WO2017013853A1 - 乳酸単位を含むaba型ブロック共重合体 - Google Patents
乳酸単位を含むaba型ブロック共重合体 Download PDFInfo
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- WO2017013853A1 WO2017013853A1 PCT/JP2016/003310 JP2016003310W WO2017013853A1 WO 2017013853 A1 WO2017013853 A1 WO 2017013853A1 JP 2016003310 W JP2016003310 W JP 2016003310W WO 2017013853 A1 WO2017013853 A1 WO 2017013853A1
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- lactic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6882—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
Definitions
- the present invention relates to an ABA type block copolymer containing lactic acid units.
- Patent Document 1 a crystalline segment made of a substantially homopolymer of poly L-lactic acid or poly D-lactic acid and an amorphous segment mainly composed of L-lactic acid and D-lactic acid are combined.
- Polylactic acid block copolymers have been proposed.
- Patent Document 2 proposes a block copolymer in which a polylactic acid segment and a vinyl polymer segment are bonded at a copolymerization ratio of 99/1 to 1/99 parts by weight.
- Patent Document 3 proposes a polylactic acid block copolymer having a segment composed of an L-lactic acid unit via a segment composed of a D-lactic acid unit at both ends of a segment mainly including an aliphatic carbonate unit.
- An object of the present invention is to provide a copolymer containing a repeating unit derived from lactic acid and having excellent physical properties such as toughness.
- ABA block comprising a polymer block A containing a repeating unit derived from lactic acid and a polymer block B containing a repeating unit represented by the formula [I] in the order of ABA. Polymer.
- R 1 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group
- R 2 and R 3 each independently represents: A hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group
- n represents an integer of 1 to 10.
- X represents —S—, —SO—.
- R 4 represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group.
- the ABA type block copolymer containing a lactic acid unit of the present invention is excellent in physical properties such as toughness.
- the polymer block A is a polymer block containing a repeating unit derived from lactic acid.
- the repeating unit derived from lactic acid is a repeating unit represented by the following formula [II].
- the carbon atom indicated by * is an asymmetric carbon atom.
- the repeating unit represented by the formula [II] contained in the polymer block A may be any of R form only, S form alone, a mixture of R form and S form, or a racemic form. Preferably only one of the bodies.
- the polymer block A includes a homopolymer consisting only of a repeating unit [II] derived from lactic acid, and a copolymer of a repeating unit [II] derived from lactic acid and a repeating unit derived from a monomer copolymerizable therewith. To do.
- Examples of the monomer that can be copolymerized with the repeating unit [II] derived from lactic acid include glycolic acid or a dimer thereof, hydroxyalkanoic acid, and ⁇ -caprolactone.
- the proportion of the repeating unit [II] derived from lactic acid in the polymer block A is 10 to 100% by weight, 20 to 100% by weight, 30 to 100% by weight, 40 to 100% by weight, 50 to 100% by weight, 60 to 100% by weight, 70 to 100% by weight, 80 to 100% by weight, 90 to 100% by weight and the like may be selected.
- the polymer block B is a polymer block containing a repeating unit represented by the formula [I].
- R 1 represents a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. Of these, R 1 is preferably a hydrogen atom.
- the alkyl group in R 1 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t
- alkyl groups having 1 to 6 carbon atoms such as -butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group and i-hexyl group.
- Examples of the aryl group for R 1 include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.
- Examples of the substituent of the “alkyl group having a substituent” include a halogen atom, an alkoxy group, and an aryl group.
- Examples of the substituent of the “aryl group having a substituent” include a halogen atom, an alkyl group, and an alkoxy group.
- the alkyl group portion of the alkyl group and alkoxy group the same groups as those exemplified for the alkyl group of R 1 can be exemplified.
- Examples of the aryl group include the same groups as those exemplified above for the aryl group for R 1 .
- R 2 and R 3 each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. Of these, R 2 and R 3 are preferably hydrogen atoms. Examples of the alkyl group in R 2 and R 3 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, and s-butyl.
- alkyl groups having 1 to 6 carbon atoms such as t-butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group and i-hexyl group.
