JPS6369825A - Block copolymer and production thereof - Google Patents
Block copolymer and production thereofInfo
- Publication number
- JPS6369825A JPS6369825A JP61214781A JP21478186A JPS6369825A JP S6369825 A JPS6369825 A JP S6369825A JP 61214781 A JP61214781 A JP 61214781A JP 21478186 A JP21478186 A JP 21478186A JP S6369825 A JPS6369825 A JP S6369825A
- Authority
- JP
- Japan
- Prior art keywords
- lactide
- polyoxyethylene
- block copolymer
- telechelic
- acid segment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 21
- -1 polyoxyethylene Polymers 0.000 claims abstract description 16
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 13
- 239000004626 polylactic acid Substances 0.000 claims abstract description 12
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 238000012643 polycondensation polymerization Methods 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 238000002844 melting Methods 0.000 abstract description 5
- 230000008018 melting Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000011261 inert gas Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract 3
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 101000972349 Phytolacca americana Lectin-A Proteins 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医療性利用、特に生物吸収可能なフィルムに
適した、ポリ乳酸を−に成分とするブロック共重合体お
よびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a block copolymer mainly composed of polylactic acid, which is suitable for medical use, particularly for bioabsorbable films, and a method for producing the same.
従来ポリ乳酸は、Ｌ−ラクタイド、又はＤｌ−−ラクタ
イドの開環重合より得られ、種々の重合度のものが知ら
れている。Conventionally, polylactic acid is obtained by ring-opening polymerization of L-lactide or Dl-lactide, and polylactic acids with various degrees of polymerization are known.
しかしながら、ポリ乳酸をフィルムに加Ｔすると、もろ
く、柔軟性に乏しく、生体内で使用覆るには吸水性に欠
けるという問題点がある。However, when polylactic acid is added to a film, it becomes brittle, has poor flexibility, and lacks water absorption for use in vivo.
本発明者らは、これらの問題点を踏まえポリ乳酸の高分
子鎖中に親水性の高いポリオキシエチレン基を導入する
ことを考え、ラクタイドとポリオキシエチレンの重合を
試みたがポリオ−キシエチレンの水酸基が、ラクタイド
の重合を阻害することにより、フィルム形成性を有しな
い、重合度の低い共重合体しか得られなかった。In view of these problems, the present inventors considered introducing a highly hydrophilic polyoxyethylene group into the polymer chain of polylactic acid, and attempted to polymerize lactide and polyoxyethylene. Since the hydroxyl groups inhibited the polymerization of lactide, only a copolymer with a low degree of polymerization and no film-forming properties was obtained.
そこで、本発明者らはさらに鋭意検Ｎを川ねた結果、エ
ステル交換タイプの反応ならばポリ乳酸鎖の重合度をそ
こねないことを見出し、ポリオ−キシエチレン基を有す
るジカルボン酸エステルであるポリオキシエチレンテレ
ケリツク酸エステルを用いることにより、柔軟性、親水
性を有し、フィルム形成性に富んだブロック共重合体を
得ることに成功し、本発明を完成させたものである。Therefore, the present inventors conducted further extensive research and found that a transesterification type reaction would not impair the degree of polymerization of polylactic acid chains. By using oxyethylene telechelic acid ester, we succeeded in obtaining a block copolymer having flexibility, hydrophilicity, and excellent film-forming properties, thereby completing the present invention.
すなわら、本発明は、
式
：
で表されポリ乳酸セグメント（Ａ）７０〜９７重量％と
ポリオキシエヂレンジカルボン酸セグメント（Ｂ）３〜
３０重量％から４ｆるブロック共重合体。That is, the present invention is represented by the formula: 70 to 97% by weight of a polylactic acid segment (A) and 3 to 97% by weight of a polyoxyethylene dicarboxylic acid segment (B)
30% to 4f block copolymer.
及び、Ｌ−ラクタイド及び又はＤ Ｌ−ラクタイドと式
（式中Ｒはアルキル基を示す）で示されるポリオキシエ
チレンテレケリツク酸エステルとを水分を除去した系中
加熱することによりエステル交換反応により綜合重合し
て前記ブロック共重合体を製造する方法である。And, by heating L-lactide and/or D L-lactide and polyoxyethylene telechelic acid ester represented by the formula (in the formula, R represents an alkyl group) in a system from which water has been removed, a transesterification reaction is carried out. This is a method for producing the block copolymer by polymerization.
本発明に用いるポリオキシエチレンテレケリツク酸エス
テル（以１１ＰＥＯエステルと略す）の分子量は１００
乃至１００００のものが使用出来、好ましくは４００乃
至４０００のものが良い。The molecular weight of the polyoxyethylene telechelic acid ester (hereinafter abbreviated as 11PEO ester) used in the present invention is 100.
