
近年、このような観点から触媒が開発され高分子量の脂肪族ポリエステルも製造されるにいたっている。たとえば、1,4-ブタンジオールとコハク酸等に触媒としてアセトアセトイル型亜鉛キレート化合物等を用いて脂肪族ポリエステルが合成され、市販されている（特開平5-3952、高分子42巻３月号251(1993)。この例では、一旦分子量が15000程度のポリエステルを合成し、これをジイソシアネートを用いて結合して分子量が、35000程度のポリマーを得ているが、この高分子量の脂肪族ポリエステルを直接作成するに至っておらず、反応温度も200℃程度と高い。更に、最近ではジオールとジカルボン酸にスズジスタノキサン（Biomacromolecules 2001, 2, 1267-1270）または、塩化ハフニウム・THF錯体（Science 2000, 290, 1140-1142）を用いて分子量が、1-10万程度の脂肪族ポリエステルが合成されるに至っている。しかし、いずれも有機溶媒を用いる溶液重縮合法であった。最近では、深刻化する環境問題を背景に、有機溶媒やスズなどの重金属触媒の使用に対する法的な規制が大きくなってきている。 In recent years, catalysts have been developed from this point of view, and high molecular weight aliphatic polyesters have also been produced. For example, an aliphatic polyester is synthesized using 1,4-butanediol and succinic acid as a catalyst using an acetoacetoyl type zinc chelate compound and the like, and is commercially available (Japanese Patent Laid-Open No. 5-3952, Polymer 42 vol. March). No. 251 (1993) In this example, a polyester having a molecular weight of about 15000 was once synthesized and bonded using diisocyanate to obtain a polymer having a molecular weight of about 35,000. The reaction temperature is as high as about 200 ° C. Recently, diol and dicarboxylic acid can be used together with tin distannoxane (Biomacromolecules 2001, 2, 1267-1270) or hafnium chloride / THF complex (Science). 2000, 290, 1140-1142) have been used to synthesize aliphatic polyesters with molecular weights of about 100,000 to 100. However, all were solution polycondensation methods using organic solvents. In the background of environmental problems serious, legal restrictions on the use of heavy metal catalysts such as organic solvents and tin has been increased.
発明者はすでに、希土類トリフラートがカルボン酸とアルコールのエステル化を触媒することを見出しており、溶媒を用いない塊状重合により８０℃の温度で高分子量と目される分子量１万のポリエステルを得ており、１８０℃では３万の分子量のポリエステルを合成している（高須昭則、平林忠道、特開2003-306535）。さらにその触媒は、有機溶媒（クロロホルム、テトラヒドロフラン、ヘキサン）と水を用いた洗浄により水層から回収することができた（A. Takasu et al., Macromolecules 2003, 1772-1774、A. Takasu et al., Macromolecules 2005, in press）。しかし、触媒を回収するためには、有機溶媒で希釈した後、繰り返し水で洗浄を行わないと高い回収率にならないという欠点があった。 The inventor has already found that the rare earth triflate catalyzes the esterification of carboxylic acid and alcohol, and obtained a polyester having a molecular weight of 10,000, which is regarded as having a high molecular weight at a temperature of 80 ° C., by bulk polymerization without using a solvent. Polyester having a molecular weight of 30,000 is synthesized at 180 ° C. (Akinori Takasu, Tadamichi Hirabayashi, JP 2003-306535). Furthermore, the catalyst could be recovered from the aqueous layer by washing with an organic solvent (chloroform, tetrahydrofuran, hexane) and water (A. Takasu et al., Macromolecules 2003, 1772-1774, A. Takasu et al. ., Macromolecules 2005, in press). However, in order to recover the catalyst, there is a disadvantage that a high recovery rate is not obtained unless the catalyst is diluted with an organic solvent and then repeatedly washed with water.
本発明は、ポリエステルを合成するための触媒であって、低温（約180℃以下）でポリエステル反応を触媒を作用し、更に分子量が1万以上のポリエステルを合成できる触媒を提供する。この触媒は、希土類トリフラートがポリスチレン樹脂に担持されているため、分液操作が必要なく回収操作が簡便である。それによって、工業的な応用範囲がより広がると考えられる。 The present invention provides a catalyst for synthesizing a polyester, which can catalyze a polyester reaction at a low temperature (about 180 ° C. or less) and can synthesize a polyester having a molecular weight of 10,000 or more. In this catalyst, since rare earth triflate is supported on a polystyrene resin, a separation operation is not necessary and a recovery operation is simple. Thereby, it is considered that the industrial application range is further expanded.