- aryl group in R 2 and R 3 include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.
- substituents of the “alkyl group having a substituent” and the “aryl group having a substituent” the same substituents as those in R 1 can be exemplified.
- n represents an integer of 1 to 10, and n is preferably 2.
- X represents —S—, —SO—, or —SO 2 —, and is preferably —S—.
- R 4 represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted aryl group.
- alkyl group in R 4 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t
- alkyl groups having 1 to 6 carbon atoms such as -butyl group, i-pentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group and i-hexyl group.
- Examples of the aryl group for R 4 include aryl groups having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group.
- substituents of the “alkyl group having a substituent” and the “aryl group having a substituent” the same substituents as those in R 1 can be exemplified.
- the carbon atom indicated by * is an asymmetric carbon atom.
- the repeating unit represented by the formula [I] contained in the polymer block B may be either the R isomer only, the S isomer only, the mixture of the R isomer and the S isomer, or the racemic isomer, the R isomer or the S isomer. It is preferable that only one of them is present.
- the polymer block B includes a homopolymer consisting only of the repeating unit [I], and a copolymer of the repeating unit [I] and a repeating unit derived from a monomer copolymerizable therewith.
- Examples of the monomer copolymerizable with the repeating unit [I] include glycolic acid or a dimer thereof, hydroxyalkanoic acid, and ⁇ -caprolactone.
- the proportion of the repeating unit [I] in the polymer block B is 10 to 100% by weight, 20 to 100% by weight, 30 to 100% by weight, 40 to 100% by weight, 50 to 100% by weight, 60 to 100% by weight. 70 to 100% by weight, 80 to 100% by weight, 90 to 100% by weight, and the like.
- the ABA type block copolymer of the present invention comprises a polymer block A containing repeating units derived from lactic acid and a polymer block B containing repeating units represented by the formula [I] in the order of ABA. It is not particularly limited as long as it is a bonded ABA type block copolymer.
- the structure of the connection part of the block A and the block B is not specifically limited.
- the terminal structure of the ABA type block copolymer may be modified with various structures. Specifically, it can be modified by alkylating or esterifying the hydroxy group at the end of the polymer.
- the weight ratio of the polymer block A and the polymer block B in the ABA type block copolymer of the present invention is not particularly limited, but the total weight of the two polymer blocks A / the weight of the polymer block B is 20/80.
- a range of ⁇ 90/10, a range of 30 / 70-80 / 20, etc. may be selected.
- the weight average molecular weight (Mw) of the ABA type block copolymer of the present invention can be selected from 2,000 to 1,000,000, 3,000 to 500,000, 5,000 to 200,000, and the like. Further, the molecular weight distribution represented by the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.0, 1 0.0-2.0 etc. can be selected.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values obtained by converting data measured by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent into the molecular weight of standard polystyrene.
- the ABA type block copolymer of the present invention comprises a polymerization catalyst comprising a cyclic monomer represented by the formula [Ia] and a monomer that can be optionally copolymerized with the formula [Ia] in the presence of a diol compound serving as a polymerization initiator.
- a polymerization catalyst comprising a cyclic monomer represented by the formula [Ia] and a monomer that can be optionally copolymerized with the formula [Ia] in the presence of a diol compound serving as a polymerization initiator.
- R 1, R 2, R 3, n, X, R 4 are the same in formula (I), R 1, R 2, R 3, n, X, and R 4.
- the cyclic monomer represented by the formula [Ia] is a known compound described in WO2013 / 119959A1.
- Examples of the monomer that can be copolymerized with the formula [Ia] include glycolic acid or a dimer thereof, hydroxyalkanoic acid, and ⁇ -caprolactone.
- diol compound used as a polymerization initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol. Neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, and 2 , 4-diethyl-1,5-pentanediol and the like.
- the amount of the polymerization initiator used is preferably 0.001 to 10 mol% with respect to the total amount of monomers used in the first step and the second step.
- the polymerization catalyst examples include metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, and aluminum, or derivatives thereof. Specifically, for example, tin chloride, tin octylate, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, alkoxytitanium, germanium oxide, zirconium oxide and the like can be mentioned, among which tin octylate is preferably used. be able to. After the first step, the second step can be continued without adding a new polymerization catalyst.
