JP6840019B2 - Polyester and its manufacturing method - Google Patents
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Description
本発明はポリエステルおよびその製造方法に関する。 The present invention relates to polyester and a method for producing the same.
汎用ポリエステル樹脂であるポリエチレンテレフタレート（ＰＥＴ）は、低コストでありながら耐熱性、耐薬品性、耐溶剤性、透明性などに優れるとされている。骨格中にナフタレン環を有するポリエチレンナフタレート（ＰＥＮ）はさらに耐熱性、耐薬品性、耐衝撃性などの特性が高い。しかし、ＰＥＮであっても耐熱性が不足するような用途も存在し、そのような用途にはエンプラ、スーパーエンプラが用いられている。その一例として、医療容器が挙げられる。医療現場では加熱による滅菌が主流であるが、オートクレーブを用いた高温高圧水蒸気滅菌では１３４℃の温度に耐える必要がある。汎用ポリエステルの改質で耐熱性を高め、オートクレーブ滅菌にも耐えうるようなポリマーが得られれば高コストのエンプラ、スーパーエンプラに置き換わることが期待できる。 Polyethylene terephthalate (PET), which is a general-purpose polyester resin, is said to be excellent in heat resistance, chemical resistance, solvent resistance, transparency, etc. at a low cost. Polyethylene naphthalate (PEN), which has a naphthalene ring in its skeleton, has higher properties such as heat resistance, chemical resistance, and impact resistance. However, there are some applications in which heat resistance is insufficient even for PEN, and engineering plastics and super engineering plastics are used for such applications. One example is a medical container. In medical practice, sterilization by heating is the mainstream, but high-temperature and high-pressure steam sterilization using an autoclave needs to withstand a temperature of 134 ° C. If a polymer that can withstand autoclave sterilization by improving heat resistance by modifying general-purpose polyester can be obtained, it can be expected to replace high-cost engineering plastics and super engineering plastics.
一方、ポリエチレンナフタレートの共重合成分としてイソソルビド成分を用いることが知られている（特許文献１、２）。しかしながら、これらの文献はイソソルビド成分を少量使用したものであり、高度な耐熱性については記載されていない。 On the other hand, it is known that an isosorbide component is used as a copolymerization component of polyethylene naphthalate (Patent Documents 1 and 2). However, these documents use a small amount of isosorbide component and do not describe high heat resistance.
本発明の目的は、汎用ポリエステルの耐熱性、すなわちガラス転移点を向上させた高耐熱ポリエステルおよびその製造方法を提供することである。 An object of the present invention is to provide a highly heat-resistant polyester having improved heat resistance of a general-purpose polyester, that is, a glass transition point, and a method for producing the same.
本発明者らは、剛直な骨格を有するジオールであるイソソルビドをＰＥＮに共重合することで耐熱性を向上させる、特に酸成分であるナフタレンジカルボン酸に対して３５モル％以上含有させることで、高いガラス転移点を有するポリエステルを得られることを見出した。これまでにもイソソルビドを共重合したポリエステルの報告は存在しているが、ＰＥＴ共重合であるためガラス転移点が１２０℃未満であるか、２０モル％を超えるような高い存在比で共重合させた報告例が存在していない。そのため、イソソルビド共重合ＰＥＮによる耐熱ポリエステルには検討の余地があり、高い耐熱性を有するポリエステルを合成することが期待できる。 The present inventors improve the heat resistance by copolymerizing isosorbide, which is a diol having a rigid skeleton, with PEN, and particularly by containing 35 mol% or more of the acid component naphthalenedicarboxylic acid. It has been found that a polyester having a glass transition point can be obtained. There have been reports of polyesters copolymerized with isosorbide, but since they are PET copolymerized, they are copolymerized at a high abundance ratio such that the glass transition point is less than 120 ° C. or more than 20 mol%. There are no reported cases. Therefore, there is room for study on heat-resistant polyesters made from isosorbide copolymerized PEN, and it can be expected that polyesters having high heat resistance will be synthesized.