A number between 10,000 and 10,000 can be used, preferably between 400 and 4,000.
ＰＥＯエステルのアルキル基は飽和脂肪族アルキル基で
あれば好ましく、特にメチル基が好ましい。The alkyl group of the PEO ester is preferably a saturated aliphatic alkyl group, particularly preferably a methyl group.
ＰＥＯエステルは、ポリオキシエチレンテレケリツク酸
エステル（日本触媒化学■業■より販売されている）を
常法によりエステル化して調整する。メチルエステルを
得るためにはメタノール中でパラトルエンスルホン酸等
の触媒を用いてエステル化するとＰＥＯメチルニスデル
が得られる。PEO ester is prepared by esterifying polyoxyethylene telechelic acid ester (sold by Nippon Shokubai Kagaku ■) by a conventional method. In order to obtain methyl ester, PEO methylnisder is obtained by esterification using a catalyst such as para-toluenesulfonic acid in methanol.
本発明に用いるラクタイドは、１−−ラクタイドであれ
ば融点９７℃以−ヒのものを用い、ＤＬ−ラクタイドで
あれば融点１２７°Ｃ以上のものを用いる。使用するラ
クタイドは、し体、Ｄｌ体の単独のみならず１体とＤｌ
体との混合物であってもよい。The lactide used in the present invention is 1-lactide with a melting point of 97°C or higher, and DL-lactide with a melting point of 127°C or higher. The lactide used is not only single lactide and Dl body, but also one body and Dl body.
It may be a mixture with the body.
Ｐ Ｅ Ｏエステルとラクタイドは目的の共重合体の組
成に応じラクタイド１００重量部に対しＰＥＯエステル
５〜１００重聞部の範囲から選ばれた最が用いられる。The amount of PEO ester and lactide used is selected from the range of 5 to 100 parts by weight of PEO ester per 100 parts by weight of lactide, depending on the composition of the desired copolymer.
重合は、ＰＥＯエステルとラクタイドを真空乾燥し、不
活性ガス置換し水分を完全に除去した後、不活性ガス置
換下、少量の乾燥溶媒に加熱溶解し、ジエチル亜鉛など
の触媒をラクタイドの数％程度加え、５０〜１００℃程
度の温度で撹拌下０．５〜数時間反応させることによっ
て行われる。For polymerization, PEO ester and lactide are vacuum-dried, replaced with inert gas to completely remove moisture, and then heated and dissolved in a small amount of dry solvent under inert gas replacement, and a catalyst such as diethylzinc is added to a few percent of lactide. The reaction is carried out by stirring at a temperature of about 50 to 100° C. for 0.5 to several hours.
本発明において、ポリマーの物性は以下の通りの方法で
分析した。In the present invention, the physical properties of the polymer were analyzed by the following method.
数平均分子量
ＧＰＣを用い、ポリマーをＴＨＦに０．１ｗｔ％の割合
で溶解させ、スヂレンスタンダードによって分子量を得
た。Number average molecular weight Using GPC, the polymer was dissolved in THF at a ratio of 0.1 wt%, and the molecular weight was obtained using a sutylene standard.
ＮＭＲ
ポリマーを１％ＴＭＳ、重クロロホルム溶媒に溶解させ
測定した。NMR The polymer was dissolved in 1% TMS and deuterated chloroform solvent and measured.
粘度測定
クロロホルムを溶媒に用い、０．５ｇ／ｄ、Ｉｌの溶液
で３０±０．１℃で測定し、η３．／Ｃを算出した。Viscosity measurement Using chloroform as a solvent, the viscosity was measured at 30±0.1°C with a solution of 0.5 g/d, Il, and η3. /C was calculated.
引張強度、初期ヤング率、伸度
ホットプレス（５０Ｋｆｌ ／ ｃ＃ｉ）によりフィル
ム作成後５＃Ｘ２０１Ｍの試料を切り取り引張試験機に
て測定した。Tensile strength, initial Young's modulus, and elongation were measured using a tensile tester after a film was prepared using a hot press (50 Kfl/c#i) and a 5#x201M sample was cut out.
以下の実施例は本発明の好適な具体例であるが、本発明
を限定するものではない。The following examples are preferred embodiments of the invention, but are not intended to limit the invention.
