TWI717765B - Anti-biological adhesion film and preparation method thereof, and anti-biological adhesion copolymer - Google Patents

Anti-biological adhesion film and preparation method thereof, and anti-biological adhesion copolymer Download PDF

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TWI717765B
TWI717765B TW108121808A TW108121808A TWI717765B TW I717765 B TWI717765 B TW I717765B TW 108121808 A TW108121808 A TW 108121808A TW 108121808 A TW108121808 A TW 108121808A TW I717765 B TWI717765 B TW I717765B
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formula
hydrophobic
integer
biological adhesion
film
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TW202100589A (en
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趙啟民
曾惠馨
劉冠妙
林奕辰
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中山醫學大學
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一種抗生物沾黏膜，包含一膜體，膜體包括疏水性聚合物，及吸附於該疏水性聚合物且具有式I的結構的抗生物沾黏共聚物，該式I中，m為1至5的整數，n為15至25的整數，Y1及Y2之其中一者為

Figure 108121808-A0305-02-0001-14
，另一者為
Figure 108121808-A0305-02-0001-12
，R1為氫或甲基，R2為伸 甲基或伸乙基，R3為單鍵或
Figure 108121808-A0305-02-0001-4
，o為1至3的整數，Z1及Z2各自獨立地為-O-或-NH-，A為式II或式III的結構。本發明另提供一種該抗生物沾黏共聚物，及一種該抗生物沾黏膜的製法。本發明抗生物沾黏膜及抗生物沾黏共聚物具有很好的抗生物沾黏的能力。 An anti-biological adhesion film, comprising a film body, the film body comprising a hydrophobic polymer, and an anti-biological adhesion copolymer adsorbed on the hydrophobic polymer and having a structure of formula I, in the formula I, m is 1 to 5 is an integer, n is an integer from 15 to 25, and one of Y 1 and Y 2 is
Figure 108121808-A0305-02-0001-14
, The other is
Figure 108121808-A0305-02-0001-12
, R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 108121808-A0305-02-0001-4
, O is an integer from 1 to 3, Z 1 and Z 2 are each independently -O- or -NH-, and A is a structure of formula II or formula III. The present invention also provides the anti-biological adhesion copolymer and a method for preparing the anti-biological adhesion membrane. The anti-biological adhesion film and the anti-biological adhesion copolymer of the present invention have good anti-biological adhesion ability.

Figure 108121808-A0305-02-0001-5
Figure 108121808-A0305-02-0001-5

Figure 108121808-A0305-02-0001-13
Figure 108121808-A0305-02-0001-13

Figure 108121808-A0305-02-0002-8
Figure 108121808-A0305-02-0002-8

Description

抗生物沾黏膜及其製法、抗生物沾黏共聚物 Anti-biological adhesion film and preparation method thereof, and anti-biological adhesion copolymer

本發明是有關於一種共聚物及其應用，特別是指一種抗生物沾黏共聚物、包含其的抗生物沾黏膜，及該抗生物沾黏膜的製法。The present invention relates to a copolymer and its application, in particular to an anti-biological adhesion copolymer, an anti-biological adhesion film containing the copolymer, and a preparation method of the anti-biological adhesion film.

為減少水資源的消耗，生物廢水的淨化為現今的重要課題。使用薄膜過濾(membrane filtration)技術來淨化生物廢水，分離生物廢水中的生物類物質(例如蛋白質、細菌、病毒、細胞、生物組織等)以淨化生物廢水，是一種具有成本效益、節能及節省空間的淨化方式。然而，在淨化過程中，生物廢水中的生物類物質會附著或黏附在薄膜的表面或孔洞內，在薄膜的表面或孔洞內產生生物積垢(biofouling)，進而導致薄膜的使用壽命縮短且增加淨化的成本。In order to reduce the consumption of water resources, the purification of biological wastewater is an important issue today. The use of membrane filtration technology to purify biological wastewater and separate biological substances (such as proteins, bacteria, viruses, cells, biological tissues, etc.) in biological wastewater to purify biological wastewater is cost-effective, energy-saving and space-saving Way of purification. However, in the purification process, the biological substances in the biological wastewater will adhere to or adhere to the surface or the holes of the film, causing biofouling on the surface or the holes of the film, thereby shortening the service life of the film and increasing The cost of purification.

現有技術開發出許多改善方法來避免薄膜被生物類物質污染，例如增強薄膜的親水性、降低薄膜的表面能，或調節薄膜的表面電荷等方式，使薄膜具有抗生物類物質沾黏的能力。以增加薄膜的親水性而言，現有技術中例如有透過使用具有抗生物沾黏性質的兩性離子(zwitterion)改質疏水性薄膜的方式，兩性離子通常以表面接枝、共混、表面吸附、仿生黏附或原位胺化等方式形成在疏水性薄膜的表面。The prior art has developed many improved methods to prevent the film from being contaminated by biological substances, such as enhancing the hydrophilicity of the film, reducing the surface energy of the film, or adjusting the surface charge of the film, so that the film has the ability to resist the adhesion of biological substances. In terms of increasing the hydrophilicity of the film, in the prior art, for example, there is a way to modify the hydrophobic film by using zwitterions with anti-biological adhesion properties. Zwitterions are usually surface grafted, blended, surface adsorbed, Bionic adhesion or in-situ amination is formed on the surface of the hydrophobic film.

然而，現有使用兩性離子改質疏水性薄膜的方法仍存有不足之處，例如透過大氣等離子體誘導的表面共聚合(atmospheric plasma-induced surface copolymerization)，雖能成功地將兩性離子接枝到聚偏二氟乙烯(PVDF)膜上，但此種製法卻有高能耗的缺點。又，或者使用共混將兩性離子結合到疏水性薄膜的方式雖然簡單，但兩性離子可能會在之後過濾生物廢水的過程中滲出。有鑒於現有技術仍有不足之處，因而仍有需要開發出一種新穎的抗生物沾黏薄膜。However, the existing methods of using zwitterions to modify hydrophobic films still have shortcomings. For example, atmospheric plasma-induced surface copolymerization can successfully graft zwitterions to the polymer. Vinylidene fluoride (PVDF) membrane, but this method has the disadvantage of high energy consumption. In addition, although the method of using blending to bind zwitterions to the hydrophobic membrane is simple, the zwitterions may leak out during the subsequent filtration of biological wastewater. In view of the shortcomings of the existing technology, there is still a need to develop a novel anti-biological adhesion film.

此外，在生醫材料領域，生醫材料的抗生物沾黏特性也是重要的課題，因此開發抗生物沾黏的材料也是產業及學界致力的目標。In addition, in the field of biomedical materials, the anti-bioadhesion properties of biomedical materials are also an important issue. Therefore, the development of anti-bioadhesion materials is also the goal of industry and academia.

因此，本發明的第一目的，即在提供一種具有優異的抗生物沾黏能力的抗生物沾黏膜。Therefore, the first objective of the present invention is to provide an anti-bioadhesion membrane with excellent anti-bioadhesion ability.

於是，本發明抗生物沾黏膜，包含： 一膜體，包括疏水性聚合物及抗生物沾黏共聚物，其中，該抗生物沾黏共聚物吸附於該疏水性聚合物且具有式I的結構； [式I]

Figure 02_image001
式I中，m為1至5的整數，n為15至25的整數， Y 1及Y 2之其中一者為
Figure 02_image017
，另一者為
Figure 02_image019
， R 1為氫或甲基， R 2為伸甲基或伸乙基， R 3為單鍵或
Figure 02_image021
，其中，o為1至3的整數， Z 1及Z 2各自獨立地為
Figure 02_image023
或
Figure 02_image025
， A為式II或式III的結構， [式II]
Figure 02_image003
[式III]
Figure 02_image005
式II及式III中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 02_image023
或
Figure 02_image025
，Q 1為
Figure 02_image027
或
Figure 02_image029
，Q 2為
Figure 02_image031
，p為0至30的整數。 Therefore, the anti-biological adhesion film of the present invention includes: a film body, including a hydrophobic polymer and an anti-biological adhesion copolymer, wherein the anti-biological adhesion copolymer is adsorbed on the hydrophobic polymer and has a structure of formula I ; [Formula I]
Figure 02_image001
In formula I, m is an integer from 1 to 5, n is an integer from 15 to 25, and one of Y 1 and Y 2 is
Figure 02_image017
, The other is
Figure 02_image019
, R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 02_image021
, Where o is an integer from 1 to 3, Z 1 and Z 2 are each independently
Figure 02_image023
or
Figure 02_image025
, A is the structure of formula II or formula III, [formula II]
Figure 02_image003
[Formula III]
Figure 02_image005
In formula II and formula III, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 02_image023
or
Figure 02_image025
，Q 1 is
Figure 02_image027
or
Figure 02_image029
, Q 2 is
Figure 02_image031
, P is an integer from 0 to 30.

