JPH0441526A - Production of spherical polyamino acid particle - Google Patents
Production of spherical polyamino acid particleInfo
- Publication number
- JPH0441526A JPH0441526A JP15129390A JP15129390A JPH0441526A JP H0441526 A JPH0441526 A JP H0441526A JP 15129390 A JP15129390 A JP 15129390A JP 15129390 A JP15129390 A JP 15129390A JP H0441526 A JPH0441526 A JP H0441526A
- Authority
- JP
- Japan
- Prior art keywords
- organic solvent
- solvent
- polyamino acid
- spherical particles
- amino acid
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 239000002245 particle Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 33
- 239000012798 spherical particle Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims 2
- 238000005476 soldering Methods 0.000 claims 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 4
- -1 N-carboxy amino acid anhydride Chemical class 0.000 abstract description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 150000008065 acid anhydrides Chemical class 0.000 abstract 2
- 239000012046 mixed solvent Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229940024606 amino acid Drugs 0.000 description 7
- 235000001014 amino acid Nutrition 0.000 description 7
- 150000001413 amino acids Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 3
- 229960003136 leucine Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 108010050934 polyleucine Proteins 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920001308 poly(aminoacid) Polymers 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- JHWZWIVZROVFEM-UHFFFAOYSA-N 4-(2-methylpropyl)-1,3-oxazolidine-2,5-dione Chemical compound CC(C)CC1NC(=O)OC1=O JHWZWIVZROVFEM-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AHLPHDHHMVZTML-BYPYZUCNSA-N L-Ornithine Chemical compound NCCC[C@H](N)C(O)=O AHLPHDHHMVZTML-BYPYZUCNSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZGEYCCHDTIDZAE-BYPYZUCNSA-N L-glutamic acid 5-methyl ester Chemical compound COC(=O)CC[C@H](N)C(O)=O ZGEYCCHDTIDZAE-BYPYZUCNSA-N 0.000 description 1
- 239000004395 L-leucine Substances 0.000 description 1
- 235000019454 L-leucine Nutrition 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- AHLPHDHHMVZTML-UHFFFAOYSA-N Orn-delta-NH2 Natural products NCCCC(N)C(O)=O AHLPHDHHMVZTML-UHFFFAOYSA-N 0.000 description 1
- UTJLXEIPEHZYQJ-UHFFFAOYSA-N Ornithine Natural products OC(=O)C(C)CCCN UTJLXEIPEHZYQJ-UHFFFAOYSA-N 0.000 description 1
- 101100079450 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) NCA3 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229960003104 ornithine Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002510 pyrogen Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
Description
【発明の詳細な説明】
し産業上の利用分野］
本発明は、クロマトグラフィー用充填剤等に用いられる
ポリアミノ酸球状粒子の製造力；去に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the production ability of polyamino acid spherical particles used as packing materials for chromatography and the like.
［従来技術と問題点］
クロマトグラフィー用充填剤としてはシリカゲルや合成
高分子等各種の素材が用途に応じて使用される。[Prior Art and Problems] Various materials such as silica gel and synthetic polymers are used as packing materials for chromatography depending on the purpose.
近年ポリアミノ酸の持つアフィニティーを利用し光学分
割剤や発熱物質吸着剤として応用する例が示されている
。In recent years, examples have been shown in which the affinity of polyamino acids is utilized as optical resolution agents and pyrogen adsorbents.
これらに用いられるポリアミノ酸球状粒子の製法として
は、ポリアミノ酸重合液を水に懸濁させ有機溶媒を蒸発
させる懸濁蒸発法が通常用いられるが工程が煩雑であり
有機溶剤を蒸発させる等工業的な方法としては問題が多
い。As for the manufacturing method of polyamino acid spherical particles used for these, a suspension evaporation method is usually used in which a polyamino acid polymerization solution is suspended in water and the organic solvent is evaporated, but the process is complicated and it is difficult to manufacture the polyamino acid spherical particles by evaporating the organic solvent. There are many problems with this method.
重合時に球状粒子を生成させる乳化重合法は簡便なポリ
マー球状粒子の製造方法として一般的であるがポリアミ
ノ酸球状粒子の製造に応用された例は無い。Emulsion polymerization, which generates spherical particles during polymerization, is a common and simple method for producing spherical polymer particles, but there is no example of it being applied to the production of polyamino acid spherical particles.