本発明によれば、発明の課題は下記発明により達成される。 According to the present invention, the subject of the invention is achieved by the following invention.
１．ジカルボン酸成分由来の構成単位中、２，６−ナフタレンジカルボン酸由来の構成
単位を９５〜１００モル％を含み、ジオール成分由来の構成単位中、イソソルビド由来の構成単位を３５〜１００モル％含む、固有粘度が０．４０〜０．７５ｄｌ／ｇの範囲であり、且つ非架橋であるポリエステル。
２．ガラス転移点が１５０℃以上である、前項１に記載のポリエステル。
３．ジカルボン酸成分由来の構成単位中、２，６−ナフタレンジカルボン酸由来の構成単位を９５〜１００モル％、テレフタル酸および／またはイソフタル酸由来の構成単位を０〜５モル％含む前項１または２に記載のポリエステル。
４．ジオール成分由来の構成単位中、イソソルビド由来の構成単位を３５〜１００モル％、炭素原子数２〜４のアルキレングリコール由来の構成単位を０〜６５モル％含む前項１〜３のいずれか１項に記載のポリエステル。
５．Ｔｉを７５ｐｐｍ以上含有し、Ｐを５０ｐｐｍ以上含有する前項１〜４のいずれか１項に記載のポリエステル。
６．２，６−ナフタレンジカルボン酸を９５〜１００モル％を含むジカルボン酸成分と、イソソルビドを３５〜１００モル％含むジオール成分とを、エステル化反応もしくはエステル交換反応させた後、触媒としてトリメリット酸チタンを用いて重縮合反応を行う前項１記載のポリエステルの製造方法。
1. 1. The structural unit derived from the dicarboxylic acid component contains 95 to 100 mol% of the structural unit derived from 2,6-naphthalenedicarboxylic acid, and the structural unit derived from the diol component contains 35 to 100 mol% of the structural unit derived from isosorbide . A polyester having an intrinsic viscosity in the range of 0.40 to 0.75 dl / g and which is non-crosslinked .
2. 2. The polyester according to item 1 above, wherein the glass transition point is 150 ° C. or higher.
3. 3. During constitutional unit derived from dicarboxylic acid component, 2,6-naphthalene 95 to 100 mol% of constitutional unit derived from dicarboxylic acid, claim 1 or 2 before, including a constitutional unit derived from terephthalic acid and / or isophthalic acid 0-5 mol% The polyester described in.
4. During constitutional unit derived from a diol component, 35 to 100 mol% of constitutional unit derived from isosorbide, any one of claim 1 to 3 before containing 0-65 mol% of constitutional unit derived from an alkylene glycol having 2 to 4 carbon atoms The polyester described in.
5. Containing Ti or 75 ppm, the polyester according to any one of claim 1 to 4 before containing P or 50 ppm.
After a dicarboxylic acid component containing 95 to 100 mol% of 6.2,6-naphthalenedicarboxylic acid and a diol component containing 35 to 100 mol% of isosorbide are subjected to an esterification reaction or a transesterification reaction, trimellitic acid is used as a catalyst. process for producing a polyester of the previous claim 1, wherein performing the polycondensation reaction with an acid titanium.
ガラス転移点１５０℃以上とオートクレーブ処理にも耐えうる高耐熱ポリエステルを得られる。また、そのガラス転移点はポリエステル中に含まれるイソソルビド含有量に対して線型に変化することが確認できたため、容易に所望の耐熱性を有するポリエステルの合成が可能となった。 A highly heat-resistant polyester having a glass transition point of 150 ° C. or higher and capable of withstanding autoclaving can be obtained. Further, since it was confirmed that the glass transition point changes linearly with respect to the isosorbide content contained in the polyester, it became possible to easily synthesize a polyester having a desired heat resistance.
