JP2006143810A - Copolymer of lactic acid and method for producing the same - Google Patents
Copolymer of lactic acid and method for producing the same Download PDFInfo
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本発明は、ガラス転位温度（Ｔｇ）が６５℃以上の耐熱性に優れた共重合ポリ乳酸に関するものである。 The present invention relates to a copolymerized polylactic acid having a glass transition temperature (Tg) of 65 ° C. or more and excellent heat resistance.
近年、環境問題に対する意識の高まりから、生分解性樹脂、特に、ポリ乳酸を利用した商品の開発が行われている。しかしながら、Ｌ−ポリ乳酸のＴｇは５８℃と通常の樹脂に比べて低く、成形サイクルが長くなるなど成形材料として取り扱うには問題があった。（特許文献１参照） In recent years, due to increasing awareness of environmental issues, products using biodegradable resins, particularly polylactic acid, have been developed. However, the Tg of L-polylactic acid is 58 ° C., which is lower than that of ordinary resins, and there is a problem in handling as a molding material such as a longer molding cycle. (See Patent Document 1)
本発明の課題は、Ｔｇがポリ乳酸よりも高く、成形サイクルの短縮が可能な成形材料として優れた特性を有する共重合ポリ乳酸を提供することにある。 An object of the present invention is to provide a copolymerized polylactic acid having a Tg higher than that of polylactic acid and having excellent characteristics as a molding material capable of shortening the molding cycle.
本発明者らは、上記の課題を解決するために鋭意研究した結果、ポリ乳酸に、芳香族ポリエステル構成単位を導入することにより、共重合ポリ乳酸のＴｇが、ポリ乳酸単独のＴｇよりも格段に上がることを見出し、さらには、その重合方法として、ポリ乳酸をアシドリシス後、アセチル化し、脱酢酸により縮重合することが有効であることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have introduced an aromatic polyester structural unit into polylactic acid, so that the Tg of the copolymerized polylactic acid is much higher than the Tg of polylactic acid alone. Further, as a polymerization method thereof, it was found that it is effective to acetylate polylactic acid after acidosis and then perform polycondensation by deacetic acid, and the present invention was completed.
すなわち、本発明の要旨は次の通りである。
（１）乳酸からなる構成単位（Ａ）と、芳香族カルボン酸成分（ｂ１）、芳香族アルコール成分（ｂ２）、および芳香族ヒドロキシカルボン酸成分（ｂ３）の少なくとも一つの成分からなる芳香族ポリエステル構成単位（Ｂ）が、（Ａ）／（Ｂ）＝２０／８０〜９５／５（モル比）の割合で共重合されてなることを特徴とする共重合ポリ乳酸。
（２）ポリ乳酸を芳香族カルボン酸でアシドリシス後、芳香族アルコールと共に、アセチル化し、脱酢酸により縮重合することを特徴とする共重合ポリ乳酸の製造方法。
（３）ポリ乳酸を芳香族ヒドロキシカルボン酸でアシドリシス後、アセチル化し、脱酢酸により縮重合することを特徴とする共重合ポリ乳酸の製造方法。
（４）ポリ乳酸を芳香族カルボン酸と芳香族ヒドロキシカルボン酸でアシドリシス後、芳香族アルコールと共に、アセチル化し、脱酢酸により縮重合することを特徴とする共重合ポリ乳酸の製造方法。
That is, the gist of the present invention is as follows.
(1) An aromatic polyester comprising a structural unit (A) composed of lactic acid and at least one of an aromatic carboxylic acid component (b1), an aromatic alcohol component (b2), and an aromatic hydroxycarboxylic acid component (b3) A copolymer polylactic acid, wherein the structural unit (B) is copolymerized at a ratio of (A) / (B) = 20/80 to 95/5 (molar ratio).
(2) A method for producing a copolymerized polylactic acid, wherein the polylactic acid is acidified with an aromatic carboxylic acid, then acetylated with an aromatic alcohol, and subjected to condensation polymerization by deacetic acid.
(3) A method for producing a copolymerized polylactic acid, wherein the polylactic acid is acidified with an aromatic hydroxycarboxylic acid, then acetylated, and subjected to polycondensation by deacetic acid.
(4) A method for producing a copolymerized polylactic acid, characterized in that polylactic acid is acidified with an aromatic carboxylic acid and an aromatic hydroxycarboxylic acid, then acetylated with an aromatic alcohol, and subjected to polycondensation by deacetic acid.
本発明の共重合ポリ乳酸は、Ｔｇがポリ乳酸よりも高く、成形サイクルの短縮が可能な成形材料として優れた特性を有する共重合ポリ乳酸が提供される。 The copolymerized polylactic acid of the present invention provides a copolymerized polylactic acid having a Tg higher than that of polylactic acid and excellent properties as a molding material capable of shortening the molding cycle.
