JP2009242444A5 - - Google Patents
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- JP2009242444A5 JP2009242444A5 JP2008087249A JP2008087249A JP2009242444A5 JP 2009242444 A5 JP2009242444 A5 JP 2009242444A5 JP 2008087249 A JP2008087249 A JP 2008087249A JP 2008087249 A JP2008087249 A JP 2008087249A JP 2009242444 A5 JP2009242444 A5 JP 2009242444A5
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- polylactic acid
- block copolymer
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- acid
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- 229920000747 poly(lactic acid) polymer Polymers 0.000 claims description 46
- 239000004626 polylactic acid Substances 0.000 claims description 45
- 229920001400 block copolymer Polymers 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 31
- 229920000728 polyester Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 10
- -1 spiroglycol Chemical compound 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 6
- 229960002479 Isosorbide Drugs 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 150000003460 sulfonic acids Chemical class 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N 2,6-Naphthalenedicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N Isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000005712 crystallization Effects 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N dilactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002506 iron compounds Chemical class 0.000 claims description 2
- 150000002611 lead compounds Chemical class 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid group Chemical group C(C=1C(C(=O)O)=CC=CC1)(=O)O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- 229940100888 zinc compounds Drugs 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004581 coalescence Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Description
すなわち、本発明は、以下のとおりである。
１．下記３つの工程を含む乳酸および／またはその誘導体を主原料とする無溶媒下のポリ乳酸の直接重縮合工程の任意の段階で、
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルを構成するモノマー、
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルのオリゴマー、
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルから選ばれる少なくとも１つを投入することを特徴とするポリ乳酸ブロック共重合体の製造方法。
（Ａ）第１工程として、乳酸および／またはその誘導体を、下記から選ばれる少なくとも３つ以上の条件下で反応させ、数平均分子量１万未満の低分子量体を製造する工程。
（ａ−１）無触媒
（ａ−２）１００〜１８０℃の温度
（ａ−３）０．１３〜１３０００Ｐａの圧力
（ａ−４）０．３〜１５時間の反応時間
（Ｂ）第２工程として、第１工程で得られた低分子量体を、触媒存在下で反応させ、数平均分子量５千以上５万未満のプレポリマーを製造する工程。
（Ｃ）第３工程として、第２工程で得られたプレポリマーを、１２０〜１６５℃の温度で固相重合を行い、数平均分子量５万以上のポリマーを製造する工程。
２．前記芳香族ポリエステルを構成するジカルボン酸成分が、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、コハク酸、およびフタル酸から選ばれる少なくとも１つであることを特徴とする上記１に記載のポリ乳酸ブロック共重合体の製造方法。
３．前記芳香族ポリエステルのオリゴマーの数平均分子量が５００以上２万以下であることを特徴とする上記１〜２のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
４．ポリ乳酸の直接重縮合工程の任意の段階で投入する前記芳香族ポリエステルの数平均分子量が２万を超えることを特徴とする上記１〜２のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
５．芳香族ポリエステルを、乳酸単位（ｘ）と前記芳香族ポリエステル単位（ｙ）の構成比がｘ／ｙ＝９９／１〜７１／２９モル％となる添加量で投入することを特徴とする上記１〜４のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
６．前記（Ｂ）第２工程の後に、前記芳香族ポリエステルを投入することを特徴とする上記１〜５のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
７．前記（Ｂ）第２工程を、下記の条件下で行うことを特徴とする上記１〜６のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
（ｂ−１）１４０〜２４０℃の温度
（ｂ−２）０．１３〜１３０００Ｐａの圧力
８．前記（Ｂ）第２工程終了後かつ（Ｃ）第３工程開始前に、５０〜１５０℃の温度で結晶化処理を行うことを特徴とする上記１〜７のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
９．前記（Ａ）第１工程開始時から（Ｃ）第３工程終了後のいずれかの段階において、触媒失活剤を添加することを特徴とする上記１〜８のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
１０．前記（Ａ）第１工程および／または（Ｂ）第２工程において、反応槽と還流装置を接続した装置を用いることを特徴とする上記１〜９のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
１１．前記（Ａ）第１工程および／または（Ｂ）第２工程で用いる反応槽が、二つ以上の反応室から構成されていることを特徴とする上記１０に記載のポリ乳酸ブロック共重合体の製造方法。
１２．前記（Ａ）第１工程、（Ｂ）第２工程および（Ｃ）第３工程から選ばれるいずれか一つ以上の工程において、揮発成分のうち、水を除去し、かつ、乳酸およびラクチドまたはそれらの低分子量重合体を（Ａ）第１工程および／または（Ｂ）第２工程の反応槽に戻すことを特徴とする上記１〜１１のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
１３．前記（Ｂ）第２工程の触媒として、錫化合物、チタン化合物、鉛化合物、亜鉛化合物、コバルト化合物、鉄化合物、リチウム化合物、希土類化合物、およびスルホン酸化合物から選択されるいずれか１種以上を用いることを特徴とする上記１〜１２のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
１４．前記（Ｂ）第２工程の触媒として、錫化合物から選択される１種以上およびスルホン酸化合物から選択される１種以上を用いることを特徴とする上記１〜１３のいずれかに記載のポリ乳酸ブロック共重合体の製造方法。
１５．錫化合物が、酢酸錫（ＩＩ）および／またはオクチル酸錫（ＩＩ）であり、スルホン酸化合物が、メタンスルホン酸および／またはエタンスルホン酸であることを特徴とする上記１４に記載のポリ乳酸ブロック共重合体の製造方法。
That is, the present invention is as follows.