またポリアミノ酸粉末の製造方法としてモノマーである
アミノ酸−Ｎ−カルボン酸無水物（ＮＣＡ）を溶解する
が、ポリアミノ酸を溶解しない有機溶媒中でアミノ酸−
Ｎ−カルボン酸無水物を重合させる方法が公知であるが
得られるポリアミノ酸は微小粒子が集合したクラスター
状でありその粒径も不揃いである。In addition, as a method for producing polyamino acid powder, the monomer amino acid N-carboxylic anhydride (NCA) is dissolved in an organic solvent that does not dissolve the polyamino acid.
Although a method of polymerizing N-carboxylic acid anhydride is known, the resulting polyamino acid is in the form of a cluster of fine particles and its particle size is irregular.
［本発明が解決しようとする課題］
本発明の課題は、重合時に粒径の揃った球状粒子を生成
できる工業的に優れたポリアミノ酸球状粒子の製造方法
を提供することである。[Problems to be Solved by the Present Invention] An object of the present invention is to provide an industrially excellent method for producing polyamino acid spherical particles that can produce spherical particles with uniform particle sizes during polymerization.
［課題を解決するための手段］
これらの問題を鑑み、本発明者らは鋭意検討を重ねた結
果、重合時にポリアミノ酸球状粒子を製造できることを
見い出し本発明を完成するに至った。[Means for Solving the Problems] In view of these problems, the present inventors have made extensive studies, and as a result have found that polyamino acid spherical particles can be produced during polymerization, and have completed the present invention.
すなわち本発明はアミノ酸−Ｎ−カルボン酸無水物を溶
媒中で重合し、ポリアミノ酸を得る方法において、アミ
ノ酸−Ｎ−カルボン酸無水物を溶解するが、ポリアミノ
酸を溶解しない第一の有機溶媒中でアミノ酸−Ｎ−カル
ボン酸無水物を重合させる際に、該有機溶媒と相溶しな
い第二の有機溶媒を加え撹はん後重合させることを特徴
とするポリアミノ酸球状粒子の製造法である。That is, the present invention provides a method for obtaining a polyamino acid by polymerizing an amino acid-N-carboxylic acid anhydride in a solvent, in which a first organic solvent that dissolves the amino acid-N-carboxylic acid anhydride but does not dissolve the polyamino acid; When polymerizing amino acid-N-carboxylic acid anhydride, a second organic solvent that is incompatible with the organic solvent is added, stirred, and then polymerized.
前述のようにポリアミノ酸球状粒子の製造方法は一度重
合液を調製したのち球状粒子を製造する煩雑な方法であ
り、ビニルポリマーにおける乳化重合のような簡便で工
業的にも優れた方法の開発が望まれている。As mentioned above, the method for producing polyamino acid spherical particles is a complicated method in which spherical particles are produced after a polymerization solution is prepared, and it is difficult to develop a simple and industrially superior method such as emulsion polymerization for vinyl polymers. desired.
本発明の方法は重合溶媒にアミノ酸−Ｎ−カルボン酸無
水物を溶解するが、ポリアミノ酸を溶解しない第一の有
機溶媒と、該有機溶媒と相溶しない第二の有機溶媒を併
用することにより粒径の揃ったポリアミノ酸球状粒子を
重合時に得ることが可能となった。The method of the present invention dissolves amino acid-N-carboxylic acid anhydride in a polymerization solvent, but by using together a first organic solvent that does not dissolve polyamino acids and a second organic solvent that is not compatible with the organic solvent. It became possible to obtain polyamino acid spherical particles with uniform particle size during polymerization.
本発明に用いられるアミノ酸はアラニン、ロイシン、バ
リンのような中性アミノ酸がある。Amino acids used in the present invention include neutral amino acids such as alanine, leucine, and valine.
さらにアスパラギン酸やグルタミン酸等の酸性アミノ酸
をエステル化したもの、たとえばそれらのアミノ酸のア
ルキルエステルやベンジルエステルを用いることができ
る。Furthermore, esterification of acidic amino acids such as aspartic acid and glutamic acid, such as alkyl esters and benzyl esters of these amino acids, can also be used.