因此，本發明的第二目的，即在提供一種具有優異的抗生物沾黏能力的抗生物沾黏共聚物。Therefore, the second objective of the present invention is to provide an anti-bioadhesion copolymer with excellent anti-bioadhesion ability.

於是，本發明抗生物沾黏共聚物，具有式I的結構： [式I]

Figure 02_image001
； 式I中，m為1至5的整數； n為15至25的整數； Y 1及Y 2之其中一者為
Figure 02_image017
，另一者為
Figure 02_image019
； R 1為氫或甲基； R 2為伸甲基或伸乙基； R 3為單鍵或
Figure 02_image021
，其中，o為1至3的整數； Z 1及Z 2各自獨立地為
Figure 02_image023
或
Figure 02_image025
；及 A為式II或式III的結構， [式II]
Figure 02_image003
[式III]
Figure 02_image005
式II及式III中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 02_image023
或
Figure 02_image025
，Q 1為
Figure 02_image027
或
Figure 02_image029
，Q 2為
Figure 02_image031
，p為0至30的整數。 Therefore, the anti-biological adhesion copolymer of the present invention has the structure of formula I: [Formula I]
Figure 02_image001
; In formula I, m is an integer from 1 to 5; n is an integer from 15 to 25; one of Y 1 and Y 2 is
Figure 02_image017
, The other is
Figure 02_image019
; R 1 is hydrogen or methyl; R 2 is ethylene or ethylene; R 3 is a single bond or
Figure 02_image021
, Where o is an integer from 1 to 3; Z 1 and Z 2 are each independently
Figure 02_image023
or
Figure 02_image025
; And A is the structure of formula II or formula III, [formula II]
Figure 02_image003
[Formula III]
Figure 02_image005
In formula II and formula III, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 02_image023
or
Figure 02_image025
，Q 1 is
Figure 02_image027
or
Figure 02_image029
, Q 2 is
Figure 02_image031
, P is an integer from 0 to 30.

因此，本發明的第三目的，即在提供一種抗生物沾黏共聚物的製法。Therefore, the third object of the present invention is to provide a method for preparing an anti-bioadhesion copolymer.

於是，本發明抗生物沾黏膜的製法，包含以下步驟： (a) 提供具有式 I-1結構的兩親性化合物，以及疏水性聚合物或疏水性膜體； (b) 使該兩親性化合物的乙烯基與式II-1或式III-1所示的兩性離子化合物進行自由基加成聚合反應，以生成該式I所示的抗生物沾黏共聚物；及 一步驟(I)或一步驟(II)，其中，該步驟(I)是在該步驟(b)前，使該兩親性化合物的苯基吸附於該疏水性聚合物或該疏水性膜體；該步驟(II)是在該步驟(b)後，使該抗生物沾黏共聚物的苯基吸附於該疏水性聚合物或該疏水性膜體， [式I-1]

Figure 02_image007
[式II-1]
Figure 02_image009
[式III-1]
Figure 02_image011
式I-1中，m為1至5的整數，n為15至25的整數，Y 3及Y 4之其中一者為
Figure 02_image017
，另一者為
Figure 02_image033
，其中，R 1為氫或甲基，R 2為伸甲基或伸乙基，R 3為單鍵或
Figure 02_image021
，其中，o為1至3的整數，Z 1及Z 2各自獨立地為
Figure 02_image023
或
Figure 02_image025
， 式II-1及式III-1中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 02_image023
或
Figure 02_image025
，Q 1為
Figure 02_image027
或
Figure 02_image029
，Q 2為
Figure 02_image031
。 Therefore, the method for preparing the anti-biological adhesion membrane of the present invention includes the following steps: (a) providing an amphiphilic compound having the structure of formula I-1, and a hydrophobic polymer or a hydrophobic membrane; (b) making the amphiphilic The vinyl group of the compound undergoes radical addition polymerization with the zwitterionic compound represented by formula II-1 or formula III-1 to produce the anti-bioadhesive copolymer represented by formula I; and one step (I) or A step (II), wherein the step (I) is to adsorb the phenyl group of the amphiphilic compound to the hydrophobic polymer or the hydrophobic membrane before the step (b); the step (II) After this step (b), the phenyl group of the anti-bioadhesive copolymer is adsorbed on the hydrophobic polymer or the hydrophobic membrane, [Formula I-1]
Figure 02_image007
[Formula II-1]
Figure 02_image009
[Formula III-1]
Figure 02_image011
In formula I-1, m is an integer from 1 to 5, n is an integer from 15 to 25, and one of Y 3 and Y 4 is
Figure 02_image017
, The other is
Figure 02_image033
, Where R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 02_image021
, Where o is an integer from 1 to 3, and Z 1 and Z 2 are each independently
Figure 02_image023
or
Figure 02_image025
, In formula II-1 and formula III-1, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 02_image023
or
Figure 02_image025
，Q 1 is
Figure 02_image027
or
Figure 02_image029
, Q 2 is
Figure 02_image031
.

本發明的功效在於：本發明抗生物沾黏共聚物透過該A的基團從而具有很好的抗生物沾黏能力。本發明抗生物沾黏膜，透過具有抗生物沾黏能力的該抗生物沾黏共聚物，且該抗生物沾黏共聚物中具有疏水性的苯基而能穩固地吸附於該疏水性聚合物，繼而該抗生物沾黏膜的表面不易有生物積垢產生。The effect of the present invention is that the anti-bioadhesion copolymer of the present invention penetrates the A group to have a good anti-bioadhesion ability. The anti-biological adhesion membrane of the present invention can be firmly adsorbed on the hydrophobic polymer through the anti-biological adhesion copolymer having anti-biological adhesion ability, and the hydrophobic phenyl group in the anti-biological adhesion copolymer, Then, the surface of the anti-biological adhesion mucosa is not prone to biofouling.

本發明的另一功效在於：本發明抗生物沾黏膜的製法，利用該兩親性化合物做為該兩性離子化合物與該疏水性聚合物或疏水性膜體之間的連接橋樑，該兩親性化合物中具有疏水性的苯基而能穩固地吸附於該疏水性聚合物或疏水性膜體，該兩親性化合物中的乙烯基則能與該兩性離子化合物進行自由基加成聚合反應，從而製得具有很好的抗生物沾黏能力的該抗生物沾黏膜。Another effect of the present invention is that the method for preparing the anti-biological adhesion membrane of the present invention uses the amphiphilic compound as a connection bridge between the zwitterionic compound and the hydrophobic polymer or hydrophobic membrane. The compound has a hydrophobic phenyl group and can be firmly adsorbed to the hydrophobic polymer or hydrophobic membrane, and the vinyl group in the amphiphilic compound can undergo radical addition polymerization with the zwitterionic compound, thereby The anti-biological adhesion mucosa with good anti-biological adhesion ability is prepared.