以下、本発明を詳細に説明する。
＜ポリエステル＞
本発明におけるポリエステルとは、ジカルボン酸成分由来の構成単位中、ナフタレンジカルボン酸由来の成分を９５〜１００モル％を含み、ジオール成分由来の構成単位中、イソソルビド由来の成分を３５〜１００モル％含むポリエステルである。
Hereinafter, the present invention will be described in detail.
<Polyester>
The polyester in the present invention contains 95 to 100 mol% of a component derived from naphthalene carboxylic acid in a constituent unit derived from a dicarboxylic acid component, and 35 to 100 mol% of a component derived from isosorbide in a constituent unit derived from a diol component. It is polyester.
ジカルボン酸成分由来の構成単位中、ナフタレンジカルボン酸を９７〜１００モル％を含むことが好ましく、実質的に１００モル％含むことが好ましい。ナフタレンジカルボン酸としては、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸が挙げられ、２，６−ナフタレンジカルボン酸が好ましい。 Among the structural units derived from the dicarboxylic acid component, it is preferable to contain 97 to 100 mol% of naphthalene carboxylic acid, and it is preferable to contain substantially 100 mol%. Examples of the naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is preferable.
他の酸成分としては、テレフタル酸、イソフタル酸，ジフェニルケトンジカルボン酸，アンスラセンジカルボン酸などを挙げることができ、テレフタル酸、イソフタル酸が好ましい。他の酸成分は０〜５モル％を含み、０〜３モル％を含むことが好ましい。 Examples of other acid components include terephthalic acid, isophthalic acid, diphenylketonedicarboxylic acid, anthracendicarboxylic acid and the like, and terephthalic acid and isophthalic acid are preferable. The other acid component contains 0 to 5 mol%, preferably 0 to 3 mol%.
ジオール成分由来の構成単位中、イソソルビドを４３〜１００モル％含むことが好ましい。他のジオール成分として炭素原子数２〜４のアルキレングリコールが好ましい。具体的なアルキレングリコールとしては、エチレングリコール、トリメチレングリコール、テトラメチレングリコールを挙げられ、なかでもエチレングリコールが特に好ましい。他のジオール成分は０〜６５モル％を含み、０〜５７モル％を含むことが好ましい。 It is preferable to contain 43 to 100 mol% of isosorbide in the structural unit derived from the diol component. As another diol component, an alkylene glycol having 2 to 4 carbon atoms is preferable. Specific examples of the alkylene glycol include ethylene glycol, trimethylene glycol, and tetramethylene glycol, and ethylene glycol is particularly preferable. The other diol component contains 0 to 65 mol%, preferably 0 to 57 mol%.
本発明のポリエステルのガラス転移点は１５０℃以上であることが好ましく、１６０℃以上であることがさらに好ましい。ガラス転移点が上記温度以上であれば、耐熱性の点で好ましい。なお、ガラス転移点の上限は限定されないが、３２０℃以下が好ましく、３００℃以下がより好ましい。ガラス転移点が上記温度以下であれば、成形時の取り扱い性の点で好ましい。 The glass transition point of the polyester of the present invention is preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. When the glass transition point is equal to or higher than the above temperature, it is preferable in terms of heat resistance. The upper limit of the glass transition point is not limited, but is preferably 320 ° C. or lower, more preferably 300 ° C. or lower. When the glass transition point is equal to or lower than the above temperature, it is preferable in terms of handleability during molding.
本発明のポリエステルの固有粘度は、０．３０〜０．７５ｄｌ／ｇの範囲であることが好ましく、０．３５〜０．７０ｄｌ／ｇの範囲であることがより好ましく、０．４０〜０．６５ｄｌ／ｇの範囲であることがさらに好ましい。固有粘度が下限以上であれば強度に優れ、上限以下であれば流動性に優れる。 The intrinsic viscosity of the polyester of the present invention is preferably in the range of 0.30 to 0.75 dl / g, more preferably in the range of 0.35 to 0.70 dl / g, and 0.40 to 0. It is more preferably in the range of 65 dl / g. If the intrinsic viscosity is at least the lower limit, the strength is excellent, and if it is at least the upper limit, the fluidity is excellent.