以下、本発明を詳細に説明する。
本発明の共重合ポリ乳酸は、乳酸からなる構成単位（Ａ）と、芳香族カルボン酸成分（ｂ１）、芳香族アルコール成分（ｂ２）、および芳香族ヒドロキシカルボン酸成分（ｂ３）の少なくとも一つの成分からなる芳香族ポリエステル構成単位（Ｂ）が、（Ａ）／（Ｂ）＝２０／８０〜９５／５（モル比）の割合で共重合されてなるものである。
Hereinafter, the present invention will be described in detail.
The copolymer polylactic acid of the present invention comprises at least one of a structural unit (A) comprising lactic acid, an aromatic carboxylic acid component (b1), an aromatic alcohol component (b2), and an aromatic hydroxycarboxylic acid component (b3). The aromatic polyester structural unit (B) composed of the components is copolymerized at a ratio of (A) / (B) = 20/80 to 95/5 (molar ratio).
本発明の共重合ポリ乳酸において、乳酸からなる構成単位（Ａ）の割合は、共重合ポリ乳酸全体に対して、２０〜９５モル％であることが必要であり、３０〜８５モル％がより好ましく、４０〜７５モル％がさらに好ましい。
乳酸からなる構成単位（Ａ）の割合が２０モル％よりも少ない場合には、芳香族ポリエステル構成成分の適切な重合温度においてポリ乳酸が分解しやすくなり好ましくない。
In the copolymerized polylactic acid of the present invention, the proportion of the structural unit (A) composed of lactic acid needs to be 20 to 95 mol% with respect to the entire copolymerized polylactic acid, and more preferably 30 to 85 mol%. Preferably, 40 to 75 mol% is more preferable.
When the proportion of the structural unit (A) composed of lactic acid is less than 20 mol%, polylactic acid tends to decompose at an appropriate polymerization temperature of the aromatic polyester constituent component, which is not preferable.
本発明の共重合ポリ乳酸において、乳酸からなる構成単位（Ａ）の共重合成分が、芳香族カルボン酸成分（ｂ１）と芳香族アルコール成分（ｂ２）の２成分からなる場合には、共重合ポリ乳酸全体に占める（ｂ１）と（ｂ２）のモル比の割合は、４０：６０〜６０：４０にすることが好ましく、４５：５５〜５５：４５にすることがより好ましく、５０：５０にすることが最も好ましい。各成分の割合が上記の範囲をはずれると、得られる共重合ポリ乳酸の重合度が上がらないので好ましくない。 In the copolymerized polylactic acid of the present invention, when the copolymer component of the structural unit (A) composed of lactic acid is composed of two components, an aromatic carboxylic acid component (b1) and an aromatic alcohol component (b2), copolymerization is performed. The ratio of the molar ratio of (b1) and (b2) to the whole polylactic acid is preferably 40:60 to 60:40, more preferably 45:55 to 55:45, and 50:50 Most preferably. If the proportion of each component is out of the above range, the degree of polymerization of the copolymerized polylactic acid obtained is not preferable.
本発明の共重合ポリ乳酸において、乳酸からなる構成単位（Ａ）の共重合成分が、芳香族ヒドロキシカルボン酸成分（ｂ３）を含む場合には、共重合ポリ乳酸全体に占める（ｂ３）の割合は９０モル％以下が好ましく、より好ましくは５５モル％以下、３５モル％以下とすることが最適である。 In the copolymerized polylactic acid of the present invention, when the copolymer component of the structural unit (A) comprising lactic acid contains the aromatic hydroxycarboxylic acid component (b3), the proportion of (b3) in the total copolymerized polylactic acid Is preferably 90 mol% or less, more preferably 55 mol% or less and 35 mol% or less.
本発明の共重合ポリ乳酸を構成する、乳酸からなる構成単位（Ａ）としては、乳酸の構造単位がＬ−乳酸であるポリ（Ｌ−乳酸）、構造単位がＤ−乳酸であるポリ（Ｄ−乳酸）、およびこれらの混合物または共重合体を出発物質として用いることができる。 As the structural unit (A) comprising lactic acid constituting the copolymer polylactic acid of the present invention, poly (L-lactic acid) in which the structural unit of lactic acid is L-lactic acid and poly (D-lactic acid in which the structural unit is D-lactic acid) -Lactic acid), and mixtures or copolymers thereof can be used as starting materials.