実施例１
ＰＥＯメヂメチステル２ｇとＤｌ−−ラクタイド２０９
とを５００蛇のナス型フラス」に装入し、５０℃で加熱
しながら１０時間真空乾燥、窒素置換し水分を完全に除
去した。窒素置換した］ヘルエン５ｄを加え、８０℃で
反応物を溶解さＶた後、触媒ジエチル亜鉛１ｙ（ラクタ
イドの５ｗｔ％）を加え１時間撹拌しながら重合した。Example 1 PEO medimethister 2g and Dl--lactide 209
The mixture was placed in a 500-sized eggplant-shaped flask and dried under vacuum for 10 hours while heating at 50°C, and the water was completely removed by replacing the mixture with nitrogen. After the reactant was dissolved at 80° C., the catalyst diethylzinc 1y (5 wt % of lactide) was added and polymerized with stirring for 1 hour.
重合終了後無水酢酸５ ｍｌを加え末端アセチル化を行
なうことによって、重合を停止させた。生成物をｎ−ヘ
キサン中に注ぎ再沈殿させ、単離したあとエーテルで３
回洗浄し乾燥後２０．７ｇ（収率９４％）のポリマー（
数平均分子機３１，０００．η８．／ＣＯ，４４）を得
た。このもののＮＭＲスペクトルを調べたところ乳酸鎖
（ＰＬＡ鎖）に基づく特性スペク１〜ル（１，４及び５
．０ＤＤｍ）とＰＦＯ鎖に基づく特性スペクトル（３，
５ｐｐｍ）を検出した。それぞれのモル比（Ｐ Ｌ Ａ
／ Ｐ Ｅ Ｏ）は９２／８であった。After the polymerization was completed, 5 ml of acetic anhydride was added to carry out terminal acetylation to terminate the polymerization. The product was reprecipitated by pouring it into n-hexane, isolated and diluted with ether for 3 hours.
After washing twice and drying, 20.7 g (yield 94%) of polymer (
Number average molecular machine 31,000. η8. /CO,44) was obtained. When we investigated the NMR spectrum of this product, we found characteristic spectra 1 to 1 (1, 4 and 5) based on lactic acid chains (PLA chains).
．． 0DDm) and characteristic spectra based on PFO chains (3,
5 ppm) was detected. Each molar ratio (PLA
/PEO) was 92/8.
Ｉ Ｒで調べた結果、１３００ｃｍ−’ 〜１０００ｃ
ｍ−１にＰ ＩＥ Ｏ鎖に基づく特性吸収が見られ、１
７５０ｃｍ−１にエステルの特性吸収が見られ、これら
ＭＮＲとＩＲの結果よりブロック共重合体であることが
確認された。As a result of checking with IR, 1300cm-'~1000c
A characteristic absorption based on the PIE O chain is seen at m-1, and 1
A characteristic absorption of ester was observed at 750 cm-1, and the MNR and IR results confirmed that it was a block copolymer.
このブロック共重合体を６０℃でボッ１ヘプレスしてフ
ィルムを作成し、引張試験の結果、引張強度２．２Ｋｇ
／１ＩＩＩＩｌ、初期ヤング率３．８Ｋｇ／ｍｍ２、伸
度９９％である柔軟性の良いフィルムが得られ１こ 。This block copolymer was pressed into a ball at 60°C to create a film, and as a result of a tensile test, the tensile strength was 2.2 kg.
A flexible film with an initial Young's modulus of 3.8 Kg/mm2 and an elongation of 99% was obtained.
実施例２
ＰＥＯメヂメチステルを４ｇ、ＤＬ−ラクタイドのかわ
りに１−ラクタイド２０ｇを使用づ−る以外は実施例１
と同じ方法で重合した結果、１８．２ｇのブロック共重
合体（数平均分子邑２５．０００η８．／ｃｏ、６７、
融点１７０℃）を得た。この共重合体のモル比（Ｐ Ｌ
Ａ ／ Ｐ Ｅ Ｏ）は９６／４であった。Example 2 Example 1 except that 4 g of PEO medimethister and 20 g of 1-lactide were used instead of DL-lactide.
As a result of polymerization in the same manner as above, 18.2 g of block copolymer (number average molecular weight 25.000 η8./co, 67,
(melting point: 170°C). The molar ratio of this copolymer (PL
A/PEO) was 96/4.
この共重合体を１２０℃でホットプレスし、フィルムを
作成し、引張試験を行なった結果、引張強度２．８Ｎ９
／ｍｍ２、初期ヤング率４．２Ｋｇ／ｌｌ１ｍ２、伸度
４５％である柔軟性の良いフィルムが得られた。This copolymer was hot-pressed at 120°C to create a film, and a tensile test was performed. As a result, the tensile strength was 2.8N9.
A flexible film having an initial Young's modulus of 4.2 kg/1 m 2 and an elongation of 45% was obtained.