＜ポリエステルの製造方法＞
本発明のポリエステルの製造方法は、２，６−ナフタレンジカルボン酸を９５〜１００モル％を含むジカルボン酸成分と、イソソルビドを３５〜１００モル％含むジオール成分とを、エステル化反応もしくはエステル交換反応させた後、重縮合反応を行う方法が好ましく採用される。
<Polyester manufacturing method>
In the method for producing a polyester of the present invention, a dicarboxylic acid component containing 95 to 100 mol% of 2,6-naphthalenedicarboxylic acid and a diol component containing 35 to 100 mol% of isosorbide are subjected to an esterification reaction or a transesterification reaction. After that, a method of carrying out a polycondensation reaction is preferably adopted.
エステル化反応もしくはエステル交換反応は、２６０〜２８０℃、１〜２時間の条件で反応させることが好ましい。この際反応触媒を用いることができ、酢酸マンガンが好ましく使用される。反応触媒の添加量は、酸成分に対して、１５〜５０ｍｍｏｌ％の範囲が好ましい。 The esterification reaction or transesterification reaction is preferably carried out under the conditions of 260 to 280 ° C. for 1 to 2 hours. At this time, a reaction catalyst can be used, and manganese acetate is preferably used. The amount of the reaction catalyst added is preferably in the range of 15 to 50 mmol% with respect to the acid component.
また、重縮合反応は、２９０〜３００℃、１〜３時間の条件で反応させることが好ましい。この際反応触媒を用いることができ、アンチモン化合物やチタン化合物が好ましく、チタン化合物がより好ましく使用される。チタン化合物としてはトリメリット酸チタンが特に好ましく使用される。チタン化合物を使用すると反応性が高く、イソソルビドの含有割合や固有粘度を大きくすることが可能となり好ましい。反応触媒の添加量は、酸成分に対して、２０〜１２０ｍｍｏｌ％の範囲が好ましい。また、得られるポリエステル中のチタン（Ｔｉ）含有量は、５５ｐｐｍ 以上が好ましく、７５ｐｐｍ以上がより好ましい。また上限は特に制限されないが、２４０ｐｐｍ以下が好ましい。 Further, the polycondensation reaction is preferably carried out under the conditions of 290 to 300 ° C. for 1 to 3 hours. At this time, a reaction catalyst can be used, and an antimony compound and a titanium compound are preferable, and a titanium compound is more preferably used. As the titanium compound, titanium trimellitic acid is particularly preferably used. It is preferable to use a titanium compound because it has high reactivity and can increase the content ratio of isosorbide and the intrinsic viscosity. The amount of the reaction catalyst added is preferably in the range of 20 to 120 mmol% with respect to the acid component. The titanium (Ti) content in the obtained polyester is preferably 55 ppm or more, more preferably 75 ppm or more. The upper limit is not particularly limited, but is preferably 240 ppm or less.
＜用途、添加剤＞
本発明のポリエステルは、耐熱性に優れることから加熱殺菌の必要な容器類に好適に用いることができる。また、本発明のポリエステルは、本発明の効果を損なわない範囲であれば、例えば滑剤，顔料，染料，酸化防止剤，光安定剤，遮光剤（例えばカーボンブラック，酸化チタン等）の如きそれ自体公知の添加剤を、必要に応じて含有させることもできる。
<Use, additives>
Since the polyester of the present invention has excellent heat resistance, it can be suitably used for containers that require heat sterilization. Further, the polyester of the present invention itself, such as a lubricant, a pigment, a dye, an antioxidant, a light stabilizer, and a light-shielding agent (for example, carbon black, titanium oxide, etc.), as long as the effect of the present invention is not impaired. Known additives can also be included, if desired.