1. In any stage of the direct polycondensation step of polylactic acid in the absence of a solvent using lactic acid and / or a derivative thereof as a main raw material , including the following three steps:
A monomer constituting an aromatic polyester comprising at least one selected from isosorbide, spiroglycol, and bisphenol A as a constituent ;
An aromatic polyester oligomer comprising at least one member selected from isosorbide, spiroglycol, and bisphenol A ;
A method for producing a polylactic acid block copolymer, comprising charging at least one selected from aromatic polyesters containing at least one selected from isosorbide, spiroglycol, and bisphenol A as a constituent component .
(A) A step of producing a low molecular weight product having a number average molecular weight of less than 10,000 by reacting lactic acid and / or a derivative thereof under at least three conditions selected from the following as the first step.
(A-1) No catalyst
(A-2) Temperature of 100 to 180 ° C
(A-3) 0.13 to 13000 Pa pressure
(A-4) Reaction time of 0.3 to 15 hours
(B) As a 2nd process, the low molecular weight body obtained at the 1st process is made to react in catalyst presence, and the process of manufacturing a prepolymer with a number average molecular weight of 5,000 or more and less than 50,000.
(C) As a third step, a step of producing a polymer having a number average molecular weight of 50,000 or more by subjecting the prepolymer obtained in the second step to solid phase polymerization at a temperature of 120 to 165 ° C.
2. Dicarboxylic acid component constituting the aromatic polyester is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, according to the above 1, wherein the succinic acid, and at least one is selected from phthalic acid A method for producing a polylactic acid block copolymer.
3. Method for producing a polylactic acid block copolymer according to any one of 1-2, wherein the number-average molecular weight of the oligomer of the aromatic polyester is from 500 to 20,000 or less.
4). The number average molecular weight of the aromatic polyester Le to introduce at any stage of the direct polycondensation process of the polylactic acid is equal to or more than 20,000 polylactic acid block copolymer according to any one of the above 1-2 Production method.
5. The 1, wherein placing the aromatic polyester, the addition amount of the composition ratio of lactic acid units (x) and the aromatic polyester unit (y) is the x / y = 99 / 1~71 / 29 mol% The manufacturing method of the polylactic acid block copolymer in any one of -4.
6). Wherein (B) after the second step, the production method of polylactic acid block copolymer according to any one of the above 1 to 5, characterized in that introducing the aromatic polyester Le.
7). (B) The method for producing a polylactic acid block copolymer according to any one of 1 to 6 above , wherein the second step is performed under the following conditions.
(B-1) 140-240 ° C. (b-2) 0.13-13000 Pa pressure The polylactic acid block according to any one of 1 to 7 above , wherein crystallization treatment is performed at a temperature of 50 to 150 ° C. after the completion of the (B) second step and (C) before the start of the third step. A method for producing a copolymer.
9. 9. The polylactic acid block according to any one of 1 to 8 above , wherein a catalyst deactivator is added at any stage from the start of the (A) first process to the end of the (C) third process. A method for producing a copolymer.
10. The polylactic acid block copolymer as described in any one of 1 to 9 above, wherein in the (A) first step and / or (B) second step, a device in which a reaction vessel and a reflux device are connected is used. Manufacturing method.