- metals such as tin, zinc, titanium, bismuth, zirconium, germanium, antimony, and aluminum, or derivatives thereof.
- tin chloride, tin octylate, zinc chloride, zinc acetate, lead oxide, lead carbonate, titanium chloride, alkoxytitanium, germanium oxide, zirconium oxide and the like can be mentioned, among which tin
- the first step and the second step can be performed in the presence or absence of an organic solvent.
- the organic solvent only needs to be inert to the reaction and dissolve the monomer, and examples thereof include toluene, xylene, and cyclohexane.
- the reaction temperature is not particularly limited, but is preferably 50 to 170 ° C, more preferably 80 to 150 ° C.
- the reaction time is preferably 0.5 to 72 hours, more preferably 2 to 48 hours for each of the first step and the second step.
- the reaction system in which the first step has been performed After the first step, without isolating the product, by adding the lactide that is polymerized in the second step and, if necessary, the monomer that can be copolymerized with the lactide, to the reaction system in which the first step has been performed.
- the reaction can be carried out in one pot.
- the polymer block A is produced at both ends of the polymer block B obtained in the first step.
- Examples of the monomer copolymerizable with lactide include glycolic acid or a dimer thereof, hydroxyalkanoic acid, and ⁇ -caprolactone.
- the obtained ABA block polymer can be purified by a known purification method.
- the ABA type block copolymer of the present invention is a car interior material; a housing for home appliances; a container; a packaging material; a building material; a compost bag; a tape; a band; Medical materials such as sutures, vascular stents, biological cell carriers, drug carriers; ship bottom paints; antibacterial agents; sustained-release preparations;
- ABA block polymer 1 (129.80 g) was obtained by drying under reduced pressure at 60 ° C.
- the obtained ABA type block polymer 1 was subjected to GPC analysis and found to have a weight average molecular weight (Mw) of 101600 and a molecular weight distribution (Mw / Mn) of 1.87.
- the tensile strength (MPa) of each specimen was measured according to JIS K 7161-1: 2014. Izod impact strength (kj / m 2 ) was measured according to JIS K 7110: 1999. The Picat softening temperature (° C.) was measured according to JIS K 7206: 1999. The results are shown in Table 1.
- the tensile strength of the ABA block polymer 1 was about 1 ⁇ 2 compared to polylactic acid (TE-2000).
- the ABA type block polymer 1 Izod impact strength was about 15 times that of polylactic acid (TE-2000). Therefore, the ABA block polymer 1 has higher toughness than polylactic acid (TE-2000).