本発明者は、希土類トリフラートがジカルボン酸とジオールとの重縮合の有効な触媒となることから（高須昭則、平林忠道、特開2003-306535）、この触媒をポリスチレン樹脂に担時させたものを用いてエステル化を行った。まず、エタノールと2当量の酢酸の室温（２７℃）でのエステル化を検討したところ48時間で８０％進行した。次に、この触媒を用いたジオールとジカルボン酸との重縮合の場合も、120℃で重合が進行し、数平均分子量1万以上のポリエステルが合成できた。期待通り分液操作の必要なく、テトラヒドロフランにポリエステルを溶解させ、濾過するだけで触媒が回収でき本発明を完成させた。 The inventor of the present invention uses a rare earth triflate as an effective catalyst for polycondensation of a dicarboxylic acid and a diol (Akinori Takasu, Tadashi Hirabayashi, JP 2003-306535). Was used for esterification. First, when esterification of ethanol and 2 equivalents of acetic acid at room temperature (27 ° C.) was examined, 80% progressed in 48 hours. Next, also in the case of polycondensation of diol and dicarboxylic acid using this catalyst, polymerization proceeded at 120 ° C., and a polyester having a number average molecular weight of 10,000 or more could be synthesized. As expected, the catalyst could be recovered by simply dissolving the polyester in tetrahydrofuran and filtering without the need for a liquid separation operation, thus completing the present invention.
即ち、本発明は、ジオールとジカルボン酸またはヒドロキシカルボン酸からポリエステルを合成するための触媒であって、下式
That is, the present invention is a catalyst for synthesizing a polyester from a diol and a dicarboxylic acid or hydroxycarboxylic acid,
で表されるポリエステル合成触媒である。式中Xは希土類元素を表し、Ｘは希土類元素を表し、好ましくはＳｃ，Ｙ，ＹｂまたはＳｍを表す。Ｒはジビニルベンゼンを１％含むポリスチレン樹脂を表す。本発明の触媒はこれらの混合物であってもよい。この触媒は、ジビニルベンゼンを１％含むポリスチレン樹脂を二硫化炭素中で、塩化５−フェニル吉草酸で処理をし、Friedel-Craftsアシル化と還元反応を繰り返して調製した樹脂に、塩化スルホン酸で硫酸化を行い、塩化スカンジウムとトリフルオロメタンスルホン酸(TfOH)と反応させることで調製できる（Angew. Chem. Int. Ed. 2000, 39, 567）。 It is the polyester synthesis catalyst represented by these. In the formula, X represents a rare earth element, X represents a rare earth element, and preferably represents Sc, Y, Yb or Sm. R represents a polystyrene resin containing 1% of divinylbenzene. The catalyst of the present invention may be a mixture thereof. This catalyst was prepared by treating polystyrene resin containing 1% divinylbenzene with 5-phenylvaleric acid chloride in carbon disulfide and repeating Friedel-Crafts acylation and reduction reaction with sulfonic acid chloride. It can be prepared by sulfating and reacting with scandium chloride and trifluoromethanesulfonic acid (TfOH) (Angew. Chem. Int. Ed. 2000, 39, 567).
このポリエステルに用いるジオール、ジカルボン酸、ヒドロキシカルボン酸については特に制限がないが、エチレングリコール、１,４−ブタンジオール、１,６−へキサンジオール、デカメチレングリコール、ネオペンチルグリコール、１，４−シクロへキサンジメタノール、コハク酸、メチルコハク酸、アジピン酸、スベリン酸、セバシン酸、ドデカン酸、フタル酸などやこれらの無水物、例えば、無水コハク酸、無水アジピン酸を用いてもよい。また、乳酸、グリコール酸、リンゴ酸などを用いることも望ましい。また、複数種のこれらを用いてもよい。 The diol, dicarboxylic acid, and hydroxycarboxylic acid used in this polyester are not particularly limited, but ethylene glycol, 1,4-butanediol, 1,6-hexanediol, decamethylene glycol, neopentyl glycol, 1,4- Cyclohexane dimethanol, succinic acid, methyl succinic acid, adipic acid, suberic acid, sebacic acid, dodecanoic acid, phthalic acid, and the like, and anhydrides thereof such as succinic anhydride and adipic anhydride may be used. It is also desirable to use lactic acid, glycolic acid, malic acid or the like. Moreover, you may use multiple types of these.