ポリ乳酸の重合方法としては、縮重合法、開環重合法などの方法を採用することができる。例えば、縮重合法ではＬ−乳酸またはＤ−乳酸あるいはこれらの混合物を直接脱水縮重合することができる。また、開環重合法では乳酸の環状２量体であるラクチドを、オクチル酸錫等の触媒を使用して重合することができる。ラクチドにはＬ−乳酸の２量体であるＬ−ラクチド、Ｄ−乳酸の２量体であるＤ−ラクチド、さらにＬ−乳酸とＤ−乳酸からなるＤＬ−ラクチドがあり、これらを必要に応じて混合して重合することができる。 As a polymerization method of polylactic acid, methods such as a condensation polymerization method and a ring-opening polymerization method can be employed. For example, in the condensation polymerization method, L-lactic acid, D-lactic acid or a mixture thereof can be directly subjected to dehydration condensation polymerization. In the ring-opening polymerization method, lactide, which is a cyclic dimer of lactic acid, can be polymerized using a catalyst such as tin octylate. Lactide includes L-lactide, which is a dimer of L-lactic acid, D-lactide, which is a dimer of D-lactic acid, and DL-lactide composed of L-lactic acid and D-lactic acid. Can be mixed and polymerized.
また、ポリ乳酸の分子量を増大させるために少量の鎖延長剤、例えば、ジイソシアネート化合物、エポキシ化合物、酸無水物などを使用することもできる。 Moreover, in order to increase the molecular weight of polylactic acid, a small amount of chain extender, for example, a diisocyanate compound, an epoxy compound, an acid anhydride, etc. can be used.
ポリ乳酸の重量平均分子量は通常５万〜１００万の範囲にあるものを用いることができ、このような分子量を有するポリ乳酸は、たとえば、カーギルダウ社、三井化学等から販売されている。 A polylactic acid having a weight average molecular weight in the range of 50,000 to 1,000,000 can be used. Polylactic acid having such a molecular weight is sold by, for example, Cargill Dow, Mitsui Chemicals, and the like.
また、本発明において、乳酸からなる構成単位（Ａ）を導入する方法として、出発物質にラクチドを用いる場合には、触媒添加し減圧にするなど、重合段階でラクチドが一部重合系外に放出されることが多いので、ラクチドを重合反応釜に投入する際は、目標組成よりも若干過剰に投入する必要がある。 In the present invention, as a method for introducing the structural unit (A) comprising lactic acid, when lactide is used as a starting material, a part of the lactide is released from the polymerization system in the polymerization stage, for example, by adding a catalyst and reducing the pressure. For this reason, when lactide is charged into the polymerization reaction kettle, it is necessary to charge it slightly in excess of the target composition.
本発明において用いられる、芳香族カルボン酸成分（ｂ１）としては、テレフタル酸、イソフタル酸、オルトフタル酸、２，６−ナフタレンジカルボン酸、ビフェニルジカルボン酸、５−スルホイソフタル酸等が例示できる。これらは無水物であってもよい。上記した芳香族カルボン酸の中でも、テレフタル酸とイソフタル酸が特に好ましい。 Examples of the aromatic carboxylic acid component (b1) used in the present invention include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and 5-sulfoisophthalic acid. These may be anhydrous. Among the above aromatic carboxylic acids, terephthalic acid and isophthalic acid are particularly preferable.
本発明において用いられる、芳香族アルコール成分（ｂ２）としては、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＣ、ビスフェノールＺ、ビスフェノールＡＰ、４，４′−ビフェノール等を用いることができる。上記した芳香族アルコールの中でも、ビスフェノールＡが特に好ましい。 As the aromatic alcohol component (b2) used in the present invention, bisphenol A, bisphenol S, bisphenol C, bisphenol Z, bisphenol AP, 4,4′-biphenol and the like can be used. Among the above-mentioned aromatic alcohols, bisphenol A is particularly preferable.
本発明において用いられる、芳香族ヒドロキシカルボン酸成分（ｂ３）としては、ｐ−ヒドロキシ安息香酸、ｍ−ヒドロキシ安息香酸、ｏ−ヒドロキシ安息香酸等を例示することができる。上記した芳香族ヒドロキシカルボン酸の中でも、ｐ−ヒドロキシ安息香酸が特に好ましい。 Examples of the aromatic hydroxycarboxylic acid component (b3) used in the present invention include p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid and the like. Of the above-mentioned aromatic hydroxycarboxylic acids, p-hydroxybenzoic acid is particularly preferable.
本発明の共重合ポリ乳酸の数平均分子量は４，０００以上とすることが好ましく、８，０００以上であることがより好ましく、１２，０００以上であることがさらに好ましく、１５，０００以上であることが特に好ましい。数平均分子量が４，０００未満では、成形材料として用いることが困難である。 The number average molecular weight of the copolymerized polylactic acid of the present invention is preferably 4,000 or more, more preferably 8,000 or more, further preferably 12,000 or more, and 15,000 or more. It is particularly preferred. If the number average molecular weight is less than 4,000, it is difficult to use as a molding material.
また、共重合ポリ乳酸の分子量分布の分散度は、特に限定されないが、８以下が好ましく、５以下がより好ましい。ここで、分子量分布の分散度とは、重量平均分子量を数平均分子量で除した値のことである。 Further, the degree of dispersion of the molecular weight distribution of the copolymerized polylactic acid is not particularly limited, but is preferably 8 or less, and more preferably 5 or less. Here, the degree of dispersion of the molecular weight distribution is a value obtained by dividing the weight average molecular weight by the number average molecular weight.