以下就本發明內容進行詳細說明：The content of the present invention will be described in detail below:

於本文中，該「抗生物沾黏(anti-biofouling)」泛指抵抗生物類物質的沾黏或堆積，該生物類物質的種類沒有特別限制，例如但不限於蛋白質、細菌、病毒、細胞、生物組織、微生物或藻類等。As used herein, the "anti-biofouling" generally refers to resistance to adhesion or accumulation of biological substances. The types of biological substances are not particularly limited, such as but not limited to proteins, bacteria, viruses, cells, Biological tissues, microorganisms or algae, etc.

於本文中，該「疏水性聚合物」泛指具有疏水性且適用於形成疏水性膜體的聚合物。於本文中，該「疏水性膜體」尤其是指具有過濾能力的疏水性膜體。As used herein, the "hydrophobic polymer" generally refers to a polymer that is hydrophobic and is suitable for forming a hydrophobic film. In this context, the "hydrophobic membrane" especially refers to a hydrophobic membrane with filtering ability.

於本文中，該「兩性離子化合物(zwitterionic)」泛指具有抗生物沾黏能力的兩性離子化合物。As used herein, the “zwitterionic compound (zwitterionic)” generally refers to a zwitterionic compound with anti-biological adhesion ability.

本發明抗生物沾黏膜包含一膜體。該膜體包括疏水性聚合物，及吸附於該疏水性聚合物的抗生物沾黏共聚物。The anti-biological adhesion membrane of the present invention includes a membrane body. The film body includes a hydrophobic polymer and an anti-biological adhesion copolymer adsorbed on the hydrophobic polymer.

該疏水性聚合物的具體種類沒有特別限制，例如但不限於聚偏二氟乙烯、聚四氟乙烯或上述的任意組合。在本發明的一些具體例，該疏水性聚合物是選自於聚偏二氟乙烯。The specific type of the hydrophobic polymer is not particularly limited, such as but not limited to polyvinylidene fluoride, polytetrafluoroethylene or any combination of the above. In some specific examples of the present invention, the hydrophobic polymer is selected from polyvinylidene fluoride.

該抗生物沾黏共聚物具有式I的結構； [式I]

Figure 02_image001
式I中，m為1至5的整數。n為15至25的整數。 Y 1及Y 2之其中一者為
Figure 02_image017
，另一者為
Figure 02_image019
。其中，R 1為氫或甲基。R 2為伸甲基或伸乙基。R 3為單鍵或
Figure 02_image021
， o為1至3的整數。Z 1及Z 2各自獨立地為
Figure 02_image023
或
Figure 02_image025
。 A為式II或式III的結構， [式II]
Figure 02_image003
[式III]
Figure 02_image005
式II及式III中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 02_image023
或
Figure 02_image025
，Q 1為
Figure 02_image027
或
Figure 02_image029
，Q 2為
Figure 02_image031
，p為0至30的整數。 較佳地，該式I中，該Y 2為
Figure 02_image017
。 在本發明的一些具體例，該式I中，該R 3為單鍵。 在本發明的一些具體例，該式I中，該Z 1及Z 2各自獨立地為
Figure 02_image023
。 在本發明的一些具體例，該式I中，該A為式I的結構。 The anti-biological adhesion copolymer has a structure of formula I; [formula I]
Figure 02_image001
In formula I, m is an integer from 1 to 5. n is an integer from 15 to 25. One of Y 1 and Y 2 is
Figure 02_image017
, The other is
Figure 02_image019
. Wherein, R 1 is hydrogen or methyl. R 2 is ethylene or ethylene. R 3 is a single bond or
Figure 02_image021
, O is an integer from 1 to 3. Z 1 and Z 2 are each independently
Figure 02_image023
or
Figure 02_image025
. A is the structure of Formula II or Formula III, [Formula II]
Figure 02_image003
[Formula III]
Figure 02_image005
In formula II and formula III, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 02_image023
or
Figure 02_image025
，Q 1 is
Figure 02_image027
or
Figure 02_image029
, Q 2 is
Figure 02_image031
, P is an integer from 0 to 30. Preferably, in the formula I, the Y 2 is
Figure 02_image017
. In some specific examples of the present invention, in the formula I, the R 3 is a single bond. In some specific examples of the present invention, in the formula I, the Z 1 and Z 2 are each independently
Figure 02_image023
. In some specific examples of the present invention, in the formula I, the A is the structure of the formula I.

在本發明抗生物沾黏膜的一種實施態樣，該膜體是由該疏水性聚合物及該抗生物沾黏共聚物所共同構成。In one embodiment of the anti-biological adhesion membrane of the present invention, the membrane body is composed of the hydrophobic polymer and the anti-biological adhesion copolymer.

在本發明抗生物沾黏膜的另一種實施態樣，在該膜體中，該疏水性聚合物是構成一疏水性層，且抗生物沾黏共聚物是吸附於該疏水性層。In another embodiment of the anti-biological adhesion film of the present invention, in the film body, the hydrophobic polymer forms a hydrophobic layer, and the anti-biological adhesion copolymer is adsorbed on the hydrophobic layer.

本發明抗生物沾黏膜的製法，包含以下步驟： (a) 提供具有式 I-1結構的兩親性化合物，以及疏水性聚合物或疏水性膜體； (b) 使該兩親性化合物的乙烯基與式II-1或式III-1所示的兩性離子化合物進行自由基加成聚合反應，以生成該式I所示的抗生物沾黏共聚物；及 一步驟(I)或一步驟(II)，其中，該步驟(I)是在該步驟(b)前，使該兩親性化合物的苯基吸附於該疏水性聚合物或該疏水性膜體；該步驟(II)是在該步驟(b)後，使該抗生物沾黏共聚物的苯基吸附於該疏水性聚合物或該疏水性膜體； [式I-1]

Figure 02_image007
[式II-1]
Figure 02_image009
[式III-1]
Figure 02_image011
式I-1中，m為1至5的整數。n為15至25的整數。Y 3及Y 4之其中一者為
Figure 02_image017
，另一者為
Figure 02_image033
，其中，R 1為氫或甲基，R 2為伸甲基或伸乙基，R 3為單鍵或
Figure 02_image021
，其中，o為1至3的整數，Z 1及Z 2各自獨立地為
Figure 02_image023
或
Figure 02_image025
。 式II-1及式III-1中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 02_image023
或
Figure 02_image025
，Q 1為
Figure 02_image027
或
Figure 02_image029
，Q 2為
Figure 02_image031
。 The preparation method of the anti-biological adhesion film of the present invention includes the following steps: (a) providing an amphiphilic compound having the structure of formula I-1, and a hydrophobic polymer or a hydrophobic membrane; (b) making the amphiphilic compound The vinyl group and the zwitterionic compound represented by formula II-1 or formula III-1 undergo free radical addition polymerization to produce the anti-bioadhesive copolymer represented by formula I; and one step (I) or one step (II), wherein the step (I) is before the step (b), the phenyl group of the amphiphilic compound is adsorbed on the hydrophobic polymer or the hydrophobic membrane; the step (II) is After the step (b), the phenyl group of the anti-bioadhesive copolymer is adsorbed on the hydrophobic polymer or the hydrophobic membrane; [Formula I-1]
Figure 02_image007
[Formula II-1]
Figure 02_image009
[Formula III-1]
Figure 02_image011
In formula I-1, m is an integer of 1 to 5. n is an integer from 15 to 25. One of Y 3 and Y 4 is
Figure 02_image017
, The other is
Figure 02_image033
, Where R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 02_image021
, Where o is an integer from 1 to 3, and Z 1 and Z 2 are each independently
Figure 02_image023
or
Figure 02_image025
. In formula II-1 and formula III-1, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 02_image023
or
Figure 02_image025
，Q 1 is
Figure 02_image027
or
Figure 02_image029
, Q 2 is
Figure 02_image031
.

在該步驟(a)，較佳地，在該式I-1中，該Y 2為

Figure 02_image017
。在本發明的一些具體例，在該式I-1中，該R 3為單鍵。在本發明的一些具體例，在該式I-1中，該Z 1及Z 2各自獨立地為
Figure 02_image023
。 In this step (a), preferably, in the formula I-1, the Y 2 is
Figure 02_image017
. In some specific examples of the present invention, in the formula I-1, the R 3 is a single bond. In some specific examples of the present invention, in the formula I-1, the Z 1 and Z 2 are each independently
Figure 02_image023
.