11. 11. The polylactic acid block copolymer according to 10 above , wherein the reaction vessel used in the (A) first step and / or (B) second step is composed of two or more reaction chambers. Production method.
12 In any one or more steps selected from (A) the first step, (B) the second step, and (C) the third step, water is removed from the volatile components, and lactic acid and lactide or those The method for producing a polylactic acid block copolymer according to any one of 1 to 11 above , wherein the low molecular weight polymer is returned to the reaction tank of (A) the first step and / or (B) the second step. .
13. As the catalyst in the second step (B), any one or more selected from tin compounds, titanium compounds, lead compounds, zinc compounds, cobalt compounds, iron compounds, lithium compounds, rare earth compounds, and sulfonic acid compounds are used. The method for producing a polylactic acid block copolymer as described in any one of 1 to 12 above .
14 The polylactic acid according to any one of 1 to 13 above, wherein as the catalyst in the second step (B), one or more selected from tin compounds and one or more selected from sulfonic acid compounds are used. A method for producing a block copolymer.
15. 15. The polylactic acid block according to 14 above , wherein the tin compound is tin (II) acetate and / or tin (II) octylate, and the sulfonic acid compound is methanesulfonic acid and / or ethanesulfonic acid. A method for producing a copolymer.
本発明のポリ乳酸ブロック共重合体の製造方法では、乳酸および／またはその誘導体を主原料とする無溶媒下のポリ乳酸の直接重縮合工程の任意の段階で、芳香族ポリエステルを構成するモノマー、芳香族ポリエステルのオリゴマー、芳香族ポリエステルのから選ばれる少なくとも１つを投入する。 In the method for producing a polylactic acid block copolymer of the present invention, a monomer constituting an aromatic polyester at any stage of a direct polycondensation step of polylactic acid in the absence of a solvent using lactic acid and / or a derivative thereof as a main raw material, At least one selected from oligomers of aromatic polyesters and aromatic polyesters is added.
本発明において、ポリ乳酸の直接重縮合工程は下記３つの工程からなる。
（Ａ）第１工程として、乳酸および／またはその誘導体を、下記から選ばれる少なくとも３つ以上の条件下で反応させ、数平均分子量１万未満の低分子量体を製造する工程。
（ａ−１）無触媒
（ａ−２）１００〜１８０℃の温度
（ａ−３）０．１３〜１３００Ｐａの圧力
（ａ−４）０．３〜１５時間の反応時間
（Ｂ）第２工程として、第１工程で得られた低分子量体を、触媒存在下、数平均分子量５千以上５万未満のプレポリマーを製造する工程。
（Ｃ）第３工程として、第２工程で得られたプレポリマーを、１２０〜１６５℃の温度で固相重合を行い、数平均分子量５万以上のポリマーを製造する工程。
In the present invention, the direct polycondensation step of polylactic acid comprises the following three steps.
(A) A step of producing a low molecular weight product having a number average molecular weight of less than 10,000 by reacting lactic acid and / or a derivative thereof under at least three conditions selected from the following as the first step.
(A-1) Non-catalyst (a-2) Temperature of 100 to 180 ° C. (a-3) Pressure of 0.13 to 1300 Pa (a-4) Reaction time of 0.3 to 15 hours (B) Second step As a process for producing a prepolymer having a number average molecular weight of 5,000 or more and less than 50,000, in the presence of a catalyst, the low molecular weight product obtained in the first step.
(C) A step of producing a polymer having a number average molecular weight of 50,000 or more by subjecting the prepolymer obtained in the second step to solid phase polymerization at a temperature of 120 to 165 ° C. as the third step.
なお、ポリ乳酸直接重縮合工程に投入する芳香族ポリエステルのオリゴマーの数平均分子量が５００以上２万以下であることが好ましく、高分子量および高ガラス転移点を有し、熱安定性および色相にも優れるポリ乳酸ブロック共重合体を効率的に得ることができるという点で１千以上２万以下であることがより好ましい。また、ポリ乳酸直接重縮合工程に投入する芳香族ポリエステルの数平均分子量は２万を超えることが好ましく、２．５万を超えることが高分子量および高ガラス転移点を有し、熱安定性および色相にも優れるポリ乳酸ブロック共重合体を効率的に得ることができるという点でより好ましい。 In addition, it is preferable that the number average molecular weight of the oligomer of the aromatic polyester to be charged into the polylactic acid direct polycondensation step is 500 or more and 20,000 or less, which has a high molecular weight and a high glass transition point, and also has good thermal stability and hue. It is more preferably from 1,000 to 20,000 in that an excellent polylactic acid block copolymer can be obtained efficiently. The number average molecular weight of the aromatic polyester Le to be introduced into the polylactide direct polycondensation step is preferably more than 20,000, to be greater than 25,000 have a high molecular weight and high glass transition temperature, thermal stability And a polylactic acid block copolymer having an excellent hue is more preferable in that it can be obtained efficiently.