また、共重合ポリ乳酸のガラス転移温度（Ｔｇ）は、少なくともポリ乳酸のＴｇである５８℃よりも高くなければならない。 The glass transition temperature (Tg) of the copolymerized polylactic acid must be at least higher than 58 ° C., which is the Tg of polylactic acid.
本発明の共重合ポリ乳酸を得るための製造方法としては、アシドリシス工程、アセチル化工程、続いて、脱酢酸による縮重合工程を経る溶融重合法によって製造することができる。 As a production method for obtaining the copolymerized polylactic acid of the present invention, it can be produced by an acid polymerization process, an acetylation process, and then a melt polymerization process through a condensation polymerization process by deacetic acid.
アシドリシス工程は、カルボン酸末端基をもつモノマーでポリ乳酸をアシドリシス化する工程である。本発明の共重合ポリ乳酸が、乳酸からなる構成単位（Ａ）と、芳香族カルボン酸成分（ｂ１）および芳香族アルコール成分（ｂ２）からなる場合（以下、構成（１）という）には芳香族カルボン酸によってアシドリシス化し、乳酸からなる構成単位（Ａ）と芳香族ヒドロキシカルボン酸成分（ｂ３）からなる場合（以下、構成（２）という）には芳香族ヒドロシシカルボン酸によってアシドリシス化し、乳酸からなる構成単位（Ａ）と、芳香族カルボン酸成分（ｂ１）および芳香族アルコール成分（ｂ２）および芳香族ヒドロキシカルボン酸成分（ｂ３）からなる場合（以下、構成（３）という）には芳香族カルボン酸と芳香族ヒドロキシカルボン酸両方で、ポリ乳酸をアシドリシス化する。
アシドリシス工程では、ポリ乳酸とアシドリシスするモノマーを反応容器に仕込み、攪拌しながら、２００〜２４０℃で２〜８時間、解重合を行なう。アシドリシスするモノマーは一括で投入しても、また分割して投入してもいずれでもかまわない。
The acidolysis step is a step of acidifying polylactic acid with a monomer having a carboxylic acid end group. When the copolymerized polylactic acid of the present invention comprises a structural unit (A) comprising lactic acid, an aromatic carboxylic acid component (b1) and an aromatic alcohol component (b2) (hereinafter referred to as constitution (1)), the fragrance In the case where it is acidified with an aromatic carboxylic acid and composed of a structural unit (A) comprising lactic acid and an aromatic hydroxycarboxylic acid component (b3) (hereinafter referred to as constitution (2)), it is acidified with an aromatic hydroxycarboxylic acid, And the aromatic carboxylic acid component (b1), the aromatic alcohol component (b2) and the aromatic hydroxycarboxylic acid component (b3) (hereinafter referred to as the configuration (3)) Polylactic acid is acidified with both aromatic carboxylic acid and aromatic hydroxycarboxylic acid.
In the acidolysis step, polylactic acid and the acidolysis monomer are charged into a reaction vessel, and depolymerization is performed at 200 to 240 ° C. for 2 to 8 hours while stirring. The monomers that undergo acidosis may be added all at once or dividedly.
アセチル化工程は、ヒドロキシ末端を無水酢酸によって、アセチル化する工程である。構成（１）の場合には芳香族アルコールと無水酢酸を、構成（２）の場合は無水酢酸を、構成（３）の場合は芳香族アルコールと無水酢酸を反応容器に仕込み、攪拌しながら、１００〜１５０℃で１〜８時間アセチル化を行なう。この工程において、アシドリシスされたポリ乳酸のヒドロキシ末端および芳香族アルコール、芳香族ヒドロキシカルボン酸のヒドロキシ末端がアセチル化される。ヒドロキシ末端をもつモノマーは、あらかじめアシドリシス工程で反応容器に投入しておいても、また、アセチル化工程前に投入してもいずれでもかまわない。 The acetylation step is a step of acetylating the hydroxy terminal with acetic anhydride. In the case of the configuration (1), aromatic alcohol and acetic anhydride are charged, in the case of the configuration (2), acetic anhydride is charged, and in the case of the configuration (3), the aromatic alcohol and acetic anhydride are charged into a reaction vessel, Acetylation is performed at 100 to 150 ° C. for 1 to 8 hours. In this step, the hydroxy terminal of the acidified polylactic acid and the hydroxy terminal of the aromatic alcohol or aromatic hydroxycarboxylic acid are acetylated. The monomer having a hydroxy terminus may be previously charged into the reaction vessel in the acidolysis step or may be charged before the acetylation step.
