JP2019537508A - 高分子量の親水性添加剤を含有するイソポーラス自己集合ブロックコポリマーフィルム及びその製造方法 - Google Patents
高分子量の親水性添加剤を含有するイソポーラス自己集合ブロックコポリマーフィルム及びその製造方法 Download PDFInfo
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- JP2019537508A JP2019537508A JP2019527322A JP2019527322A JP2019537508A JP 2019537508 A JP2019537508 A JP 2019537508A JP 2019527322 A JP2019527322 A JP 2019527322A JP 2019527322 A JP2019527322 A JP 2019527322A JP 2019537508 A JP2019537508 A JP 2019537508A
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Abstract
Description
本発明は、イソポーラス(isoporous)ブロックコポリマー(「BCP」)フィルム及びその製造方法に関する。
膜ファウリング及び膜圧縮は、膜濾過プロセスにおけるフラックス劣化の2つの主な原因である。膜ファウリングは、膜性能に対する一般的に知られている障害である。使用中に溶液又は粒子状物質が膜上に堆積すると、それは発生する。膜ファウリングは、膜性能の低下を招く。膜ファウリングメカニズムはよく理解されており、ファウリングによるフラックス劣化は、汚損防止膜の設計、プロセスの改善、及び現場洗浄技術によって、多くのろ過用途で完全に回復することができる。
本発明及びその付随する利点の多くをより完全に理解することは、添付の図面と関連して考慮したときに以下の詳細な説明を参照することによってよりよく理解されるにつれて、容易に得られるであろう。
図面に示された本発明の好ましい実施形態を説明する際に、明確にするために特定の用語を使用する。しかしながら、本発明は、そのように選択された特定の用語に限定されることを意図するものではなく、各特定の用語は、同様の目的を達成するために同様に動作するすべての技術的均等物を包含することを理解されたい。本発明のいくつかの好ましい実施形態は例示目的で記載されており、本発明は図面に具体的に示されていない他の形態で具体化され得ることが理解される。いくつかの実施形態では、フィルムは膜であり、これ膜はフィルムのサブセットである。本発明の文脈において、「高分子量」は、本発明の材料を含むマジョリティブロックコポリマーの分子量の50%以上であると定義される。フィルムは、約1nmから200nmの間と定義されるメソ細孔を有する。本発明の文脈において、イソポーラス(isoporous)とは、実質的に狭い孔径分布を有することを意味する。フィルムは対称又は非対称のどちらかである。
少なくとも1つのブロックコポリマーを少なくとも1つの溶媒及び少なくとも1つの高分子量親水性ポリマーと混合することによってポリマー溶液を配合するステップと;
前記ポリマー溶液をフィルムに成形するステップと;
前記溶媒(複数可)の一部を蒸発させるステップと;
前記フィルムを凝固浴に浸漬するステップと;
場合により、前記BCPフィルムを水ですすぐステップと;
を含む。ポリマー溶液BCPフィルムキャスティング溶液溶媒のための溶媒は、アセトアルデヒド、酢酸、アセトン、アセトニトリル、ベンゼン、クロロホルム、シクロヘキサン、ジクロロメタン、ジメトキシエタン、ジメチルスルホキシド、ジメチルアセトアミド、ジメチルホルムアミド、1,4−ジオキサン、エタノール、酢酸エチル、ギ酸ヘキサン、メタノール、N−メチル−2−ピロリドン、プロパノールピリジン、スルホラン、テトラヒドロフラン、又はトルエン、のうちの少なくとも1つを含む。
(1)ポリ(イソプレン−b−スチレン−b−4−ビニル−ピリジン)(ISV)(モル質量50〜500kg/mol)のようなブロックコポリマー;
(2)1,4−ジオキサン、及び場合によりテトラヒドロフラン(THF)又はアセトンなどの溶媒。
他の公知のブロックコポリマーが本明細書に開示された1SVポリマーの代わりになり得ることは当業者には容易に明らかであろう。本明細書に記載のISVは、以下のような分子量を有する。:
ISV22: 94,000Da;
ISV28: 124,000Da;
ISV29: 91,000Da;
ISV43: 53,000Da。
(1−最後の4つのデータ点の平均/最初の4つのデータ点の平均)×100
図6は、高分子量PVP K90又は低分子量PEG400を組み込んだことを除いて、同一の4つのISV22 BCPフィルム(フィルムID: L160520及びLI60422)について70分の時間間隔にわたるフラックス低下を示す。PVP−K90を組み込んだフィルムは、小分子量PEG400を有するフィルムよりも有意に少ないフラックス低下を示した。
Claims (20)
- 少なくとも1つのブロックコポリマーと、少なくとも1つの高分子量親水性ポリマーとを含むブロックコポリマー(BCP)フィルムであって、細孔の少なくとも一部がイソポーラス及びメソポーラスである、ブロックコポリマー(BCP)フィルム。
- 少なくとも1つの親水性ブロックと、少なくとも1つの高分子量親水性ポリマーとを含むブロックコポリマー(BCP)フィルムであって、細孔の少なくとも一部がイソポーラス及びメソポーラスである、ブロックコポリマー(BCP)フィルム。
- 前記フィルムが対称又は非対称のいずれかである、請求項1に記載のイソポーラスBCPフィルム。
- 前記フィルムが経時的に減少したフラックス低下を示す、請求項1に記載のイソポーラスBCPフィルム。
- 前記高分子量親水性ポリマーが、ポリ(アクリレート)、ポリ(メタクリレート)、ポリ(アクリル酸)、ポリ(アクリルアミド)、ポリ(ビニルピリジン)、ポリ(ビニルピロリドン)、ポリ(ビニルアルコール)、天然由来のポリマー(セルロース、キトサン、複合炭水化物を包含するがこれらに限定されない)、ポリ(エーテル)、ポリ(無水マレイン酸)、ポリ(スチレンスルホネート)、ポリ(アリルアミン塩酸塩)、ポリ(スルホン)、ポリ(エーテルスルホン)、ポリ(エチレングリコール)、又はこれらの置換等価物、を含む、請求項1に記載のイソポーラスBCPフィルム。
- 前記高分子量親水性ポリマーが、前記BCPに対して0.1〜15重量%の範囲で存在する、請求項1に記載のイソポーラスBCPフィルム。
- 当該イソポーラスBCPフィルムが低減したタンパク質吸着を示す、請求項1に記載のイソポーラスBCPフィルム。
- 湿潤剤(例えばグリセロール)溶液への曝露後の乾燥時に、当該フィルムは増大したフラックス保持力を示す、請求項1に記載のイソポーラスBCPフィルム。
- 前記高分子量親水性ポリマーがポリ(ビニルピロリドン)であり、前記ポリ(ビニルピロリドン)の平均分子量が360,000Daである、請求項1に記載のイソポーラスBCPフィルム。
- 前記材料が分離又は濾過用途に使用される、請求項1に記載のイソポーラスBCPフィルム。
- 前記材料が、シリンジフィルター、カプセル、カートリッジ、フラットシート、らせん巻き、又は中空繊維を包含するがこれらに限定されないフィルターデバイスとして包装されている、請求項1に記載のイソポーラスBCPフィルム。
- 少なくとも1つのBCPがAB又はABCトリブロックコポリマーである、請求項1に記載のイソポーラスBCPフィルム。
- 以下のステップ:
(a)少なくとも1つのブロックコポリマーを少なくとも1つの溶媒及び少なくとも1つの高分子量親水性ポリマーと混合することによってポリマー溶液を配合するステップと;
(b)前記ポリマー溶液をフィルムに成形するステップと;
(c)前記溶媒(複数可)の一部を蒸発させるステップと;
(d)前記フィルムを凝固浴に浸漬するステップと;
(e)場合により、前記BCPフィルムを水ですすぐステップと;
を含む、イソポーラスメソポーラスブロックコポリマー(BCP)フィルムを形成するための方法であって、前記細孔の少なくとも一部がイソポーラス及びメソポーラスである、方法。 - 以下のステップ:
(a)少なくとも1つのブロックコポリマーを少なくとも1つの溶媒及び少なくとも1つの高分子量親水性ポリマーと混合することによってポリマー溶液を配合するステップであって、ここで少なくとも1つのBCPは親水性ブロックを含む、ステップと;
(b)前記ポリマー溶液をフィルムに成形するステップと;
(c)前記溶媒(複数可)の一部を蒸発させるステップと;
(d)前記フィルムを凝固浴に浸漬するステップと;
(e)場合により、前記BCPフィルムを水ですすぐステップと;