- the Picat softening temperature of ABA type block polymer 1 was equivalent to that of polylactic acid (TE-2000).
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Abstract
Description
本願は、2015年7月17日に出願された日本国特許出願第2015-143335号に対し優先権を主張し、その内容をここに援用する。
そのような欠点を改良するため、ポリ乳酸を様々なブロックポリマーにする試みが行われている。
重合体ブロックAは、乳酸由来の繰り返し単位を含む重合体ブロックである。乳酸由来の繰り返し単位とは、下記式〔II〕で表される繰り返し単位である。式〔II〕中、*で示した炭素原子は、不斉炭素原子である。重合体ブロックAに含まれる式〔II〕で表される繰り返し単位は、R体のみ、S体のみ、R体とS体の混合物、またはラセミ体のいずれであってもよく、R体またはS体のいずれか一方のみであるのが好ましい。
重合体ブロックBは、式〔I〕で表される繰り返し単位を含む重合体ブロックである。
R1におけるアルキル基としては、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、i-プロピル基、i-ブチル基、s-ブチル基、t-ブチル基、i-ペンチル基、ネオペンチル基、2-メチルブチル基、2,2-ジメチルプロピル基、i-ヘキシル基などの炭素数1~6のアルキル基などを挙げることができる。
R1におけるアリール基としては、フェニル基、ナフチル基などの炭素数6~10のアリール基などを挙げることができる。
「置換基を有するアルキル基」の置換基としては、ハロゲン原子、アルコキシ基、アリール基等が挙げられる。
「置換基を有するアリール基」の置換基としては、ハロゲン原子、アルキル基、アルコキシ基等を挙げることができる。
上記アルキル基およびアルコキシ基のアルキル基部分については、上記R1のアルキル基において例示されたものと同様の基を挙げることができる。アリール基としては、上記R1のアリール基において例示されたものと同様の基を挙げることができる。
R2、R3におけるアルキル基としては、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、i-プロピル基、i-ブチル基、s-ブチル基、t-ブチル基、i-ペンチル基、ネオペンチル基、2-メチルブチル基、2,2-ジメチルプロピル基、i-ヘキシル基などの炭素数1~6のアルキル基などを挙げることができる。
R2、R3におけるアリール基としては、フェニル基、ナフチル基などの炭素数6~10のアリール基などを挙げることができる。
「置換基を有するアルキル基」および「置換基を有するアリール基」の置換基としては、上記R1における置換基と同様のものを挙げることができる。
nは1~10いずれかの整数を示し、nが2であるのが好ましい。
R4におけるアルキル基としては、メチル基、エチル基、n-プロピル基、n-ブチル基、n-ペンチル基、n-ヘキシル基、i-プロピル基、i-ブチル基、s-ブチル基、t-ブチル基、i-ペンチル基、ネオペンチル基、2-メチルブチル基、2,2-ジメチルプロピル基、i-ヘキシル基などの炭素数1~6のアルキル基などを挙げることができる。
R4におけるアリール基としては、フェニル基、ナフチル基などの炭素数6~10のアリール基などを挙げることができる。
「置換基を有するアルキル基」および「置換基を有するアリール基」の置換基としては、上記R1における置換基と同様のものを挙げることができる。
本発明のABA型ブロック共重合体は、乳酸由来の繰り返し単位を含む重合体ブロックAと、式〔I〕で表される繰り返し単位を含む重合体ブロックBが、A-B-Aの順で結合してなるABA型ブロック共重合体である限り特に限定されない。ブロックAとブロックBの連結部位の構造は特に限定されない。また、ABA型ブロック共重合体の末端構造は各種の構造で変性されていてもよい。具体的には、重合体末端のヒドロキシ基をアルキル化やエステル化することにより、変性することができる。
本発明におけるABA型ブロック共重合体の製造方法を以下説明するが、以下の製法に限定されない。
式〔Ia〕で表される環状モノマーは、WO2013/119959A1に記載されている公知の化合物である。
重合開始剤の使用量は、第一工程および第二工程で使用するモノマー全量に対して、0.001~10モル%とするのが好ましい。
有機溶媒としては、反応に不活性であって、かつモノマーを溶解可能であればよく、例えばトルエン、キシレン、シクロヘキサン等が挙げられる。
本発明のABA型ブロック共重合体は、自動車の内装材;家電製品の筐体;容器;包装材料;建築用資材;コンポストバッグ;テープ;バンド;文房具;繊維;園芸用品;土嚢;カード;食器;縫合糸、脈管ステント、生体細胞担持体、薬剤担持体などの医療用材料;船底塗料;抗菌剤;徐放製剤;分散剤などの用途に用いることができる。
窒素気流袋中で500mLナスフラスコに3,6-ビス(2-(メチルチオ)エチル-1,4-ジオキサン-2,5-ジオン(40.21g、152mmol)およびジエチレングリコール(0.0732g、0.7mmol)とオクチル酸スズ(0.235g、0.6mmol)を添加し、130℃にて3時間撹拌した。次いで、140℃にて6時間攪拌した。一部をサンプリングしてGPC分析を行ったところ、重量平均分子量(Mw)33200、分子量分布(Mw/Mn)1.97のポリマーが生成していた。
その後、反応系内にラクチド(92.55g、642mmol)を添加し、140℃にて9時間撹拌した。得られた溶液にトルエン(450g)とテトラヒドロフラン(100g)を添加した後、その溶液をイソプロパノール(4L)に注ぎ入れた。析出したポリマー、ろ取した後、窒素気流下にて風乾させた。さらに、60℃にて減圧乾燥することでABA型ブロック重合体1(129.80g)を得た。得られたABA型ブロック重合体1をGPC分析したところ、重量平均分子量(Mw)101600、分子量分布(Mw/Mn)1.87であった。