また、本発明のポリエステルには、リン化合物を熱安定性や色調改善の観点から添加することができる。このようなリン化合物としてはリン酸系、亜リン酸系、ホスホン酸系、ホスフィン酸系、ホスフィンオキサイド系、亜ホスホン酸系、亜ホスフィン酸系、ホスフィン系の１種または２種以上を用いることが好ましい。なかでもホスホノ酢酸トリエチル等のホスホン酸系化合物が好ましく使用される。ポリエステル中のリン（Ｐ）含有量は、３５ｐｐｍ以上が好ましく、５０ｐｐｍ以上がより好ましい。また上限は特に制限されないが、１５０ｐｐｍ以下が好ましい。 Further, a phosphorus compound can be added to the polyester of the present invention from the viewpoint of thermal stability and color tone improvement. As such a phosphorus compound, one or more of phosphoric acid-based, phosphorous acid-based, phosphonic acid-based, phosphinic acid-based, phosphine oxide-based, phosphonic acid-based, phosphinic acid-based, and phosphine-based are used. Is preferable. Of these, phosphonic acid compounds such as triethyl phosphonoacetate are preferably used. The phosphorus (P) content in the polyester is preferably 35 ppm or more, more preferably 50 ppm or more. The upper limit is not particularly limited, but is preferably 150 ppm or less.
以下実施例により本発明を詳細に説明するが、本発明はこれに限定されるものではない。なお、実施例中「部」とは「重量部」を意味する。評価方法は以下のとおりである。
１．ポリマー組成比（ＮＭＲ）
日本電子製ＥＣＡ−５００のプロトンＮＭＲにて各繰り返し単位を測定し、ポリマー組成比（モル比）を算出した。
２．ガラス転移点（Ｔｇ）
ポリエステル１０ｍｇを用いてＰｅｒｋｉｎＥｌｍｅｒ製のＤＳＣを使用して、ＪＩＳ Ｋ７１２１に準拠して窒素雰囲気下（窒素流量：５０ｍｌ／ｍｉｎ）、昇温速度：１０℃／ｍｉｎの条件下で測定した。
３．固有粘度
ポリエステルを重量比が６：４のフェノール：トリクロロエタン混合溶媒に試料を溶解して、３５℃の温度にて、オストワルド粘度計を用いて測定した。単位は［ｄｌ／ｇ］で示す。
４．ポリエステル中のチタン元素およびリン元素の含有量
蛍光Ｘ線元素分析装置（理学製、Ｒａｔａｆｌｅｘ ＲＵ２００）により測定した。
Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. In the examples, "part" means "part by weight". The evaluation method is as follows.
1. 1. Polymer composition ratio (NMR)
Each repeating unit was measured by proton NMR of ECA-500 manufactured by JEOL Ltd., and the polymer composition ratio (molar ratio) was calculated.
2. 2. Glass transition point (Tg)
Measurements were made using 10 mg of polyester using a DSC manufactured by PerkinElmer under a nitrogen atmosphere (nitrogen flow rate: 50 ml / min) and a heating rate of 10 ° C./min in accordance with JIS K7121.
3. 3. Intrinsic Viscosity The sample was dissolved in a phenol: trichloroethane mixed solvent having a weight ratio of 6: 4 and measured at a temperature of 35 ° C. using an Ostwald viscometer. The unit is indicated by [dl / g].
4. The contents of titanium element and phosphorus element in polyester were measured by a fluorescent X-ray element analyzer (Rataflex RU200, manufactured by Rigaku).