芳香族ポリエステルを構成する固体状モノマー、芳香族ポリエステルのオリゴマー、ポリ乳酸直接重縮合工程に投入する芳香族ポリエステルの形状および大きさは、球状またはペレット状で、長径が５ｍｍ以下であることが好ましく、３ｍｍ以下であることがより好ましく、１ｍｍ以下であることが生産性の点から特に好ましい。液状モノマーは液状のまま使用することが好ましい。 The solid monomer constituting the aromatic polyester, the oligomer of the aromatic polyester, and the shape and size of the aromatic polyester charged into the polylactic acid direct polycondensation step are preferably spherical or pellets, and the major axis is preferably 5 mm or less. 3 mm or less is more preferable, and 1 mm or less is particularly preferable from the viewpoint of productivity. The liquid monomer is preferably used in a liquid state.
芳香族ポリエステルを構成するモノマー、芳香族ポリエステルのオリゴマー、ポリ乳酸直接重縮合工程に投入する芳香族ポリエステル全体の添加量はポリ乳酸単位（ｘ）と芳香族ポリエステル単位（ｙ）の構成比がｘ／ｙ＝９９／１〜７１／２９モル％に相当する量が好ましく、高分子量および高ガラス転移点を有し、熱安定性および色相にも優れるポリ乳酸ブロック共重合体を効率的に得ることができるという点でｘ／ｙ＝９９／１〜８０／２０がより好ましく、ｘ／ｙ＝９５／５〜８５／１５が特に好ましい。また、モノマー、オリゴマー、ポリマーの比率は限定されないが、ポリマーの割合が多い方が高分子量および高ガラス転移点を有し、熱安定性および色相にも優れるポリ乳酸ブロック共重合体を効率的に得ることができるという点で好ましい。 The monomer constituting the aromatic polyester, the oligomer of the aromatic polyester, and the total amount of the aromatic polyester added to the polylactic acid direct polycondensation step are such that the composition ratio of the polylactic acid unit (x) to the aromatic polyester unit (y) is x. An amount corresponding to / y = 99/1 to 71/29 mol% is preferable, and a polylactic acid block copolymer having a high molecular weight, a high glass transition point, and excellent thermal stability and hue is efficiently obtained. X / y = 99/1 to 80/20 is more preferable, and x / y = 95/5 to 85/15 is particularly preferable. The ratio of monomers, oligomers, and polymers is not limited, but the higher the polymer ratio, the higher the molecular weight and the high glass transition point, and the more efficient the polylactic acid block copolymer with excellent thermal stability and hue. It is preferable in that it can be obtained.
芳香族ポリエステルを構成するモノマーは（Ａ）第１工程前〜（Ｂ）第２工程前の段階で投入することが好ましく、重合性の点から（Ａ）第１工程前の段階で投入することがより好ましい。また、オリゴマーおよびポリマーは（Ｂ）第２工程前〜（Ｃ）第３工程後の段階で投入することが好ましく、混合性の点から（Ｂ）第２工程後〜（Ｃ）第３工程後の段階で投入することがより好ましい。 The monomer constituting the aromatic polyester is preferably added at the stage before (A) the first process to (B) before the second process, and (A) from the point of polymerizability, it is introduced at the stage before the first process. Is more preferable. In addition, the oligomer and polymer are preferably added at the stage of (B) before the second step to (C) after the third step. From the viewpoint of mixing properties, (B) after the second step to (C) after the third step. It is more preferable to input at this stage.
次に、第３工程について説明する。本発明において、（Ｃ）第３工程は、第２工程で得られたプレポリマーを、１２０〜１６５℃の温度で固相重合を行い、数平均分子量５万以上のポリマーを製造する工程である。 Next, the third step will be described. In the present invention, (C) the third step is a step of producing a polymer having a number average molecular weight of 50,000 or more by subjecting the prepolymer obtained in the second step to solid phase polymerization at a temperature of 120 to 165 ° C. .