更進一步地說，在該步驟(a)中，是使具有式IV結構的化合物與具有式V結構的化合物進行開環反應，得到該兩親性化合物， [式IV]

Figure 02_image013
[式V]
Figure 02_image015
式IV中，m為1至5的整數，n為15至25的整數。 式V中，R 1為氫或甲基，R 2為伸甲基或伸乙基，R 3為單鍵或
Figure 02_image021
，其中，o為1至3的整數， Z 2為
Figure 02_image023
或
Figure 02_image025
，Z 4為
Figure 02_image035
或
Figure 02_image037
。 其中，該具有式IV結構的化合物的重量平均分子量範圍為5500至9500，數目平均分子量的範圍為2000至3000，馬來酸酐單體單元的含量範圍為22.5至42wt%。 Furthermore, in this step (a), the compound having the structure of formula IV and the compound having the structure of formula V are subjected to a ring-opening reaction to obtain the amphiphilic compound, [Formula IV]
Figure 02_image013
[Formula V]
Figure 02_image015
In formula IV, m is an integer from 1 to 5, and n is an integer from 15 to 25. In formula V, R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 02_image021
, Where o is an integer from 1 to 3, and Z 2 is
Figure 02_image023
or
Figure 02_image025
, Z 4 is
Figure 02_image035
or
Figure 02_image037
. Wherein, the weight average molecular weight of the compound having the structure of formula IV ranges from 5500 to 9500, the number average molecular weight ranges from 2000 to 3000, and the content of maleic anhydride monomer units ranges from 22.5 to 42wt%.

在本發明的一些具體實施例，是進行該步驟(I)，也就是先使該兩親性化合物的苯基吸附於疏水性聚合物或該疏水性膜體，再使該兩親性化合物的乙烯基與式II-1或式III-1所示的兩性離子化合物進行自由基加成聚合反應生成該式I所示的抗生物沾黏共聚物。In some specific embodiments of the present invention, this step (I) is performed, that is, the phenyl group of the amphiphilic compound is first adsorbed to the hydrophobic polymer or the hydrophobic membrane, and then the amphiphilic compound is The vinyl group and the zwitterionic compound represented by formula II-1 or formula III-1 undergo free radical addition polymerization to generate the anti-bioadhesive copolymer represented by formula I.

其中，在該步驟(I)的第一種態樣，該兩親性化合物的苯基是吸附於該疏水性膜體。該疏水性膜體的構成材料的具體種類沒有特別限制，例如但不限於聚偏二氟乙烯、聚四氟乙烯或上述的任意組合。在本發明的一些具體例，該疏水性膜體是由聚偏二氟乙烯所構成。Wherein, in the first aspect of the step (I), the phenyl group of the amphiphilic compound is adsorbed on the hydrophobic membrane. The specific type of the constituent material of the hydrophobic membrane is not particularly limited, such as but not limited to polyvinylidene fluoride, polytetrafluoroethylene, or any combination of the foregoing. In some specific examples of the present invention, the hydrophobic membrane is composed of polyvinylidene fluoride.

在該步驟(I)的第二種態樣， 該兩親性化合物的苯基是吸附於該疏水性聚合物，且該步驟(I)還包括以下子步驟：(I-1)使包括該疏水性聚合物及該兩親性化合物的混合物進行一成膜程序。其中，該疏水性聚合物的具體種類沒有特別限制，例如但不限於聚偏二氟乙烯、聚四氟乙烯或上述的任意組合；在本發明的一些具體例，該疏水性聚合物是選自於聚偏二氟乙烯。該成膜程序的具體方式及條件沒有特別限制，可使用現有的薄膜製備工藝，尤其是過濾膜的製備工藝，只要不損及該抗生物沾黏膜的抗生物沾黏的能力即可。在本發明的一些具體例中，該成膜程序例如但不限於濕式相轉化法(wet phase inversion method)。In the second aspect of the step (I), the phenyl group of the amphiphilic compound is adsorbed on the hydrophobic polymer, and the step (I) further includes the following sub-steps: (I-1) making the The mixture of the hydrophobic polymer and the amphiphilic compound undergoes a film forming process. Wherein, the specific type of the hydrophobic polymer is not particularly limited, such as but not limited to polyvinylidene fluoride, polytetrafluoroethylene or any combination of the above; in some specific examples of the present invention, the hydrophobic polymer is selected from In polyvinylidene fluoride. The specific method and conditions of the film forming procedure are not particularly limited, and the existing film preparation process, especially the preparation process of the filter membrane, can be used, as long as the anti-biological adhesion ability of the anti-biological adhesion membrane is not damaged. In some specific examples of the present invention, the film forming procedure is for example, but not limited to, a wet phase inversion method.

雖然在本發明的一些具體實施例是進行該步驟(I)，但可以理解的是，本發明當然也可以是進行該步驟(II)且不會損及該抗生物沾黏膜的抗生物沾黏能力，也就是先使該兩親性化合物的乙烯基與式II-1或式III-1所示的兩性離子化合物進行自由基加成聚合反應生成該式I所示的抗生物沾黏共聚物後，再使該式I所示的抗生物沾黏共聚物的苯基吸附該疏水性聚合物或該疏水性膜體。Although this step (I) is carried out in some specific embodiments of the present invention, it is understandable that the present invention can of course also carry out this step (II) without damaging the anti-bioadhesion of the anti-bioadhesion membrane. Ability, that is, firstly make the vinyl group of the amphiphilic compound and the zwitterionic compound represented by formula II-1 or formula III-1 undergo free radical addition polymerization to form the anti-biological adhesion copolymer represented by formula I Then, the phenyl group of the anti-bioadhesive copolymer represented by formula I is allowed to adsorb the hydrophobic polymer or the hydrophobic film.

且在該步驟(II)的第一種態樣，該抗生物沾黏共聚物的苯基是吸附於該疏水性膜體。該疏水性膜體的構成材料的具體種類沒有特別限制，例如但不限於聚偏二氟乙烯、聚四氟乙烯或上述的任意組合。And in the first aspect of the step (II), the phenyl group of the anti-bioadhesive copolymer is adsorbed on the hydrophobic membrane. The specific type of the constituent material of the hydrophobic membrane is not particularly limited, such as but not limited to polyvinylidene fluoride, polytetrafluoroethylene, or any combination of the foregoing.

在該步驟(II)的第二種態樣， 該抗生物沾黏共聚物的苯基是吸附於該疏水性聚合物，且該步驟(II)還包括以下子步驟：(II-1)使包括該抗生物沾黏共聚物及該疏水性聚合物的混合物進行一成膜程序。其中，該疏水性聚合物的具體種類沒有特別限制，例如但不限於聚偏二氟乙烯、聚四氟乙烯或上述的任意組合。該成膜程序的具體操作方式及條件沒有特別限制，可使用現有的薄膜製備工藝，尤其是過濾膜的製備工藝，只要不損及該抗生物沾黏膜的抗生物沾黏的能力即可。In the second aspect of the step (II), the phenyl group of the anti-bioadhesive copolymer is adsorbed on the hydrophobic polymer, and the step (II) further includes the following sub-steps: (II-1) The mixture including the anti-biological adhesion copolymer and the hydrophobic polymer undergoes a film forming process. Wherein, the specific type of the hydrophobic polymer is not particularly limited, such as but not limited to polyvinylidene fluoride, polytetrafluoroethylene or any combination of the above. The specific operation mode and conditions of the film forming procedure are not particularly limited, and the existing film preparation process, especially the preparation process of the filter membrane, can be used, as long as the anti-biological adhesion ability of the anti-biological adhesion membrane is not damaged.