［実施例１］
２，６−ナフタレンジカルボン酸ジメチル９７．７ｇ（０．４０ｍｏｌ）、エチレングリコール２０．９ｇ（０．４０ｍｏｌ）、およびイソソルビド５８．５ｇ（０．４０ｍｏｌ）を酢酸マンガン２９ｍｇ（３０ｍｍｏｌ％）存在下で、３００ｍＬのフラスコ中で撹拌し、生成するメタノールを系外に留出させながらエステル交換反応を行った。反応温度は２７０℃で１．５時間反応させた。ついで、ホスホノ酢酸トリエチル（ＴＥＰＡ）３４．９ｍｇ（３９ｍｍｏｌ％）と三酸化二アンチモン２３ｍｇ（２０ｍｍｏｌ％）を加え、反応温度２９５℃で徐々に減圧し、最終的に７７Ｐａ（０．５８ｍｍＨｇ）の減圧下で重縮合反応を行い、式（１）のポリマー（ポリマー１）を得た。反応は所定のトルクに到達したところで終了とした。得られた生成物は粘度の高い暗褐色の透明ポリマーであった。ガラス転移点は１５１℃、固有粘度は０．４７４ｄｌ／ｇであった。１ＨＮＭＲ分析よりポリマーのジオール成分中のイソソルビド量は３５モル％であった。
[Example 1]
97.7 g (0.40 mol) of dimethyl 2,6-naphthalenedicarboxylic acid, 20.9 g (0.40 mol) of ethylene glycol, and 58.5 g (0.40 mol) of isosorbide in the presence of 29 mg (30 mmol%) of manganese acetate. The mixture was stirred in a 300 mL flask, and the transesterification reaction was carried out while distilling the produced methanol out of the system. The reaction temperature was 270 ° C. for 1.5 hours. Then, 34.9 mg (39 mmol%) of triethyl phosphonoacetate (TEPA) and 23 mg (20 mmol%) of diantimony trioxide were added, and the pressure was gradually reduced at a reaction temperature of 295 ° C., and finally under a reduced pressure of 77 Pa (0.58 mmHg). The polycondensation reaction was carried out in 1 to obtain the polymer of the formula (1) (polymer 1). The reaction was terminated when the predetermined torque was reached. The product obtained was a dark brown transparent polymer with high viscosity. The glass transition point was 151 ° C. and the intrinsic viscosity was 0.474 dl / g. 1 From 1 HNMR analysis, the amount of isosorbide in the diol component of the polymer was 35 mol%.
［実施例２］
ＩＶが十分に高いイソソルビド共重合ＰＥＮを得るため、仕込み組成、触媒を変更した。エチレングリコールを１６．７ｇ（０．３２ｍｏｌ）とした以外は実施例１と同様にエステル交換反応を実施した。反応完了後、ＴＥＰＡ、三酸化二アンチモンの他にトリメリット酸チタン４．５ｍｇ（０．３ｍｏｌ％）を加えて重合反応を行った。得られた生成物は粘度の高い暗褐色の透明ポリマーであった。ガラス転移点は１５１℃、固有粘度は０．４７３ｄｌ／ｇであった。これは実施例１とほぼ同様のポリマーであり、ＩＶの向上は確認できなかった。
[Example 2]
In order to obtain an isosorbide copolymerized PEN having a sufficiently high IV, the charged composition and catalyst were changed. The transesterification reaction was carried out in the same manner as in Example 1 except that ethylene glycol was adjusted to 16.7 g (0.32 mol). After completion of the reaction, in addition to TEPA and diantimony trioxide, 4.5 mg (0.3 mol%) of titanium trimellitic acid was added to carry out a polymerization reaction. The product obtained was a dark brown transparent polymer with high viscosity. The glass transition point was 151 ° C. and the intrinsic viscosity was 0.473 dl / g. This was almost the same polymer as in Example 1, and no improvement in IV could be confirmed.