縮重合工程は、アセチル化されたポリ乳酸およびアセチル化した芳香族アルコールを脱酢酸して縮重合する工程である。例えば、２００〜２５０℃まで重合温度を昇温し、さらに系内を１３０Ｐａ以下の減圧にし、高真空下で３〜１０時間縮重合反応を行なう。 The polycondensation step is a step of decondensing acetylated polylactic acid and acetylated aromatic alcohol to perform polycondensation. For example, the polymerization temperature is raised to 200 to 250 ° C., the pressure inside the system is reduced to 130 Pa or less, and the condensation polymerization reaction is performed under high vacuum for 3 to 10 hours.
本発明の共重合ポリ乳酸の分子量を制御する方法としては、重合時の共重合ポリ乳酸溶融物を所定の粘度で重合を終了する方法などが挙げられる。 Examples of the method for controlling the molecular weight of the copolymerized polylactic acid of the present invention include a method of terminating the polymerization of the copolymerized polylactic acid melt at the time of polymerization with a predetermined viscosity.
本発明の共重合ポリ乳酸を製造する際には、触媒を用いなくても重合は可能ではあるが、テトラブチルチタネ−トなどの有機チタン酸化合物、酢酸亜鉛、酢酸マグネシウムなどのアルカリ金属、アルカリ土類金属の酢酸塩、ヒドロキシブチルスズオキサイド、オクチル酸スズなどの有機錫化合物をアシドリシス工程などで用いてもかまわない。
その際の触媒使用量は、生成するポリマーの質量に対し、1．０質量％以下を用いるのが好ましい。１．０質量％を超える場合には、内容物への触媒の溶出が懸念される等の問題があるので好ましくない。
When the copolymerized polylactic acid of the present invention is produced, polymerization is possible without using a catalyst, but an organic titanate compound such as tetrabutyl titanate, an alkali metal such as zinc acetate and magnesium acetate, Organic tin compounds such as alkaline earth metal acetates, hydroxybutyltin oxide and tin octylate may be used in the acidolysis process.
In this case, the amount of the catalyst used is preferably 1.0% by mass or less based on the mass of the polymer to be produced. If it exceeds 1.0% by mass, there is a problem such as concern about elution of the catalyst into the contents, which is not preferable.
また、本発明の共重合ポリ乳酸には、必要に応じて硬化剤、各種添加剤、酸化チタン、亜鉛華、カーボンブラック等の顔料、染料、ポリエステル樹脂、ウレタン樹脂、オレフィン樹脂、アクリル樹脂、アルキド樹脂、セルロース誘導体等を配合することができる。 The copolymerized polylactic acid of the present invention includes a curing agent, various additives, pigments such as titanium oxide, zinc white, carbon black, dyes, polyester resins, urethane resins, olefin resins, acrylic resins, alkyds as necessary. Resins, cellulose derivatives and the like can be blended.
また、本発明の共重合ポリ乳酸には、必要に応じて、顔料分散剤、紫外線吸収剤、離型剤、顔料分散剤、滑剤等の添加剤を配合することができる。 The copolymerized polylactic acid of the present invention can be blended with additives such as a pigment dispersant, an ultraviolet absorber, a release agent, a pigment dispersant, and a lubricant, as necessary.
以下、実施例によって本発明を具体的に説明するが、本発明はこれらによって限定されるものではない。
（１）共重合ポリ乳酸の構成
1Ｈ−ＮＭＲ分析（バリアン社製，３００ＭＨｚ）より求めた。また、1Ｈ−ＮＭＲスペクトル上に帰属・定量可能なピークが認められない構成モノマーを含む樹脂については、封管中２３０℃で３時間メタノール分解を行った後に、ガスクロマトグラム分析に供し、定量分析を行った。
（２）共重合ポリ乳酸の数平均分子量
数平均分子量は、ＧＰＣ分析（島津製作所製の送液ユニットＬＣ−１０ＡＤｖｐ型及び紫外−可視分光光度計ＳＰＤ−６ＡＶ型を使用、検出波長：２５４ｎｍ、溶媒：クロロホルム、ポリスチレン換算）により求めた。
（３）共重合ポリ乳酸のガラス転移温度（Ｔｇ）
共重合ポリ乳酸１０ｍｇをサンプルとし、ＤＳＣ（示差走査熱量測定）装置（パーキンエルマー社製 ＤＳＣ７）を用いて昇温速度１０℃／分の条件で測定を行ない、得られた昇温曲線中のガラス転移に由来する２つの折曲点温度の中間値を求め、これをＴｇとした。
実施例１
カーギルダウ社製ポリ乳酸６２５０Ｄ（Ｌ−ポリ乳酸）１１８４ｇ（１４４モル％）とテレフタル酸２６６ｇ（１４モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、ビスフェノールＡ ３６５ｇ（１４モル％）と、無水酢酸４０８ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２４０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／テレフタル酸／ビスフェノールＡ＝７２モル％／１４モル％／１４モル％であった。