在該步驟(b)，該自由基加成聚合反應所使用的自由基起始劑、溶劑及具體操作條件沒有特別限制，可使用任何現有的自由基加成聚合反應工藝中所用的自由基起始劑、溶劑以及操作條件。在本發明的一些具體實施例，該自由基加成聚合反應的反應時間範圍例如但不限於0.5至4小時。In this step (b), the free radical initiator, solvent and specific operating conditions used in the free radical addition polymerization reaction are not particularly limited, and any existing free radical addition polymerization process used in the free radical initiator can be used. Starting agent, solvent and operating conditions. In some specific embodiments of the present invention, the reaction time range of the radical addition polymerization reaction is, for example, but not limited to 0.5 to 4 hours.

本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further described with reference to the following embodiments, but it should be understood that the embodiments are for illustrative purposes only, and should not be construed as limiting the implementation of the present invention.

[合成例1] 兩親性化合物的合成 將35克的苯乙烯馬來酸酐共聚物(購自於Cray Valley Hydrocarbon Specialty Chemicals，分子量為5500 g/mol)，與65克的丙烯酸-2-羥乙酯(購自於Sigma-Aldrich，分子量為116.12 g/mol，)在60℃下反應24小時，得到高粘度的液體。將該高黏度的液體加入水中，得到白色結晶，即為合成例1的兩親性化合物。 並利用核磁共振光譜儀(NMR，廠商Agilent，型號Varian Unity 400 MHz)及傅里葉變換衰減全反射紅外光譜儀 (ATR-FTIR，)分析該合成例1的兩親性化合物，分別得到圖1的氫核磁共振光譜( 1H NMR spectrum) ，以及圖2的ATR-FTIR光譜；以及利用酸鹼滴定量測該合成例1的兩親性化合物的酸價，得知其酸價為170至185mg NaOH/g。 [Synthesis Example 1] Synthesis of amphiphilic compound 35 grams of styrene maleic anhydride copolymer (purchased from Cray Valley Hydrocarbon Specialty Chemicals, molecular weight 5500 g/mol), and 65 grams of acrylic acid-2-hydroxyethyl The ester (purchased from Sigma-Aldrich, with a molecular weight of 116.12 g/mol) was reacted at 60°C for 24 hours to obtain a high-viscosity liquid. The high-viscosity liquid is added to water to obtain white crystals, which are the amphiphilic compound of Synthesis Example 1. And using nuclear magnetic resonance spectrometer (NMR, manufacturer Agilent, model Varian Unity 400 MHz) and Fourier transform attenuated total reflection infrared spectrometer (ATR-FTIR,) to analyze the amphiphilic compound of synthesis example 1, respectively, obtain the hydrogen in Figure 1 1 H NMR spectrum, and the ATR-FTIR spectrum of Figure 2; and the acid value of the amphiphilic compound of Synthesis Example 1 was measured by acid-base titration, and the acid value was 170 to 185 mg NaOH/ g.

[實施例1] 1. 疏水性膜體的製備： 將6wt%的聚乙二醇(PEG，做為成孔劑，購自於Sigma-Aldrich，Mw 為 600 g/mol)，及79wt%的N-甲基吡咯烷酮(NMP，購自於美國Mallinckrodt Chemical Co.)混合後在75℃以超音波震盪處理30分鐘，使PEG均勻地分散在NMP中，然後，再加入15wt%的聚偏二氟乙烯的粉末(PVDF，購自於Sigma-Aldrich，Mw為534,000 g/mol)，並在75℃攪拌24小時，得到PVDF溶液。先利用超音波清洗機將該PVDF溶液進行脫氣處理15分鐘，再利用塗佈機(廠商為德國Erichsen，型號360)將該PVDF溶液塗佈在一玻璃板上，形成一薄膜(厚度為120μm)，並立即將該薄膜浸入凝固浴(由去離子水及乙醇所組成，去離子水與乙醇的體積比為1：1)中，使該薄膜定型。然後，將該薄膜從該凝固浴中取出並轉移到浸漬液(由去離子水及乙醇所組成，去離子水與乙醇的體積比為1：1)中後在25℃靜置24小時以除去剩餘的凝固浴。之後，從浸漬液中取出該薄膜，並為了穩定該薄膜的孔結構，將該薄膜與甲醇及正己烷進行溶劑交換三次且每次30分鐘，製得由PVDF所構成的疏水性膜體。 2. 包括兩親性化合物的疏水性膜體的製備： 將數片的該疏水性膜體(每一片膜的面積為2cm×2cm)，加到合成例1兩親性化合物的甲醇溶液(由合成例1兩親性化合物及甲醇所組成，濃度為0.9M)中並浸泡40分鐘，使合成例1兩親性化合物吸附於該等疏水性膜體，即製得數片包括兩親性化合物的疏水性膜體。並可選擇性地將該等包括兩親性化合物的疏水性膜體進行以下清洗程序：將該等包括兩親性化合物的疏水性膜體轉移至去離子水中並靜置30分鐘，接著，用去離子水洗滌該等包括兩親性化合物的疏水性膜體3次，去除沒有吸附的合成例1兩親性化合物。 3. 抗生物沾黏膜的製備： 將該等包括兩親性化合物的疏水性膜體浸入偶氮二異丁腈的甲醇溶液[由偶氮二異丁腈(AIBN)及甲醇所組成，濃度為0.03M)中並在空氣中靜置1小時。然後，將該等包括兩親性化合物的疏水性膜體轉移至磺基甜菜鹼甲基丙烯酸酯的甲醇水溶液[由磺基甜菜鹼甲基丙烯酸酯(SBMA)及甲醇所組成，甲醇與水的體積比為3：7，濃度為0.3M)中，形成一反應液。將該反應液在80℃以及攪拌速率60 rpm的條件，使該等包括兩親性化合物的疏水性膜體與SBMA進行自由基加成聚合反應4小時，即製得數片的實施例1的抗生物沾黏膜。並可選擇性地將該等實施例1的抗生物沾黏膜進行以下的清洗程序：將該等實施例1的抗生物沾黏膜轉移至去離子水中以除去沒有反應的殘餘SBMA後，在空氣中乾燥2小時。 利用該傅里葉變換衰減全反射紅外光譜儀分析該實施例1的抗生物沾黏膜，得到圖3的ATR-FTIR光譜。 [Example 1] 1. Preparation of hydrophobic membrane: 6wt% polyethylene glycol (PEG, as a pore former, purchased from Sigma-Aldrich, Mw of 600 g/mol), and 79wt% of N-methylpyrrolidone (NMP, purchased from Mallinckrodt Chemical, USA Co.) was mixed and treated with ultrasonic vibration at 75°C for 30 minutes to uniformly disperse the PEG in the NMP, and then 15wt% polyvinylidene fluoride powder (PVDF, purchased from Sigma-Aldrich, Mw 534,000 g/mol), and stirred at 75°C for 24 hours to obtain a PVDF solution. First use an ultrasonic cleaning machine to degas the PVDF solution for 15 minutes, and then use a coating machine (manufacturer: Erichsen, Germany, model 360) to coat the PVDF solution on a glass plate to form a thin film (with a thickness of 120μm) ), and immediately immerse the film in a coagulation bath (composed of deionized water and ethanol, and the volume ratio of deionized water to ethanol is 1:1) to shape the film. Then, the film was taken out of the coagulation bath and transferred to an immersion solution (composed of deionized water and ethanol, the volume ratio of deionized water to ethanol is 1:1), and then stood at 25°C for 24 hours to remove The remaining coagulation bath. After that, the film was taken out from the immersion liquid, and in order to stabilize the pore structure of the film, the film was solvent-exchanged with methanol and n-hexane three times for 30 minutes each time to prepare a hydrophobic film body composed of PVDF. 2. Preparation of hydrophobic membranes including amphiphilic compounds: Add several pieces of this hydrophobic membrane (each membrane area is 2cm×2cm) to the methanol solution of the amphiphilic compound in Synthesis Example 1 (composed of the amphiphilic compound and methanol in Synthesis Example 1, with a concentration of 0.9 M) and soak for 40 minutes to allow the amphiphilic compound of Synthesis Example 1 to be adsorbed on the hydrophobic membranes, that is, several hydrophobic membranes including amphiphilic compounds are prepared. The hydrophobic membranes containing amphiphilic compounds can be selectively subjected to the following cleaning procedure: the hydrophobic membranes containing amphiphilic compounds are transferred to deionized water and left for 30 minutes, and then The hydrophobic membranes including amphiphilic compounds were washed with deionized water three times to remove the amphiphilic compounds of Synthesis Example 1 that were not adsorbed. 3. Preparation of anti-biological adhesion mucosa: The hydrophobic membranes including amphiphilic compounds are immersed in a methanol solution of azobisisobutyronitrile (composed of azobisisobutyronitrile (AIBN) and methanol, with a concentration of 0.03M) and placed in the air. Leave it for 1 hour. Then, the hydrophobic membrane body including the amphiphilic compound was transferred to a methanol aqueous solution of sultaine methacrylate [composed of sultaine methacrylate (SBMA) and methanol, the combination of methanol and water The volume ratio is 3:7, and the concentration is 0.3M) to form a reaction solution. Under the conditions of 80°C and 60 rpm agitation, the hydrophobic membranes including amphiphilic compounds and SBMA were subjected to free radical addition polymerization for 4 hours to obtain several pieces of Example 1 Anti-biological adhesion to mucous membranes. Optionally, the anti-biological adhesion membrane of Example 1 can be subjected to the following cleaning procedure: After the anti-biological adhesion membrane of Example 1 is transferred to deionized water to remove unreacted residual SBMA, in the air Dry for 2 hours. The Fourier transform attenuated total reflection infrared spectrometer was used to analyze the anti-biological adhesion film of Example 1 to obtain the ATR-FTIR spectrum of FIG. 3.