本発明において合成されるポリエステルに特に制限はなく、合成されたポリマーまたは化合物に主結合として、本発明の触媒の作用により生成されたエステル結合が含まれておればよく、エステル結合以外の結合が含まれることを除外するものではない。このポリエステルは、上記のジオールとジカルボン酸またはヒドロキシカルボン酸により生成すれば、芳香族、脂肪族またはこれらの混合のいずれでもよい。このポリエステルの数平均分子量（Ｍｎ）は、実用的には５０００以上、特に１００００以上であることが望ましい。 The polyester synthesized in the present invention is not particularly limited, and the synthesized polymer or compound may contain an ester bond generated by the action of the catalyst of the present invention as a main bond. It does not exclude inclusion. This polyester may be aromatic, aliphatic, or a mixture thereof as long as it is produced from the above diol and dicarboxylic acid or hydroxycarboxylic acid. The number average molecular weight (Mn) of this polyester is preferably 5000 or more, particularly 10,000 or more practically.
また、本発明は、上記の触媒を用いて、ジオールとジカルボン酸またはヒドロキシカルボン酸からポリエステルを製造する方法である。前記触媒の使用量は、生成する樹脂（又は投入するジオールとジカルボン酸またはヒドロキシカルボン酸）に対して、０．００１−１５重量％、好ましくは０．０５−２重量％であることが望ましい。ジオールとジカルボン酸の投入量はほぼ化学量論比とすることが好ましい。重合においては、上記の成分以外に溶媒、酸化防止剤、紫外吸収剤、結晶核剤を適宜使用してもよい。 Moreover, this invention is a method of manufacturing polyester from diol and dicarboxylic acid or hydroxycarboxylic acid using said catalyst. The catalyst is used in an amount of 0.001 to 15% by weight, preferably 0.05 to 2% by weight, based on the resin to be produced (or diol and dicarboxylic acid or hydroxycarboxylic acid to be added). The input amount of diol and dicarboxylic acid is preferably approximately stoichiometric. In the polymerization, in addition to the above components, a solvent, an antioxidant, an ultraviolet absorber, and a crystal nucleating agent may be appropriately used.
本発明は、希土類トリフラートがジカルボン酸とジオールとの重縮合の有効な触媒となることから（高須昭則、平林忠道、特開2003-306535）、この触媒をポリスチレン樹脂に担時させたものを用いて重縮合を行ったところに特徴がある。この触媒を用いた場合も、120℃で重合が進行し、数平均分子量1万以上のポリエステルが合成できた。予想通り分液操作の必要なく、テトラヒドロフランにポリエステルを溶解させ、濾過するだけで触媒が回収できる点が特徴である。 In the present invention, since the rare earth triflate is an effective catalyst for polycondensation of dicarboxylic acid and diol (Akinori Takasu, Tadashi Hirabayashi, JP 2003-306535), a catalyst obtained by supporting this catalyst on a polystyrene resin is used. And is characterized by polycondensation. Even when this catalyst was used, polymerization proceeded at 120 ° C., and a polyester having a number average molecular weight of 10,000 or more could be synthesized. As expected, the catalyst can be recovered by dissolving polyester in tetrahydrofuran and filtering without the need for a liquid separation operation.
ジオールとジカルボン酸またはヒドロキシカルボン酸からポリエステルを合成する場合に、低温において高分子量のポリエステルを合成できる。ほとんどの触媒が、水、カルボン酸、アルコールなどのプロトン性化合物に不安定であるのに対し、この触媒の安定性は高く、溶媒を用いない塊状重合に適している。80-180℃の重合温度で高い触媒回転数を示した。前記触媒は、ポリスチレン樹脂に担時されており、重縮合後にテトラヒドロフランにポリエステルを溶解させ、濾過するだけで触媒が回収できた。 When a polyester is synthesized from a diol and a dicarboxylic acid or a hydroxycarboxylic acid, a high molecular weight polyester can be synthesized at a low temperature. While most catalysts are unstable to protic compounds such as water, carboxylic acids, and alcohols, this catalyst has high stability and is suitable for bulk polymerization without using a solvent. The catalyst rotation speed was high at the polymerization temperature of 80-180 ℃. The catalyst was supported by a polystyrene resin, and the catalyst could be recovered by simply dissolving the polyester in tetrahydrofuran after polycondensation and filtering.