またリジン、オルニチン等の塩基性アミノ酸を疎水性基
で保護したもの、例えばそれらのアミノ酸のカルボベン
ゾキシ化物、カルボエトキシ化物を挙げることができる
。Further, basic amino acids such as lysine and ornithine protected with a hydrophobic group, such as carbobenzoxidized products and carboethoxylated products of these amino acids, can also be mentioned.
本発明に用いられる有機溶媒は、アミノ酸−Ｎ−カルボ
ン酸無水物を溶解するが、ポリアミノ酸を溶解しない第
一の溶媒と、その有機溶媒と相溶しない第二の溶媒の組
合せである。The organic solvent used in the present invention is a combination of a first solvent that dissolves the amino acid-N-carboxylic anhydride but does not dissolve the polyamino acid, and a second solvent that is incompatible with the organic solvent.
アミノ酸−Ｎ−カルボン酸無水物を溶解するホルムアミ
ドのような活性水素を有しない有機溶媒であり溶解度パ
ラメーターの値が１０以上のものである。It is an organic solvent without active hydrogen, such as formamide, which dissolves amino acid-N-carboxylic acid anhydride, and has a solubility parameter value of 10 or more.
該有機溶媒と相溶しない第二の有機溶媒は活性水素を有
しないｎ−ヘキサン、ヘプタン、オクタンのような炭化
水素溶媒であり、溶解度パラメーターが８以下のもので
ある。The second organic solvent that is incompatible with the organic solvent is a hydrocarbon solvent such as n-hexane, heptane, or octane that does not have active hydrogen and has a solubility parameter of 8 or less.
アミノ酸−Ｎ−カルボン酸無水物の重合に使用される開
始剤は通常用いられる有機アミンやその組合せで良く、
トリエチルアミン等が好んで用いられる。The initiator used in the polymerization of amino acid-N-carboxylic acid anhydride may be a commonly used organic amine or a combination thereof;
Triethylamine and the like are preferably used.
得られるポリアミノ酸球状粒子の粒径は、重合時のアミ
ノ酸−Ｎ−カルボン酸無水物の温度、有機溶媒の組合せ
により制御される。The particle size of the resulting polyamino acid spherical particles is controlled by the combination of the temperature of the amino acid-N-carboxylic anhydride and the organic solvent during polymerization.
アミノ酸−Ｎ−カルボン酸無水物の濃度は通常第一の有
機溶媒の１〜２０ｗｔ％であるが、アミノ酸−Ｎ−カル
ボン酸無水物の濃度が高いほど得られる球状粒子の粒径
は大きくなる。The concentration of amino acid-N-carboxylic acid anhydride is usually 1 to 20 wt% of the first organic solvent, but the higher the concentration of amino acid-N-carboxylic acid anhydride, the larger the particle size of the obtained spherical particles becomes.
第二の溶媒に溶解度パラメーターの高い溶媒を用いるは
ど粒径の小さい球状粒子が得られる。When a solvent with a high solubility parameter is used as the second solvent, spherical particles with a small particle size can be obtained.
第二の溶媒の使用量は特に制限は無いが通常第一の溶媒
に対し０． ２〜２倍量の範囲である。There is no particular restriction on the amount of the second solvent used, but it is usually 0.00% relative to the first solvent. It is in the range of 2 to 2 times the amount.
本発明で得られる重合液にアミノ酸−Ｎ−カルボン酸無
水物溶液を追加することにより球状粒子の粒径を大きく
することも可能である。It is also possible to increase the particle size of the spherical particles by adding an amino acid-N-carboxylic acid anhydride solution to the polymerization solution obtained in the present invention.
この際はじめの重合に使用したアミノ酸−Ｎ−カルボン
酸無水物と異なるアミノ酸−Ｎ−カルボン酸無水物を加
えることにより表層と芯層の組成の異なる多層ポリアミ
ノ酸球状粒子を調製することも可能である。At this time, by adding an amino acid-N-carboxylic acid anhydride different from the amino acid-N-carboxylic acid anhydride used in the initial polymerization, it is also possible to prepare multilayer polyamino acid spherical particles with different compositions in the surface layer and core layer. be.