実施例２
カーギルダウ社製ポリ乳酸６２５０Ｄ（Ｌ−ポリ乳酸）１８４０ｇ（１６０モル％）とイソフタル酸２６６ｇ（１０モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、ビスフェノールＡ ３６５ｇ（１０モル％）と、無水酢酸４０８ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２４０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／イソフタル酸／ビスフェノールＡ＝８０モル％／１０モル％／１０モル％であった。
実施例３
カーギルダウ社製ポリ乳酸４０３１Ｄ（Ｌ−ポリ乳酸）１１８４ｇ（１４４モル％）とテレフタル酸１３３ｇ（７モル％）とイソフタル酸１３３ｇ（７モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、ビスフェノールＡ ３６５ｇ（１４モル％）と、無水酢酸４０８ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２４０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／テレフタル酸／イソフタル酸／ビスフェノールＡ＝７２モル％／７モル％／７モル％／１４モル％であった。
実施例４
カーギルダウ社製ポリ乳酸６２５０Ｄ（Ｌ−ポリ乳酸）１３６ｇ（４６モル％）とテレフタル酸１８６ｇ（２７モル％）とイソフタル酸８０ｇ（１２モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、ビスフェノールＡ ３６５ｇ（３９モル％）と、無水酢酸４０８ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２４０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／テレフタル酸／イソフタル酸／ビスフェノールＡ＝２２モル％／２７モル％／１２モル％／３９モル％であった。
実施例５
カーギルダウ社製ポリ乳酸４０３１Ｄ（Ｌ−ポリ乳酸）７０４５ｇ（１８８モル％）とテレフタル酸１８６ｇ（２モル％）とイソフタル酸８０ｇ（１モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、ビスフェノールＡ ３６５ｇ（３モル％）と、無水酢酸４０８ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２４０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／テレフタル酸／イソフタル酸／ビスフェノールＡ＝９４モル％／２モル％／１モル％／３モル％であった。
実施例６
カーギルダウ社製ポリ乳酸６２５０Ｄ（Ｌ−ポリ乳酸）１６７ｇ（８４モル％）とｐ−ヒドロキシ安息香酸１９４ｇ（２９モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で１．５時間加熱したあと、さらにｐ−ヒドロキシ安息香酸１９４ｇ（２９モル％）を投入し、オートクレーブ中で、攪拌しながら、２４０℃でさらに２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、無水酢酸２０４ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２３０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／ｐ−ヒドロキシ安息香酸＝４２モル％／５８モル％であった。
実施例７
カーギルダウ社製ポリ乳酸４０３１Ｄ（Ｌ−ポリ乳酸）５３７ｇ（１４０モル％）とｐ−ヒドロキシ安息香酸３８８ｇ（３０モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、無水酢酸２０４ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２３０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／ｐ−ヒドロキシ安息香酸＝７０モル％／３０モル％であった。
実施例８
カーギルダウ社製ポリ乳酸６２５０Ｄ（Ｌ−ポリ乳酸）１１９ｇ（６８モル％）とテレフタル酸１６ｇ（４モル％）、イソフタル酸１６ｇ（４モル％）、ビスフェノールＡ ４４ｇ（８モル％）、ｐ−ヒドロキシ安息香酸２９５ｇ（５０モル％）からなる混合物をオートクレーブ中で、攪拌しながら、２４０℃で２時間加熱してアシドリシス反応を行った。次いで、系の温度を１４０℃に降温し、無水酢酸１９６ｇを投入して、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を２３０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリ乳酸を得た。
得られた共重合ポリ乳酸の樹脂組成を調べたところ、乳酸／テレフタル酸／イソフタル酸／ビスフェノールＡ／ｐ−ヒドロキシ安息香酸＝３４モル％／４モル％／４モル％／８モル％／５０モル％であった。
比較例１
オートクレーブ中で、イソフタル酸２６６ｇ（５０モル％）、ビスフェノールＡ ３６５ｇ（５０モル％）と無水酢酸４０８ｇからなる混合物をオートクレーブ中で、攪拌しながら、系の温度を１４０℃で、攪拌しながら、４時間加熱してアセチル化反応を行なった。続いて、系の温度を３２０℃に昇温し、系の圧力を徐々に減じて１．５時間後に１３Ｐａとし、攪拌しながら、重縮合反応を行なった。８時間後、系を窒素ガスで加圧状態にしてストランド状に樹脂を払い出し、水冷後、ペレタイザーでカッティングを行ない、ペレット状の共重合ポリエステルを得た。
得られた共重合ポリエステルの樹脂組成を調べたところ、イソフタル酸／ビスフェノールＡ＝５０モル％／５０モル％であった。
比較例２
カーギルダウ製ポリ乳酸４０３１Ｄの性能を評価した。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
(1) Composition of copolymerized polylactic acid
It calculated | required from < 1 > H-NMR analysis (The product made by a Varian, 300MHz). Also, the resin containing a constituent monomer is not observed attributable-quantifiable peaks on 1 H-NMR spectrum, after the 3 hours methanolysis at 230 ° C. in a sealed tube and subjected to gas chromatography analysis, quantitative analysis Went.