本発明の触媒を用いて、ジオールとジカルボン酸またはヒドロキシカルボン酸からポリエステルを合成することができる。後述の実施例で明らかにするが、120℃の塊状重合で高分子量と目される1万2千の分子量のポリエステルを得ることができた。希土類金属は高価であるためその回収・再利用に企業化および実用化の課題が残されている。従来の水洗による方法では、手間がかかるとともに有機溶媒が水と混ざり、回収効率や廃液処理の問題が懸念されるが、本発明ではそれらが大きく改善できた。 Polyesters can be synthesized from diols and dicarboxylic acids or hydroxycarboxylic acids using the catalyst of the present invention. As will be clarified in Examples described later, a polyester having a molecular weight of 12,000, which is regarded as a high molecular weight, was obtained by bulk polymerization at 120 ° C. Since rare earth metals are expensive, there remains a problem of commercialization and practical use for their recovery and reuse. In the conventional water washing method, it takes time and the organic solvent is mixed with water, and there are concerns about the problems of recovery efficiency and waste liquid treatment. However, in the present invention, they can be greatly improved.
以上説明したように本発明の合成触媒は、Sc(OTf)3と同様アルコールとカルボン酸の反応を触媒し、ジオールとジカルボン酸からポリエステルを合成できた。樹脂に触媒が担持されているため分液操作の必要がなく、容易に回収・再利用できるようになった。
As described above, the synthesis catalyst of the present invention catalyzed the reaction between an alcohol and a carboxylic acid, similar to Sc (OTf) 3, and was able to synthesize a polyester from a diol and a dicarboxylic acid. Since the catalyst is supported on the resin, there is no need for a liquid separation operation, and it can be easily recovered and reused.
重合形式はいかなるものであってもいいが、本発明の触媒には溶媒を用いない塊状重合が適している。反応圧は、重合反応形式により当該分野で適切な圧を用いればよいが、塊状重合の場合には、脱水を促進するため0.3−3.0mmHgが好ましい。反応温度は、やはり高いほどエステル化反応の進行度は高いが、本発明の触媒を用いることにより一般（２００℃以上）よりも低い約１８０℃以下、特に８０−１８０℃で行うことができる点が本発明の特徴のひとつであると考えられる。 Any type of polymerization may be used, but bulk polymerization without using a solvent is suitable for the catalyst of the present invention. The reaction pressure may be an appropriate pressure in the field depending on the polymerization reaction mode, but in the case of bulk polymerization, 0.3 to 3.0 mmHg is preferable in order to promote dehydration. The higher the reaction temperature is, the higher the degree of progress of the esterification reaction is. However, by using the catalyst of the present invention, it can be carried out at about 180 ° C. or lower, particularly 80-180 ° C., lower than general (200 ° C. or higher). Is considered to be one of the features of the present invention.
以下、実施例にて本発明を例証するが、本発明を例証するが、本発明を限定することを意図するものではない。 The following examples illustrate the invention, but illustrate the invention but are not intended to limit the invention.
本実施例では、ジオールとしてエチレングリコール（ナカライテスク製、「EG」と略す。）1,3-プロパンジオール（東京化成、「1,3-PD」と略す。）、1,4-ブタンジオール（東京化成、「1,4-BD」と略す。）を用い、ジカルボン酸としてメチルコハク酸（アルドリッチ製、「MSA」と略す。）、コハク酸（ナカライテスク製、「SA」と略す。）、または無水メチルコハク酸（メチルコハク酸と無水酢酸から調製、「MSAn」と略す。）、無水コハク酸（ナカライテスク製、「SAn」と略す。）、ヒドロキシカルボン酸としては乳酸（アルドリッチ製）およびグリコール酸（アルドリッチ製）を用いた。触媒としてはポリスチレン樹脂担持型スカンジウムトリフラート(アルドリッチ製、「PS-Sc」と略す。）を用いた。 In this example, ethylene glycol (manufactured by Nacalai Tesque, abbreviated as “EG”) 1,3-propanediol (Tokyo Chemical Industry, abbreviated as “1,3-PD”), 1,4-butanediol (as diol) Tokyo Chemicals, abbreviated as “1,4-BD”), and methyl succinic acid (made by Aldrich, abbreviated as “MSA”), succinic acid (made by Nacalai Tesque, abbreviated as “SA”) as a dicarboxylic acid, or Methyl succinic anhydride (prepared from methyl succinic acid and acetic anhydride, abbreviated as “MSAn”), succinic anhydride (manufactured by Nacalai Tesque, abbreviated as “SAn”), hydroxycarboxylic acids such as lactic acid (Aldrich) and glycolic acid ( Aldrich) was used. As the catalyst, polystyrene resin-supported scandium triflate (manufactured by Aldrich, abbreviated as “PS-Sc”) was used.