ポリアミノ酸球状粒子の製造は、アミノ酸−Ｎ−カルボ
ン酸無水物を第一の有機溶媒に溶解し該有機溶媒と相溶
しない第二の有機溶媒を加え撹はんする。その後撹はん
速度を落し、あるいは静置し開始剤を加え重合させる。To produce polyamino acid spherical particles, an amino acid-N-carboxylic acid anhydride is dissolved in a first organic solvent, a second organic solvent that is incompatible with the organic solvent is added, and the mixture is stirred. Thereafter, the stirring speed is reduced or the mixture is allowed to stand still and an initiator is added for polymerization.
重合中の撹はん速度は小さいほど凝集の少ない粒径の均
一な球状粒子を得ることができる。The lower the stirring speed during polymerization, the less agglomeration occurs and the more uniformly sized spherical particles can be obtained.
一般にこのようにして得られるポリアミノ酸球状粒子の
平均粒径は０．５〜２０μｍの範囲であり前述の方法で
任意に制御できる。Generally, the average particle diameter of the polyamino acid spherical particles obtained in this manner is in the range of 0.5 to 20 μm, and can be arbitrarily controlled by the method described above.
以下、実施例で本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
［実施例］
実施例１゜
Ｌ−ロイシンＮＣＡ３．Ｏｇをアセトニトリル２００ｍ
１に溶解しＨ−ヘキサン３００ｍｌを加え２５°Ｃで強
力に撹はんした。[Example] Example 1゜L-leucine NCA3. Og to acetonitrile 200m
1, and 300 ml of H-hexane was added thereto, followed by vigorous stirring at 25°C.
撹はん速度を落しトリエチルアミン１１ｍｇを加え約４
時間重合させた。Reduce the stirring speed and add 11 mg of triethylamine to approx.
Polymerized for hours.
析出したポリーＬ−ロイシンを濾別し、メタルノールで
洗浄、減圧下に乾燥した。The precipitated poly-L-leucine was separated by filtration, washed with metallol, and dried under reduced pressure.
ポリ−ルーロイシン球状粒子３．１ｇを得た。平均粒径
は２μｍであった。 （写真■参照）実施例２゜
Ｌ−ロイシンＮＣＡ４０ｇをアセトニトリル２００ｍ１
に溶解しｎ−オクタン３００ｍ１を加え２５°Ｃで強力
に撹はんした。3.1 g of poly-leuleucine spherical particles were obtained. The average particle size was 2 μm. (See photo ■) Example 2 40g of L-leucine NCA was added to 200ml of acetonitrile.
300ml of n-octane was added to the solution, and the mixture was stirred vigorously at 25°C.
撹はん速度を落しトリエチルアミン９０ｍｇを加え約４
時間重合させた。Reduce the stirring speed and add 90 mg of triethylamine for approx.
Polymerized for hours.
析出したポリーＬ−ロイシンを濾別し、メタノールで洗
浄、減圧下に乾燥した。The precipitated poly-L-leucine was filtered off, washed with methanol, and dried under reduced pressure.
ポリ−ルーロイシン球状粒子２５．１ｇを得た。平均粒
径は０．７５μｍであった。 （写真■参照）
実施例３゜
実施例１．で調製した重合液３０ｍ１を開始剤としＬ−
グルタミン酸−γ−メチルエステルＮＣＡ２ｇをジオキ
サン３００ｍ１に溶解した液に加え２５°Ｃで３時間重
合させた。25.1 g of poly-leuleucine spherical particles were obtained. The average particle size was 0.75 μm. (See photo ■) Example 3゜Example 1. L-
A solution in which 2 g of glutamic acid γ-methyl ester NCA was dissolved in 300 ml of dioxane was added and polymerized at 25°C for 3 hours.
得られた球状粒子を濾別し、メタノールで洗浄、減圧下
に乾燥してポリーＬ−ロイシルーγ−メチルーＬ−グル
タメー）１．４ｇを得た。The obtained spherical particles were filtered, washed with methanol, and dried under reduced pressure to obtain 1.4 g of poly(L-leucyl-γ-methyl-L-glutamic acid).
平均粒径は３．５μｍであった。 （写真■参照）選択
反射法による赤外吸収スペクトルにより粒子の表層はポ
リーγ−メチルーＬ−グルタメトであることを確認した
。The average particle size was 3.5 μm. (See photo ①) It was confirmed by infrared absorption spectrum using selective reflection method that the surface layer of the particles was poly γ-methyl-L-glutameth.