実施例1で合成したポリマーについて、プレス成形により200mm×200mm×約2.0mmのシートを作成した後、ミリングマシンを用いて試験片の切削を行い評価試験片を作製した。また比較用としてポリ乳酸(ユニチカ社製、TE-2000)を使用して同様に評価試験片を作製した。
(プレス成形条件)
プレス条件(電熱プレス)
予熱:180℃×5分
加圧:180℃×1分
冷却:40℃×5分
(試験片切削条件)
使用機器:COESFELD社製CNCミリングマシンCPM403
(株)上島製作所製バンドソーL300
寿貿易(株)・(株)メカニクス製Shop-AceM18A小型スライス盤
Claims (1)
- 乳酸由来の繰り返し単位を含む重合体ブロックAと、式〔I〕で表される繰り返し単位を含む重合体ブロックBが、A-B-Aの順で結合してなるABA型ブロック共重合体。
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JP2017529444A JP6401864B2 (ja) | 2015-07-17 | 2016-07-13 | 乳酸単位を含むaba型ブロック共重合体 |
US15/576,419 US10240005B2 (en) | 2015-07-17 | 2016-07-13 | ABA block copolymer including lactic acid units |
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JP2015-143335 | 2015-07-17 | ||
JP2015143335 | 2015-07-17 |
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Citations (2)
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JPH11269097A (ja) * | 1998-01-20 | 1999-10-05 | Takeda Chem Ind Ltd | 新規な微粒子、その製造法および用途 |
JP2010540003A (ja) * | 2007-08-27 | 2010-12-24 | マスト バイオサージェリー アクチェンゲゼルシャフト | 治癒中の瘢痕組織を減ずるための再吸収性障壁微小膜 |
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JP4020441B2 (ja) | 1995-07-28 | 2007-12-12 | トヨタ自動車株式会社 | ポリ乳酸ブロック共重合体、その製造法及びその成型品 |
JP2007321141A (ja) | 2006-05-01 | 2007-12-13 | Toray Ind Inc | ポリ乳酸セグメントを含むブロック共重合体、その製造方法、および樹脂組成物 |
JP5293097B2 (ja) | 2008-11-07 | 2013-09-18 | 東洋紡株式会社 | ポリ乳酸系ブロック共重合体 |
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WO2012086569A1 (ja) * | 2010-12-20 | 2012-06-28 | 東レ株式会社 | 医療用生分解性粒子及び血管塞栓材料 |
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2016
- 2016-07-13 WO PCT/JP2016/003310 patent/WO2017013853A1/ja active Application Filing
- 2016-07-13 US US15/576,419 patent/US10240005B2/en not_active Expired - Fee Related
- 2016-07-13 JP JP2017529444A patent/JP6401864B2/ja not_active Expired - Fee Related
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JPH11269097A (ja) * | 1998-01-20 | 1999-10-05 | Takeda Chem Ind Ltd | 新規な微粒子、その製造法および用途 |
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LEEMHUIS, M. ET AL.: "Functionalized Poly(alpha- hydroxy acid)s via Ring-Opening Polymerization: Toward Hydrophilic Polyesters with Pendant Hydroxyl Groups", MACROMOLECULES, vol. 39, no. 10, 2006, pages 3500 - 3508, XP002546692 * |
RYNER, M. ET AL.: "Resorbable and Highly Elastic Block Copolymers from 1,5- Dioxepan-2-one and L-Lactide with Controlled Tensile Properties and Hydrophilicity", BIOMACROMOLECULES, vol. 3, 2002, pages 601 - 608, XP055348091 * |
Also Published As
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US20180155504A1 (en) | 2018-06-07 |
US10240005B2 (en) | 2019-03-26 |
JPWO2017013853A1 (ja) | 2018-03-29 |
JP6401864B2 (ja) | 2018-10-10 |
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