(2) Number average molecular weight of copolymerized polylactic acid The number average molecular weight is determined by GPC analysis (liquid feeding unit LC-10ADvp type and UV-visible spectrophotometer SPD-6AV type manufactured by Shimadzu Corporation), detection wavelength: 254 nm, solvent : Chloroform, polystyrene conversion).
(3) Glass transition temperature (Tg) of copolymer polylactic acid
Using a copolymerized polylactic acid 10 mg as a sample, measurement was performed using a DSC (Differential Scanning Calorimetry) apparatus (DSC7 manufactured by PerkinElmer Co., Ltd.) at a temperature rising rate of 10 ° C./min. An intermediate value between two bending point temperatures derived from the transition was determined, and this was defined as Tg.
Example 1
A mixture of 1184 g (144 mol%) of polylactic acid 6250D (L-polylactic acid) manufactured by Cargill Dow and 266 g (14 mol%) of terephthalic acid was heated in an autoclave at 240 ° C. for 2 hours to perform an acidolysis reaction. went. Next, the temperature of the system was lowered to 140 ° C., 365 g (14 mol%) of bisphenol A and 408 g of acetic anhydride were added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / terephthalic acid / bisphenol A = 72 mol% / 14 mol% / 14 mol%.
Example 2
A mixture of 1840 g (160 mol%) of polylactic acid 6250D (L-polylactic acid) manufactured by Cargill Dow and 266 g (10 mol%) of isophthalic acid was heated in an autoclave at 240 ° C. for 2 hours to perform an acidolysis reaction. went. Next, the temperature of the system was lowered to 140 ° C., 365 g (10 mol%) of bisphenol A and 408 g of acetic anhydride were added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / isophthalic acid / bisphenol A = 80 mol% / 10 mol% / 10 mol%.
Example 3
While stirring a mixture of 1184 g (144 mol%) of polylactic acid 4031D (L-polylactic acid), 133 g (7 mol%) of terephthalic acid and 133 g (7 mol%) of isophthalic acid (carol Dow) at 240 ° C. in an autoclave. The acidolysis reaction was carried out by heating for 2 hours. Next, the temperature of the system was lowered to 140 ° C., 365 g (14 mol%) of bisphenol A and 408 g of acetic anhydride were added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / terephthalic acid / isophthalic acid / bisphenol A = 72 mol% / 7 mol% / 7 mol% / 14 mol%.
Example 4
While stirring a mixture of 136 g (46 mol%) of polylactic acid 6250D (L-polylactic acid), 186 g (27 mol%) of terephthalic acid and 80 g (12 mol%) of isophthalic acid manufactured by Cargill Dow in an autoclave at 240 ° C. The acidolysis reaction was carried out by heating for 2 hours. Subsequently, the temperature of the system was lowered to 140 ° C., 365 g (39 mol%) of bisphenol A and 408 g of acetic anhydride were added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / terephthalic acid / isophthalic acid / bisphenol A = 22 mol% / 27 mol% / 12 mol% / 39 mol%.
Example 5
While stirring a mixture of 7045 g (188 mol%) of polylactic acid 4031D (L-polylactic acid), 186 g (2 mol%) of terephthalic acid, and 80 g (1 mol%) of isophthalic acid manufactured by Cargill Dow in an autoclave at 240 ° C. The acidolysis reaction was carried out by heating for 2 hours. Next, the temperature of the system was lowered to 140 ° C., 365 g (3 mol%) of bisphenol A and 408 g of acetic anhydride were added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 240 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / terephthalic acid / isophthalic acid / bisphenol A = 94 mol% / 2 mol% / 1 mol% / 3 mol%.
Example 6
A mixture of 167 g (84 mol%) of polylactic acid 6250D (L-polylactic acid) manufactured by Cargill Dow and 194 g (29 mol%) of p-hydroxybenzoic acid was heated at 240 ° C. for 1.5 hours with stirring in an autoclave. Then, 194 g (29 mol%) of p-hydroxybenzoic acid was further added, and the mixture was further heated at 240 ° C. for 2 hours with stirring in an autoclave to carry out an acidolysis reaction. Next, the temperature of the system was lowered to 140 ° C., 204 g of acetic anhydride was added, and the mixture was stirred and heated for 4 hours to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 230 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was investigated, it was lactic acid / p-hydroxybenzoic acid = 42 mol% / 58 mol%.
Example 7
A mixture of 537 g (140 mol%) of polylactic acid 4031D (L-polylactic acid) manufactured by Cargill Dow and 388 g (30 mol%) of p-hydroxybenzoic acid was heated in an autoclave at 240 ° C. for 2 hours with stirring. An acidolysis reaction was performed. Next, the temperature of the system was lowered to 140 ° C., 204 g of acetic anhydride was added, and the mixture was stirred and heated for 4 hours to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 230 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, it was lactic acid / p-hydroxybenzoic acid = 70 mol% / 30 mol%.