を含む、イソポーラスメソポーラスブロックコポリマー(BCP)フィルムを形成するための方法であって、前記細孔の少なくとも一部がイソポーラス及びメソポーラスである、方法。 - 少なくとも1つのブロックコポリマーが、
ポリ(ブタジエン)、ポリ(イソブチレン)、ポリ(イソプレン)、ポリ(エチレン)、ポリ(スチレン)、ポリ(メチルアクリレート)、ポリ(ブチルメタクリレート)、ポリ(エーテルスルホン)、ポリ(メチルメタクリレート)、ポリ(n−ブチルアクリレート)、ポリ(2−ヒドロキシエチルメタクリレート)、ポリ(グリシジルメタクリレート)、ポリ(アクリル酸)、ポリ(アクリルアミド)、ポリ(スルホン)、ポリ(フッ化ビニリデン)、ポリ(N、N−ジメチルアクリルアミド)、ポリ(2−ビニルピリジン)、ポリ(3−ビニルピリジン)、ポリ(4−ビニルピリジン)、ポリ(エチレングリコール)、ポリ(プロピレングリコール)、ポリ(塩化ビニル)、ポリ(テトラフルオロエチレン)、ポリ(エチレンオキサイド)、ポリ(プロピレンオキサイド)、ポリ(N−イソプロピルアクリルアミド)、ポリ(ジメチルアミノエチルメタクリレート)、ポリ(アミド酸)、ポリ(ジメチルシロキサン)、ポリ(乳酸)、ポリ(イソシアネート)、ポリ(エチルシアノアクリレート)、ポリ(アクリロニトリル)、ポリ(ヒドロキシスチレン)、ポリ(メチルスチレン)、ポリ(エチレンイミン)、ポリ(スチレンスルホネート)、ポリ(アリルアミン塩酸塩)、ポリ(ペンタフルオロスチレン)、ポリ(2−(ペルフルオロヘキシル)エチルメタクリレート)、又はこれらの置換等価物、
を含む少なくとも1つのブロックを含む、請求項13に記載の方法。 - 前記溶媒が、
a. アセトアルデヒド、
b. 酢酸、
c. アセトン、
d. アセトニトリル、
e. ベンゼン、
f. クロロホルム、
g. シクロヘキサン、
h. ジクロロメタン、
i. ジメトキシエタン、
j. ジメチルスルホキシド、
k. ジメチルアセトアミド、
l. ジメチルホルムアミド、
m. 1,4−ジオキサン、
n. エタノール、
o. 酢酸エチル
p. ギ酸
q. ヘキサン、
r. メタノール、
s. N−メチル−2−ピロリドン、
t. プロパノール、
u. ピリジン、
v. スルホラン、
w. テトラヒドロフラン、又は
x. トルエン、
のうちの少なくとも1つを含む、請求項13に記載の方法。 - 前記フィルムが基板の上に形成される、請求項13に記載の方法。
- 前記高分子量親水性ポリマーが、ポリ(アクリレート)、ポリ(メタクリレート)、ポリ(アクリル酸)、ポリ(アクリルアミド)、ポリ(ビニルピリジン)、ポリ(ビニルピロリドン)、ポリビニルアルコール、天然由来ポリマー(セルロース、キトサン、複合炭水化物を包含するがこれらに限定されない)、ポリ(エーテル)、ポリ(無水マレイン酸)、ポリ(スチレンスルホネート)、ポリ(アリルアミン塩酸塩)、ポリ(スルホン)、ポリ(エーテルスルホン)、ポリ(エチレングリコール)、又はこれらの置換等価物、を含む、請求項13に記載の方法。
- 前記高分子量親水性ポリマーが、前記BCPに対して0.1〜15質量%の範囲で存在する、請求項13に記載の方法。
- 前記ブロックコポリマーが、約5重量%〜25重量%の範囲で存在する、請求項13に記載の方法。
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KR20190103153A (ko) | 2019-09-04 |
CN110475602A (zh) | 2019-11-19 |
CN110475602B (zh) | 2022-05-03 |
KR102596197B1 (ko) | 2023-11-02 |
EP3541500A4 (en) | 2020-06-24 |
EP3541500A1 (en) | 2019-09-25 |
CA3044467A1 (en) | 2018-05-24 |
US11401411B2 (en) | 2022-08-02 |
WO2018093714A1 (en) | 2018-05-24 |
MX2019005774A (es) | 2020-02-07 |
US20220251366A1 (en) | 2022-08-11 |
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