本発明において、（Ｃ）第３工程は、高分子量および高ガラス転移点を有し、色相にも優れるポリ乳酸ブロック共重合体を効率的に得ることができるという点で、１２０〜１６５℃の温度で行うが、１４０〜１６０℃の温度で行うことがより好ましく、１４５〜１５５℃の温度で行うことがさらに好ましい。また、（Ｃ）第３工程の温度は、１段階でもよく、２段階以上の多段階でもよいが、短時間で高分子量化しやすく、色相にも優れるという点で、２段階以上の多段階とすることが好ましく、反応の進行とともに温度を段階的に上げることがより好ましく、例えば、１２０〜１４０℃の温度で反応を行った後、１４０〜１６５℃の温度で反応を行う方法などが挙げられる。 In the present invention, (C) a third step has a high molecular weight and high glass transition point, in that it is possible to obtain a polylactic acid block copolymer is excellent in hue efficiently, the from 120 to 165 ° C. is carried out at a temperature, and more preferably performed at a temperature of 140 to 160 ° C., more preferably it is carried out at a temperature of 145-155 ° C.. (C) The temperature of the third step may be one step or may be two or more steps, but it is easy to increase the molecular weight in a short time and is excellent in hue. It is preferable to increase the temperature step by step as the reaction proceeds. For example, a method in which the reaction is performed at a temperature of 120 to 140 ° C. and then the reaction is performed at a temperature of 140 to 165 ° C. .
Claims (15)
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルを構成するモノマー、
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルのオリゴマー、
イソソルビド、スピログリコール、およびビスフェノールＡから選ばれる少なくとも１つを構成成分とする芳香族ポリエステルから選ばれる少なくとも１つを投入することを特徴とするポリ乳酸ブロック共重合体の製造方法。
（Ａ）第１工程として、乳酸および／またはその誘導体を、下記から選ばれる少なくとも３つ以上の条件下で反応させ、数平均分子量１万未満の低分子量体を製造する工程。
（ａ−１）無触媒
（ａ−２）１００〜１８０℃の温度
（ａ−３）０．１３〜１３０００Ｐａの圧力
（ａ−４）０．３〜１５時間の反応時間
（Ｂ）第２工程として、第１工程で得られた低分子量体を、触媒存在下で反応させ、数平均分子量５千以上５万未満のプレポリマーを製造する工程。
（Ｃ）第３工程として、第２工程で得られたプレポリマーを、１２０〜１６５℃の温度で固相重合を行い、数平均分子量５万以上のポリマーを製造する工程。 In any stage of the direct polycondensation step of polylactic acid in the absence of a solvent using lactic acid and / or a derivative thereof as a main raw material , including the following three steps:
A monomer constituting an aromatic polyester comprising at least one selected from isosorbide, spiroglycol, and bisphenol A as a constituent ;
An aromatic polyester oligomer comprising at least one member selected from isosorbide, spiroglycol, and bisphenol A ;
A method for producing a polylactic acid block copolymer, comprising charging at least one selected from aromatic polyesters containing at least one selected from isosorbide, spiroglycol, and bisphenol A as a constituent component .
(A) A step of producing a low molecular weight product having a number average molecular weight of less than 10,000 by reacting lactic acid and / or a derivative thereof under at least three conditions selected from the following as the first step.
(A-1) No catalyst
(A-2) Temperature of 100 to 180 ° C
(A-3) 0.13 to 13000 Pa pressure
(A-4) Reaction time of 0.3 to 15 hours
(B) As a 2nd process, the low molecular weight body obtained at the 1st process is made to react in catalyst presence, and the process of manufacturing a prepolymer with a number average molecular weight of 5,000 or more and less than 50,000.
(C) As a third step, a step of producing a polymer having a number average molecular weight of 50,000 or more by subjecting the prepolymer obtained in the second step to solid phase polymerization at a temperature of 120 to 165 ° C.
（ｂ−１）１４０〜２４０℃の温度
（ｂ−２）０．１３〜１３０００Ｐａの圧力 The method for producing a polylactic acid block copolymer according to any one of claims 1 to 6, wherein the (B) second step is performed under the following conditions.
(B-1) Temperature of 140 to 240 ° C. (b-2) Pressure of 0.13 to 13000 Pa
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