[實施例2] 1. 包括兩親性化合物的疏水性膜體的製備： 提供PVDF溶液，該PVDF溶液是與實施例1中所使用的PVDF溶液相同，故於此不再贅述。 將該PVDF溶液與總重為16.8 g的合成例1兩親性化合物的NMP溶液(由合成例1兩親性化合物及NMP所組成，濃度為0.3M)混合，使合成例1兩親性化合物吸附於PVDF，得到一混合物。利用濕式相轉化法使該混合物形成包括兩親性化合物的疏水性膜體。 2. 抗生物沾黏膜的製備： 使用與實施例1中相同的方式，使該包括兩親性化合物的疏水性膜體與SBMA進行自由基加成聚合反應0.5小時，形成實施例2的抗生物沾黏膜。 [Example 2] 1. Preparation of hydrophobic membranes including amphiphilic compounds: A PVDF solution is provided, and the PVDF solution is the same as the PVDF solution used in Example 1, so it will not be repeated here. This PVDF solution was mixed with the NMP solution of the amphiphilic compound of Synthesis Example 1 (consisting of the amphiphilic compound of Synthesis Example 1 and NMP, and the concentration is 0.3 M) with a total weight of 16.8 g to make the amphiphilic compound of Synthesis Example 1 Adsorbed on PVDF to obtain a mixture. The wet phase inversion method is used to form the mixture into a hydrophobic film including an amphiphilic compound. 2. Preparation of anti-biological adhesion mucosa: In the same manner as in Example 1, the hydrophobic membrane body including the amphiphilic compound and SBMA were subjected to free radical addition polymerization for 0.5 hours to form the anti-biological adhesion film of Example 2.

[實施例3及4] 實施例3及4使用與實施例2相似的製法製備抗生物沾黏膜，差別在於：在實施例3中，該包括兩親性化合物的疏水性膜體與SBMA進行自由基加成聚合反應的時間為2小時；在實施例4中，該包括兩親性化合物的疏水性膜體與SBMA進行自由基加成聚合反應的時間為4小時。 [Examples 3 and 4] Examples 3 and 4 used similar preparation methods as Example 2 to prepare anti-biological adhering membranes. The difference is: in Example 3, the time required for the free radical addition polymerization reaction between the hydrophobic membrane containing amphiphilic compounds and SBMA It is 2 hours; in Example 4, the time for the radical addition polymerization reaction between the hydrophobic membrane body including the amphiphilic compound and SBMA is 4 hours.

[比較例1] 比較例1為一種由PVDF所構成的疏水性膜體，其製備方式是與實施例1中製備疏水性膜體的方式相同，故於此不再贅述。 [Comparative Example 1] Comparative Example 1 is a hydrophobic membrane composed of PVDF, and its preparation method is the same as the method of preparing the hydrophobic membrane in Example 1, so it will not be repeated here.

[比較例2] 比較例2為一種包括兩親性化合物的疏水性膜體，其製備方式是與實施例1中製備包括兩親性化合物的疏水性膜體的方式相同，故於此不再贅述。 [Comparative Example 2] Comparative Example 2 is a hydrophobic membrane body including an amphiphilic compound, and its preparation method is the same as the method of preparing a hydrophobic membrane body including an amphiphilic compound in Example 1, so it will not be repeated here.

[比較例3] 比較例3為一種包括兩親性化合物的疏水性膜體，其製備方式是與實施例2中製備包括兩親性化合物的疏水性膜體的方式相同，故於此不再贅述。 [Comparative Example 3] Comparative Example 3 is a hydrophobic membrane body including an amphiphilic compound, and its preparation method is the same as the method of preparing a hydrophobic membrane body including an amphiphilic compound in Example 2, so it will not be repeated here.

實施例1至4的抗生物沾黏膜、比較例1的疏水性膜體，比較例2至3的包括兩親性化合物的疏水性膜體的差異整理如表1所示： 表1   組成 製法1 製法2 自由基加成聚合 反應時間(小時) 疏水性聚合物 兩親性化合物 兩性離子化合物 兩親性化合物＋疏水性膜體 兩親性化合物＋疏水性聚合物 實施例 1 有 有 有 P --- 4 2 有 有 有 --- P 0.5 3 有 有 有 --- P 2 4 有 有 有 --- P 4 比較例 1 有 無 無 --- --- 0 2 有 有 無 P --- 0 3 有 有 無 --- P 0 註：「製法1」是指先將疏水性聚合物形成疏水性膜體後，再使兩親性化合物吸附於該疏水性膜體，形成包括兩親性化合物的疏水性膜體；「製法2」是指將含有疏水性聚合物及兩親性化合物的混合物經濕式相轉化法形成包括兩親性化合物的疏水性膜體。 The anti-biological adhesion membranes of Examples 1 to 4, the hydrophobic membranes of Comparative Example 1, and the hydrophobic membranes of Comparative Examples 2 to 3 including amphiphilic compounds are sorted out as shown in Table 1: Table 1 composition Method 1 Method 2 Free radical addition polymerization reaction time (hours) Hydrophobic polymer Amphiphilic compound Zwitterionic compound Amphiphilic compound + hydrophobic membrane Amphiphilic compound + hydrophobic polymer Example 1 Have Have Have P --- 4 2 Have Have Have --- P 0.5 3 Have Have Have --- P 2 4 Have Have Have --- P 4 Comparative example 1 Have no no --- --- 0 2 Have Have no P --- 0 3 Have Have no --- P 0 Note: "Preparation method 1" refers to the formation of a hydrophobic film with a hydrophobic polymer, and then the amphiphilic compound is adsorbed on the hydrophobic film to form a hydrophobic film including the amphiphilic compound; "preparation method 2" It means that a mixture containing a hydrophobic polymer and an amphiphilic compound is subjected to a wet phase inversion method to form a hydrophobic film including the amphiphilic compound.