Example 8
119 g (68 mol%) of polylactic acid 6250D (L-polylactic acid) manufactured by Cargill Dow, 16 g (4 mol%) of terephthalic acid, 16 g (4 mol%) of isophthalic acid, 44 g (8 mol%) of bisphenol A, p-hydroxybenzoic acid The mixture consisting of 295 g (50 mol%) of acid was heated at 240 ° C. for 2 hours with stirring in an autoclave to carry out an acidolysis reaction. Next, the temperature of the system was lowered to 140 ° C., 196 g of acetic anhydride was added, and the mixture was heated for 4 hours with stirring to carry out an acetylation reaction. Subsequently, the temperature of the system was raised to 230 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas, and the resin was discharged in a strand form. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polylactic acid.
When the resin composition of the obtained copolymer polylactic acid was examined, lactic acid / terephthalic acid / isophthalic acid / bisphenol A / p-hydroxybenzoic acid = 34 mol% / 4 mol% / 4 mol% / 8 mol% / 50 mol %Met.
Comparative Example 1
In an autoclave, a mixture of 266 g (50 mol%) of isophthalic acid, 365 g (50 mol%) of bisphenol A and 408 g of acetic anhydride was stirred in the autoclave while the temperature of the system was 140 ° C. while stirring. Acetylation reaction was performed by heating for a period of time. Subsequently, the temperature of the system was raised to 320 ° C., the pressure of the system was gradually reduced to 13 Pa after 1.5 hours, and a polycondensation reaction was performed while stirring. After 8 hours, the system was pressurized with nitrogen gas to discharge the resin in the form of a strand. After cooling with water, cutting was performed with a pelletizer to obtain a pelletized copolymer polyester.
When the resin composition of the obtained copolyester was examined, it was found to be isophthalic acid / bisphenol A = 50 mol% / 50 mol%.
Comparative Example 2
The performance of Cargill Dow polylactic acid 4031D was evaluated.
実施例１〜８で得られた共重合ポリ乳酸と、比較例１〜２の樹脂の各組成およびその特性値を表１に示した。 Table 1 shows the respective compositions and characteristic values of the copolymerized polylactic acid obtained in Examples 1 to 8 and the resins of Comparative Examples 1 and 2.
Claims (4)
A method for producing a copolymerized polylactic acid, characterized in that polylactic acid is acidified with an aromatic carboxylic acid and an aromatic hydroxycarboxylic acid, then acetylated with an aromatic alcohol, and subjected to condensation polymerization by deacetic acid.
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| JP2009242444A (en) * | 2008-03-28 | 2009-10-22 | Toray Ind Inc | Method for producing polylactic acid block copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225624A (en) * | 1988-03-04 | 1989-09-08 | Mitsubishi Gas Chem Co Inc | Manufacture of copolyester |
| JPH07501102A (en) * | 1991-11-21 | 1995-02-02 | サザン・リサーチ・インスティテュート | Polymers obtained from oxycarboxylic acids and polycarboxylic acids |
| JPH08100057A (en) * | 1994-09-29 | 1996-04-16 | Dainippon Ink & Chem Inc | Production of lactic acid copolymer |
| JP2002338666A (en) * | 2001-05-16 | 2002-11-27 | Teijin Ltd | Process for producing biodegradable copolyester |
| JP2002338669A (en) * | 2001-05-14 | 2002-11-27 | Nippon Ester Co Ltd | Process for producing liquid crystal polyester |
| JP2005220203A (en) * | 2004-02-04 | 2005-08-18 | Hitachi Ltd | Polymer synthesis apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01225624A (en) * | 1988-03-04 | 1989-09-08 | Mitsubishi Gas Chem Co Inc | Manufacture of copolyester |
| JPH07501102A (en) * | 1991-11-21 | 1995-02-02 | サザン・リサーチ・インスティテュート | Polymers obtained from oxycarboxylic acids and polycarboxylic acids |
| JPH08100057A (en) * | 1994-09-29 | 1996-04-16 | Dainippon Ink & Chem Inc | Production of lactic acid copolymer |
| JP2002338669A (en) * | 2001-05-14 | 2002-11-27 | Nippon Ester Co Ltd | Process for producing liquid crystal polyester |
| JP2002338666A (en) * | 2001-05-16 | 2002-11-27 | Teijin Ltd | Process for producing biodegradable copolyester |
| JP2005220203A (en) * | 2004-02-04 | 2005-08-18 | Hitachi Ltd | Polymer synthesis apparatus |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009242444A (en) * | 2008-03-28 | 2009-10-22 | Toray Ind Inc | Method for producing polylactic acid block copolymer |
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