［実施例３］
実施例２と同様の目的で、ＩＶが十分に高いイソソルビド共重合ＰＥＮを得るため、触媒量を増加させた。酢酸マンガン４８ｍｇ（５０ｍｍｏｌ％）、三酸化二アンチモン５７．５ｍｇ（５０ｍｍｏｌ％）、トリメリット酸チタンは添加しない、とした以外は実施例２と同様にして反応を行った。得られた生成物は粘度の高い暗褐色の透明ポリマーであった。ガラス転移点は１５６℃、固有粘度は０．３９７ｄｌ／ｇであり、ＩＶの向上は確認できなかった。イソソルビドの反応性が低く、Ｓｂ触媒では量を増加させても十分に反応が進行しないと考えられる。
[Example 3]
For the same purpose as in Example 2, the amount of catalyst was increased in order to obtain an isosorbide copolymerized PEN having a sufficiently high IV. The reaction was carried out in the same manner as in Example 2 except that 48 mg (50 mmol%) of manganese acetate, 57.5 mg (50 mmol%) of diantimony trioxide, and titanium trimellitic acid were not added. The product obtained was a dark brown transparent polymer with high viscosity. The glass transition point was 156 ° C. and the intrinsic viscosity was 0.397 dl / g, and no improvement in IV could be confirmed. The reactivity of isosorbide is low, and it is considered that the reaction does not proceed sufficiently with the Sb catalyst even if the amount is increased.
［実施例４〜７］
実施例２とグリコール成分の質量を変化させずに、イソソルビド量を０．４０〜０．５２ｍｏｌの範囲で変化させ、触媒をトリメリット酸チタン６０ｍｇ（４０ｍｍｏｌ％）に代えて、実施例２と同様の反応を行って暗褐色のポリマーを得た。組成と物性値を表１にまとめた。また、Ｔｉ含有量は７８ｐｐｍ、Ｐ含有量は５１ｐｐｍであった 。
[Examples 4 to 7]
The same as in Example 2 by changing the amount of isosorbide in the range of 0.40 to 0.52 mol and replacing the catalyst with 60 mg (40 mmol%) of titanium trimellitic acid without changing the mass of the glycol component in Example 2. Reaction was carried out to obtain a dark brown polymer. The composition and physical characteristics are summarized in Table 1. The Ti content was 78 ppm and the P content was 51 ppm.
ガラス転移点はポリエチレンナフタレートの１１９℃から最大で１７７℃まで上昇した。１ＨＮＭＲ分析から、イソソルビドの共重合量が増加すると、ガラス転移点は線形に上昇することが分かった（図１）。また、イソソルビドの増粘効果により、固有粘度は低下する傾向にあった。 The glass transition point increased from 119 ° C of polyethylene naphthalate to a maximum of 177 ° C. 1 1 HNMR analysis revealed that the glass transition point rises linearly as the amount of isosorbide copolymerization increases (Fig. 1). In addition, the intrinsic viscosity tended to decrease due to the thickening effect of isosorbide.
［実施例８］
実施例２とグリコール成分の質量を変化させずに、２，６−ナフタレンジカルボン酸ジメチル７３．３ｇ（０．３ｍｏｌ）、およびイソソルビド８７．７ｇ（０．６ｍｏｌ）をトリメリット酸チタン１２０ｍｇ（８０ｍｍｏｌ％）存在下で、実施例４−７と同様に３００ｍＬのフラスコ中で撹拌し、生成するメタノールを系外に留出させながらエステル交換反応を行った。反応温度は２７０℃で２時間反応させ。ついで、反応温度を２９５℃とし、徐々に減圧し、最終的に７７Ｐａ（０．５８ｍｍＨｇ）の減圧下で重縮合反応を行い、式（１）のポリマー（ポリマー１）を得た。反応は所定のトルクに到達したところで終了とした。ガラス転移点は２０５℃、固有粘度は０．４３７であった。また、Ｔｉ含有量は１５６ｐｐｍ、Ｐ含有量は１０２ｐｐｍであった 。
[Example 8]
120 mg (80 mmol%) of titanium trimellitic acid was added to Example 2 and 77.3 g (0.3 mol) of dimethyl 2,6-naphthalenedicarboxylic acid and 87.7 g (0.6 mol) of isosorbide without changing the mass of the glycol component. ) In the presence of the mixture, the mixture was stirred in a 300 mL flask in the same manner as in Example 4-7, and the transesterification reaction was carried out while distilling the produced methanol out of the system. The reaction temperature was 270 ° C. for 2 hours. Then, the reaction temperature was set to 295 ° C., the pressure was gradually reduced, and finally the polycondensation reaction was carried out under a reduced pressure of 77 Pa (0.58 mmHg) to obtain the polymer (polymer 1) of the formula (1). The reaction was terminated when the predetermined torque was reached. The glass transition point was 205 ° C. and the intrinsic viscosity was 0.437. The Ti content was 156 ppm and the P content was 102 ppm.