[性質評價][Property Evaluation]

將實施例1至4的抗生物沾黏膜、比較例1的疏水性膜體，及比較例2及3的包括兩親性化合物的疏水性膜體(以下皆簡稱為「待測薄膜」)進行靜態蛋白質吸附及動態蛋白質吸附的性質評價測試，測試結果如表2所示。The anti-biological adhesion membranes of Examples 1 to 4, the hydrophobic membranes of Comparative Example 1, and the hydrophobic membranes of Comparative Examples 2 and 3 including amphiphilic compounds (hereinafter all referred to as "test films") Static protein adsorption and dynamic protein adsorption properties evaluation test, the test results are shown in Table 2.

1. 靜態蛋白質吸附 先將待測薄膜(面積為2 cm ´ 1 cm)進行前處理後，再將經前處理的待測薄膜浸漬於15 mL的蛋白質水溶液中24小時。並利用紫外光-可見光分光光度計(廠商Hitachi，型號2400)，以波長為280 nm的條件，量測該蛋白質水溶液的初始濃度(C 0)以及經待測薄膜浸漬後的濃度(C 1)，再利用公式[1]算出待測薄膜的蛋白質吸附量(M)。待測薄膜的蛋白質吸附量(M)越小，代表待測薄膜在靜態環境下的抗生物沾黏的能力越佳。 其中，該前處理是將待測薄膜於15 mL的去離子水中浸泡30分鐘，使待測薄膜潤濕；之後，將待測薄膜轉移至15 mL的磷酸鹽緩衝溶液(PBS，其濃度為1M，pH值為6.9，磷酸鹽的種類為磷酸二氫鈉及磷酸氫二鈉)中浸泡30分鐘，使待測薄膜的孔隙間充滿該磷酸鹽緩衝溶液。 該蛋白質水溶液分為兩種，第一種的組成包括水及做為模擬蛋白質的牛血清白蛋白(bovine serum albumin，BSA)，初始濃度C 0為1 mg/mL；第2種的組成包括水及做為模擬蛋白質的溶菌酶(lysozyme，LYS)，初始濃度C 0為1 mg/mL。 待測薄膜的蛋白質吸附量(M)的計算公式如下： 公式[1]：M＝(C 0－C 1)×V/A M：待測薄膜的蛋白質吸附量，單位為μg/cm 2； C 0：蛋白質水溶液的初始濃度，單位為mg/mL； C 1：蛋白質水溶液經待測薄膜吸附後的濃度，單位為mg/mL； V：蛋白質水溶液的體積，單位為L； A：待測薄膜的面積，單位為cm 2。 1. Static protein adsorption Firstly, the film to be tested (with an area of 2 cm ´ 1 cm) is pre-treated, and then the pre-treated film to be tested is immersed in 15 mL of protein aqueous solution for 24 hours. And using an ultraviolet-visible spectrophotometer (manufacturer Hitachi, model 2400), with a wavelength of 280 nm, measure the initial concentration (C 0 ) of the protein aqueous solution and the concentration (C 1 ) after immersion in the film to be tested , And then use formula [1] to calculate the protein adsorption capacity (M) of the film to be tested. The smaller the protein adsorption capacity (M) of the film to be tested, the better the resistance to biological adhesion of the film to be tested in a static environment. Among them, the pretreatment is to soak the film to be tested in 15 mL of deionized water for 30 minutes to wet the film to be tested; then, transfer the film to be tested to 15 mL of phosphate buffer solution (PBS, with a concentration of 1M). , The pH value is 6.9, and the types of phosphates are sodium dihydrogen phosphate and disodium hydrogen phosphate) for 30 minutes to fill the pores of the film to be tested with the phosphate buffer solution. The protein aqueous solution is divided into two types. The first composition includes water and bovine serum albumin (BSA) as a simulated protein, with an initial concentration C 0 of 1 mg/mL; the second composition includes water And lysozyme (LYS) as a simulated protein, the initial concentration C 0 is 1 mg/mL. The calculation formula of the protein adsorption capacity (M) of the film to be tested is as follows: Formula [1]: M=(C 0 -C 1 )×V/A M: the protein adsorption capacity of the film to be tested, the unit is μg/cm 2 ; C 0 : the initial concentration of the protein aqueous solution, the unit is mg/mL; C 1 : the concentration of the protein aqueous solution after being absorbed by the film to be tested, the unit is mg/mL; V: the volume of the protein aqueous solution, the unit is L; A: the film to be tested The area of ??in cm 2 .

2. 動態蛋白質吸附 將待測薄膜(面積為4 cm 2)裝設在垂直流式過濾(dead-end filtration)設備中，之後，利用該全流式超過濾設備進行過濾程序，該過濾程序的進料溫度為25±1℃，進料壓力(feed pressure)為1.66 bar，跨膜壓力(transmembrane pressure)為68 bar，保留壓力(retentate pressure)為1.66 bar，且該過濾程序包括以下順序的步驟：(1).過濾純水1小時，此步驟的純水通量為J 0；(2).過濾蛋白質水溶液1小時；(3).將該待測薄膜翻面，並進行反洗(backwash)1小時； (4).過濾純水1小時，此步驟的純水通量為J 1； (5).過濾蛋白質水溶液1小時；(6).將該待測薄膜翻面，並進行反洗1小時； (7).過濾純水1小時，此步驟的純水通量為J 2。其中，該蛋白質水溶液包括水及做為模擬蛋白質的牛血清白蛋白，且以用紫外光-可見光分光光度計在波長280 nm測得的濃度為1 mg/mL。 完成該過濾程序後，利用公式[2]及[3]計算待測薄膜的第一次純水回復率及第二次純水回復率。待測薄膜的純水回復率(pure water flux recovery ratio，FRR)愈高，代表待測薄膜的不可逆生物積垢愈少，待測薄膜的抗生物沾黏的能力越佳。 公式[2]：第一次純水回復率(1 stFRR)＝(J 1÷J 0)×100% 公式[3]：第二次純水回復率(2 ndFRR)＝(J 2÷J 0)×100% 其中，J 0、J 1及J 2分別利用公式[4]計算得到， 公式[4]：J n＝Q÷(A×Δt) J n：第n次的純水通量，單位為L/m 2h； Q：第n次中過濾的純水的體積，單位為L； A：待測薄膜的面積，單位為m 2； Δt：第n次的過濾時間，單位為小時(h)。 2. Dynamic protein adsorption Install the membrane to be tested (with an area of 4 cm 2 ) in a vertical flow filtration (dead-end filtration) equipment, and then use the full-flow ultrafiltration equipment to perform a filtration procedure. The feed temperature is 25±1℃, the feed pressure is 1.66 bar, the transmembrane pressure is 68 bar, the retentate pressure is 1.66 bar, and the filtration procedure includes the following steps in the sequence : (1). Filter pure water for 1 hour, and the pure water flux in this step is J 0 ; (2) Filter the protein aqueous solution for 1 hour; (3). Turn over the membrane to be tested and perform backwash ) 1 hour; (4) Filter pure water for 1 hour, the pure water flux in this step is J 1 ; (5) Filter the protein aqueous solution for 1 hour; (6) Turn over the film to be tested and reverse Wash for 1 hour; (7) Filter pure water for 1 hour, and the pure water flux in this step is J 2 . Wherein, the protein aqueous solution includes water and bovine serum albumin as a simulated protein, and the concentration measured with a UV-visible spectrophotometer at a wavelength of 280 nm is 1 mg/mL. After completing the filtration procedure, use formulas [2] and [3] to calculate the first pure water recovery rate and the second pure water recovery rate of the film to be tested. The higher the pure water flux recovery ratio (FRR) of the film to be tested, the less irreversible biofouling of the film to be tested, and the better the resistance to bioadhesion of the film to be tested. Formula [2]: The first pure water recovery rate (1 st FRR)=(J 1 ÷J 0 )×100% Formula [3]: The second pure water recovery rate (2 nd FRR)=(J 2 ÷ J 0 )×100% Among them, J 0 , J 1 and J 2 are calculated by formula [4], formula [4]: J n =Q÷(A×Δt) J n : the nth pure water flow Quantity, the unit is L/m 2 h; Q: the volume of pure water filtered in the nth time, the unit is L; A: the area of the film to be tested, the unit is m 2 ; Δt: the filtration time of the nth time, the unit Is the hour (h).