実施例４゜
実施例１．で調製した重合液にＬ−ロイシンＮＣＡ２０
ｇのアセトニトリル溶液３００ｍ１を加え、２５℃で３
時間重合させた。Example 4゜Example 1. Add L-leucine NCA20 to the polymerization solution prepared in
Add 300ml of acetonitrile solution of
Polymerized for hours.
得られた球状粒子を濾別しメタノールで洗浄、減圧下に
乾燥してポリーＬ−ロイシン１３゜２ｇを得た。The obtained spherical particles were filtered, washed with methanol, and dried under reduced pressure to obtain 13.2 g of poly-L-leucine.
平均粒径は４μｍであった。 （写真■参照）［発明の
効果］
本発明は重合時に球状粒子や多層球状粒子を調製できる
工業的に優れた方法でありその粒径も０． ５〜２０μ
ｍの範囲で制御可能な方法である。The average particle size was 4 μm. (See Photo ■) [Effects of the Invention] The present invention is an industrially excellent method for preparing spherical particles and multilayer spherical particles during polymerization, and the particle size is also 0. 5~20μ
This method allows control over a range of m.
Claims (3)
し、ポリアミノ酸を得る方法において、アミノ酸−Ｎ−
カルボン酸無水物を溶解するが、ポリアミノ酸を溶解し
ない第一の有機溶媒中でアミノ酸−Ｎ−カルボン酸無水
物を重合させる際に、該有機溶媒と相溶しない第二の有
機溶媒を加え撹はん後重合させることを特徴とするポリ
アミノ酸球状粒子の製造法。(1) In a method for obtaining a polyamino acid by polymerizing an amino acid-N-carboxylic acid anhydride in a solvent, the amino acid-N-
When polymerizing the amino acid-N-carboxylic anhydride in a first organic solvent that dissolves the carboxylic anhydride but does not dissolve the polyamino acid, a second organic solvent that is incompatible with the organic solvent is added and stirred. A method for producing polyamino acid spherical particles characterized by polymerization after soldering.
し、ポリアミノ酸を得る方法において、アミノ酸−Ｎ−
カルボン酸無水物を溶解するが、ポリアミノ酸を溶解し
ない第一の有機溶媒中でアミノ酸−Ｎ−カルボン酸無水
物を重合させる際に、該有機溶媒と相溶しない第二の有
機溶媒を加え撹はん後重合させて得られる重合液にアミ
ノ酸−Ｎ−カルボン酸無水物の第一の有機溶媒溶液を更
に追加することを特徴とする多層球状粒子の製造法。(2) In a method for obtaining a polyamino acid by polymerizing an amino acid-N-carboxylic acid anhydride in a solvent, the amino acid-N-
When polymerizing the amino acid-N-carboxylic anhydride in a first organic solvent that dissolves the carboxylic anhydride but does not dissolve the polyamino acid, a second organic solvent that is incompatible with the organic solvent is added and stirred. A method for producing multilayer spherical particles, which comprises further adding a first organic solvent solution of an amino acid-N-carboxylic acid anhydride to a polymerization solution obtained by post-soldering polymerization.
ｍである請求項１及び２記載の球状粒子及び多層球状粒
子の製造法。(3) The particle size of the polyamino acid spherical particles is 0.5 to 20μ
The method for producing spherical particles and multilayer spherical particles according to claims 1 and 2, wherein m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15129390A JPH0441526A (en) | 1990-06-08 | 1990-06-08 | Production of spherical polyamino acid particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15129390A JPH0441526A (en) | 1990-06-08 | 1990-06-08 | Production of spherical polyamino acid particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0441526A true JPH0441526A (en) | 1992-02-12 |
Family
ID=15515518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15129390A Pending JPH0441526A (en) | 1990-06-08 | 1990-06-08 | Production of spherical polyamino acid particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0441526A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267385B1 (en) | 1996-09-05 | 2001-07-31 | Kabushiki Kaisha Miyasaka Gomu | Grommet |
-
1990
- 1990-06-08 JP JP15129390A patent/JPH0441526A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267385B1 (en) | 1996-09-05 | 2001-07-31 | Kabushiki Kaisha Miyasaka Gomu | Grommet |
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