イソソルビド量を０〜０．４０ｍｏｌの範囲で変化させ、触媒を酢酸マンガン、三酸化二アンチモンとして、実施例１と同様の反応を行って暗褐色のポリマーを得た。組成と物性値を表２にまとめた。この触媒条件ではイソソルビド／エチレングリコールのモル比が１．０より大きい場合は、十分に反応が進行しなかった。
The amount of isosorbide was changed in the range of 0 to 0.40 mol, the catalyst was manganese acetate and diantimony trioxide, and the same reaction as in Example 1 was carried out to obtain a dark brown polymer. The composition and physical characteristics are summarized in Table 2. Under this catalytic condition, when the molar ratio of isosorbide / ethylene glycol was greater than 1.0, the reaction did not proceed sufficiently.
上記の結果より、ポリエチレンナフタレートにイソソルビドを共重合したポリエステル樹脂は、ポリエチレンナフタレートと比べて著しく耐熱性が向上することが分かる。したがって、ポリエチレンナフタレートがもつ耐薬品性やガスバリア性などの特性を残しつつ、耐熱性を向上させたポリエステルが作製できると期待できる。また、イソソルビドの共重合量に対してガラス転移点は線型に増加することが判明した。したがって、イソソルビドとエチレングリコールの量と比を調節することで、１１９℃から２０５℃の間で所望のガラス転移点を有するポリマーを合成できる可能性が示された。その際用いる重合触媒は、三酸化二アンチモンよりトリメリット酸チタンなどチタン系触媒である方が反応性が高く、より好適であることが判明した。さらに、イソソルビドはバイオマス原料であるため、本発明は化石燃料に依存しないバイオポリマーとして、持続可能な社会の実現に貢献する。 From the above results, it can be seen that the polyester resin obtained by copolymerizing polyethylene naphthalate with isosorbide has significantly improved heat resistance as compared with polyethylene naphthalate. Therefore, it can be expected that a polyester having improved heat resistance can be produced while retaining the characteristics such as chemical resistance and gas barrier property of polyethylene naphthalate. It was also found that the glass transition point linearly increases with respect to the copolymerization amount of isosorbide. Therefore, it was shown that by adjusting the amount and ratio of isosorbide and ethylene glycol, it is possible to synthesize a polymer having a desired glass transition point between 119 ° C and 205 ° C. As the polymerization catalyst used at that time, it was found that a titanium-based catalyst such as titanium trimellitic acid has higher reactivity than diantimony trioxide and is more preferable. Furthermore, since isosorbide is a raw material for biomass, the present invention contributes to the realization of a sustainable society as a biopolymer that does not depend on fossil fuels.
本発明のポリエステルは、オートクレーブ処理にも耐えうる高耐熱ポリエステルであり、加熱砂金が必要な医療用容器、医療器具、食器等の用途に好適に使用される。 The polyester of the present invention is a highly heat-resistant polyester that can withstand autoclaving, and is suitably used for applications such as medical containers, medical instruments, and tableware that require heated gold dust.
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