以上のとおりポリ乳酸に少量のＰＦＯをＰＥＯジカルボ
ン酸セグメントとして導入しｌこ本発明のブロック共重
合体は、Ｐ ＩＥ Ｏによる親水性を有するとともにポ
リ乳酸セグメントにより生物が吸収可能であり、しかも
高重合度が得られ柔軟なフィルムを形成することができ
、医療外科用品への利用が期待できる。As described above, a small amount of PFO is introduced into polylactic acid as a PEO dicarboxylic acid segment, and the block copolymer of the present invention has hydrophilicity due to PIE O, can be absorbed by living organisms due to the polylactic acid segment, and has a high It is possible to obtain a high degree of polymerization and form a flexible film, and is expected to be used in medical and surgical supplies.
Claims (1)
ポリオキシエチレンジカルボン酸セグメント（Ｂ）３〜
３０重量％からなるブロック共重合体。 ２、Ｌ−ラクタイド及び又はＤＬ−ラクタイドと式 ▲数式、化学式、表等があります▼ （式中Ｒはアルキル基を示す）で示されるポリオキシエ
チレンテレケリック酸エステルとを水分を除去した系中
加熱することによりエステル交換反応により縮合重合し
て式 ▲数式、化学式、表等があります▼ で表わされポリ乳酸セグメント（Ａ）７０〜９７重量％
とポリオキシエチレンジカルボン酸セグメント（Ｂ）３
〜３０重量％からなるブロック共重合体を製造する方法
。[Claims] 1. Represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc.
A block copolymer consisting of 30% by weight. 2. L-lactide and/or DL-lactide and polyoxyethylene telechelic acid ester represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. When heated, condensation polymerization occurs due to transesterification reaction, which is represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Polylactic acid segment (A) 70 to 97% by weight
and polyoxyethylene dicarboxylic acid segment (B) 3
A method for producing a block copolymer consisting of ~30% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61214781A JPS6369825A (en) | 1986-09-11 | 1986-09-11 | Block copolymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61214781A JPS6369825A (en) | 1986-09-11 | 1986-09-11 | Block copolymer and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6369825A true JPS6369825A (en) | 1988-03-29 |
Family
ID=16661428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61214781A Pending JPS6369825A (en) | 1986-09-11 | 1986-09-11 | Block copolymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6369825A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02152461A (en) * | 1988-12-01 | 1990-06-12 | Nippon Sogo Igaku Kenkyusho:Kk | Tissue absorbable film |
| JPH03505535A (en) * | 1988-07-05 | 1991-12-05 | ビオコン オーワイ | Polymer film for reinforced biofunctional materials |
| EP0493008A2 (en) * | 1990-12-21 | 1992-07-01 | Toray Industries, Inc. | Polyester film and photosensitive material |
| EP0558965A2 (en) * | 1992-03-02 | 1993-09-08 | American Cyanamid Company | Reduced friction coatings for articles in contact with human or animal tissues |
| WO2011081406A3 (en) * | 2009-12-29 | 2011-12-01 | 주식회사 삼양사 | Macromolecule for delivering protein, polypeptide or peptide drugs and a production method for the same, and a slow release composition for protein, polypeptide or peptide drugs and a production method for the same |
-
1986
- 1986-09-11 JP JP61214781A patent/JPS6369825A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03505535A (en) * | 1988-07-05 | 1991-12-05 | ビオコン オーワイ | Polymer film for reinforced biofunctional materials |
| JPH02152461A (en) * | 1988-12-01 | 1990-06-12 | Nippon Sogo Igaku Kenkyusho:Kk | Tissue absorbable film |
| EP0493008A2 (en) * | 1990-12-21 | 1992-07-01 | Toray Industries, Inc. | Polyester film and photosensitive material |
| EP0558965A2 (en) * | 1992-03-02 | 1993-09-08 | American Cyanamid Company | Reduced friction coatings for articles in contact with human or animal tissues |
| WO2011081406A3 (en) * | 2009-12-29 | 2011-12-01 | 주식회사 삼양사 | Macromolecule for delivering protein, polypeptide or peptide drugs and a production method for the same, and a slow release composition for protein, polypeptide or peptide drugs and a production method for the same |
| KR101224004B1 (en) * | 2009-12-29 | 2013-01-22 | 주식회사 삼양바이오팜 | A polymer for protein, polypeptide or peptide drug delivery and a method for preparing the same, and a composition for sustained release of protein, polypeptide or peptide drug and a method for preparing the same |
| US9603931B2 (en) | 2009-12-29 | 2017-03-28 | Samyang Biopharmaceuticals Corporation | Macromolecule for delivering protein, polypeptide or peptide drugs and a production method for the same, and a slow release composition for protein, polypeptide or peptide drugs and a production method for the same |
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