撹拌機、分留コンデンサ、温度計、ガス封入管を備えた容積が５０mＬのナスフラスコに、表１に示す量のジオール、ジカルボン酸および触媒を入れ、窒素雰囲気下、7.0ミリモルずつ用いた。また、系を減圧（0.3mmHg）しつつ生成する水分を除去した。その結果、白色ワックス状の重合体が得られた。これをテトラヒドロフラン（40mL）で溶解、濾過することでPS-Scを回収した(回収率：98％) The amount of diol, dicarboxylic acid and catalyst shown in Table 1 was put into a 50 mL eggplant flask equipped with a stirrer, fractional condenser, thermometer and gas-sealed tube, and 7.0 mmol was used in a nitrogen atmosphere. Moreover, the water | moisture content produced | generated was removed, decompressing the system (0.3 mmHg). As a result, a white wax-like polymer was obtained. PS-Sc was recovered by dissolving this in tetrahydrofuran (40 mL) and filtering (recovery rate: 98%).
この結果、反応温度が高いほど分子量の大きいポリエステルが得られており、１２０℃において0.3 mmHgの減圧下で、1,4-ブタンジオールとメチルコハク酸との直接重縮合を２４時間行うことにより、分子量分子量１万以上のポリエステルを合成することができた。また、この触媒はエステル交換反応よりもカルボン酸とアルコールの縮合反応に対し、高い触媒作用を示すため、分子量分布(Mw/Mn)が１．５−１．９と狭くなることも本発明の特徴である。
As a result, a polyester having a higher molecular weight was obtained as the reaction temperature was higher. By performing direct polycondensation of 1,4-butanediol and methylsuccinic acid at 120 ° C. under a reduced pressure of 0.3 mmHg for 24 hours, a molecular weight was obtained. A polyester having a molecular weight of 10,000 or more could be synthesized. In addition, since this catalyst exhibits a higher catalytic action for the condensation reaction of carboxylic acid and alcohol than the transesterification reaction, the molecular weight distribution (Mw / Mn) is narrowed to 1.5-1.9. It is a feature.
Claims (4)
The polyester according to claim 3, wherein the diol is represented by HO (CH 2 ) n OH (n is arbitrary), and the dicarboxylic acid is represented by HOOC (CH 2 ) n COOH (n is arbitrary) or an anhydride thereof. Catalyst for synthesis.
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| JP5256498B2 (en) * | 2009-05-08 | 2013-08-07 | 国立大学法人名古屋大学 | Polymer ligand, aluminum complex and method for producing polylactide |
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| JP2003306535A (en) * | 2002-04-16 | 2003-10-31 | Japan Science & Technology Corp | Catalyst for synthesis of polyester |
| JP2003313282A (en) * | 2002-04-19 | 2003-11-06 | National Institute Of Advanced Industrial & Technology | Method for manufacturing polyester by rare earth metal compound catalyst |
| JP2006047536A (en) * | 2004-08-03 | 2006-02-16 | Fuji Xerox Co Ltd | Electrophotographic toner and manufacturing method thereof, polyester resin for electrophotographic toner and manufacturing method thereof, electrophotographic developer and image forming method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003306535A (en) * | 2002-04-16 | 2003-10-31 | Japan Science & Technology Corp | Catalyst for synthesis of polyester |
| JP2003313282A (en) * | 2002-04-19 | 2003-11-06 | National Institute Of Advanced Industrial & Technology | Method for manufacturing polyester by rare earth metal compound catalyst |
| JP2006047536A (en) * | 2004-08-03 | 2006-02-16 | Fuji Xerox Co Ltd | Electrophotographic toner and manufacturing method thereof, polyester resin for electrophotographic toner and manufacturing method thereof, electrophotographic developer and image forming method |
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