表2   靜態蛋白質吸附 動態蛋白質吸附 蛋白質吸附量M (μg/cm 2) BSA BSA LYS 第一次純水回復率(%) 第二次純水回復率(%) 實施例 1 0 0 95.3 96.6 2 83.3 --- --- --- 3 --- --- --- --- 4 33.3 --- --- --- 比較例 1 112.5 385.7 57.8 43.4 2 --- --- --- --- 3 220.8 --- --- --- 註：「---」表示無量測。 Table 2 Static protein adsorption Dynamic protein adsorption Protein adsorption capacity M (μg/cm 2 ) BSA BSA LYS The first pure water recovery rate (%) The second pure water recovery rate (%) Example 1 0 0 95.3 96.6 2 83.3 --- --- --- 3 --- --- --- --- 4 33.3 --- --- --- Comparative example 1 112.5 385.7 57.8 43.4 2 --- --- --- --- 3 220.8 --- --- --- Note: "---" means no measurement.

由表2的結果可知，相較於比較例1及3，實施例1、2及4的抗生物沾黏膜具有較佳的抗生物沾黏能力。It can be seen from the results in Table 2 that compared with Comparative Examples 1 and 3, the anti-biological adhesion films of Examples 1, 2 and 4 have better anti-biological adhesion ability.

惟以上所述者，僅為本發明的實施例而已，當不能以此限定本發明實施的範圍，凡是依本發明申請專利範圍及專利說明書內容所作的簡單的等效變化與修飾，皆仍屬本發明專利涵蓋的範圍內。However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope of the patent for the present invention.

本發明的其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中： 圖1是本發明的合成例1的兩親性化合物的 1H NMR光譜； 圖2是該合成例1的兩親性化合物的ATR-FTIR光譜；及 圖3是本發明的實施例1的抗生物沾黏膜的ATR-FTIR光譜。 The other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: Figure 1 is the 1 H NMR spectrum of the amphiphilic compound of Synthesis Example 1 of the present invention; Figure 2 is the synthesis example The ATR-FTIR spectrum of the amphiphilic compound of 1; and Fig. 3 is the ATR-FTIR spectrum of the anti-biological adhesion film of Example 1 of the present invention.

Figure 108121808-A0305-02-0002-15
Figure 108121808-A0305-02-0003-11
Figure 108121808-A0305-02-0002-15
Figure 108121808-A0305-02-0003-11

Claims (10)

一種抗生物沾黏膜，包含： 一膜體，包括疏水性聚合物及抗生物沾黏共聚物，其中，該抗生物沾黏共聚物吸附於該疏水性聚合物且具有式I的結構； [式I]
Figure 03_image001
式I中，m為1至5的整數，n為15至25的整數， Y 1及Y 2之其中一者為
Figure 03_image017
，另一者為
Figure 03_image019
， R 1為氫或甲基， R 2為伸甲基或伸乙基， R 3為單鍵或
Figure 03_image021
，其中，o為1至3的整數， Z 1及Z 2各自獨立地為
Figure 03_image023
或
Figure 03_image025
， A為式II或式III的結構， [式II]
Figure 03_image003
[式III]
Figure 03_image005
式II及式III中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 03_image023
或
Figure 03_image025
，Q 1為
Figure 03_image027
或
Figure 03_image029
，Q 2為
Figure 03_image031
，p為0至30的整數。 An anti-biological adhesion film, comprising: a film body, comprising a hydrophobic polymer and an anti-biological adhesion copolymer, wherein the anti-biological adhesion copolymer is adsorbed on the hydrophobic polymer and has a structure of formula I; I]
Figure 03_image001
In formula I, m is an integer from 1 to 5, n is an integer from 15 to 25, and one of Y 1 and Y 2 is
Figure 03_image017
, The other is
Figure 03_image019
, R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 03_image021
, Where o is an integer from 1 to 3, Z 1 and Z 2 are each independently
Figure 03_image023
or
Figure 03_image025
, A is the structure of formula II or formula III, [formula II]
Figure 03_image003
[Formula III]
Figure 03_image005
In formula II and formula III, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 03_image023
or
Figure 03_image025
，Q 1 is
Figure 03_image027
or
Figure 03_image029
, Q 2 is
Figure 03_image031
, P is an integer from 0 to 30. 如請求項1所述的抗生物沾黏膜，其中，在該膜體中，該疏水性聚合物是構成一疏水性層，且抗生物沾黏共聚物是吸附於該疏水性層。The anti-biological adhesion film according to claim 1, wherein, in the film body, the hydrophobic polymer constitutes a hydrophobic layer, and the anti-biological adhesion copolymer is adsorbed on the hydrophobic layer. 一種抗生物沾黏共聚物，具有式I的結構： [式I]
Figure 03_image001
； 式I中，m為1至5的整數； n為15至25的整數； Y 1及Y 2之其中一者為
Figure 03_image017
，另一者為
Figure 03_image019
； R 1為氫或甲基； R 2為伸甲基或伸乙基； R 3為單鍵或
Figure 03_image021
，其中，o為1至3的整數； Z 1及Z 2各自獨立地為
Figure 03_image023
或
Figure 03_image025
；及 A為式II或式III的結構， [式II]
Figure 03_image003
[式III]
Figure 03_image005
式II及式III中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 03_image023
或
Figure 03_image025
，Q 1為
Figure 03_image027
或
Figure 03_image029
，Q 2為
Figure 03_image031
，p為0至30的整數。 An anti-bioadhesion copolymer with the structure of Formula I: [Formula I]
Figure 03_image001
; In formula I, m is an integer from 1 to 5; n is an integer from 15 to 25; one of Y 1 and Y 2 is
Figure 03_image017
, The other is
Figure 03_image019
; R 1 is hydrogen or methyl; R 2 is ethylene or ethylene; R 3 is a single bond or
Figure 03_image021
, Where o is an integer from 1 to 3; Z 1 and Z 2 are each independently
Figure 03_image023
or
Figure 03_image025
; And A is the structure of formula II or formula III, [formula II]
Figure 03_image003
[Formula III]
Figure 03_image005
In formula II and formula III, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 03_image023
or
Figure 03_image025
，Q 1 is
Figure 03_image027
or
Figure 03_image029
, Q 2 is
Figure 03_image031
, P is an integer from 0 to 30. 如請求項3所述的抗生物沾黏共聚物，其中，該式I中，該Y 2為
Figure 03_image017
。 The anti-bioadhesion copolymer according to claim 3, wherein, in the formula I, the Y 2 is
Figure 03_image017
. 如請求項3所述的抗生物沾黏共聚物，其中，該式I中，該A為式II的結構。The anti-bioadhesion copolymer according to claim 3, wherein, in the formula I, the A is the structure of the formula II. 一種如請求項1所述的抗生物沾黏膜的製法，包含以下步驟： (a) 提供具有式 I-1結構的兩親性化合物，以及疏水性聚合物或疏水性膜體； (b) 使該兩親性化合物的乙烯基與式II-1或式III-1所示的兩性離子化合物進行自由基加成聚合反應，以生成該式I所示的抗生物沾黏共聚物；及 一步驟(I)或一步驟(II)，其中，該步驟(I)是在該步驟(b)前，使該兩親性化合物的苯基吸附於該疏水性聚合物或該疏水性膜體；該步驟(II)是在該步驟(b)後，使該抗生物沾黏共聚物的苯基吸附於該疏水性聚合物或該疏水性膜體； [式I-1]
Figure 03_image007
[式II-1]
Figure 03_image009
[式III-1]
Figure 03_image011
式I-1中， Y 3及Y 4之其中一者為
Figure 03_image017
，另一者為
Figure 03_image033
，其中，R 1為氫或甲基，R 2為伸甲基或伸乙基，R 3為單鍵或
Figure 03_image021
，其中，o為1至3的整數，Z 1及Z 2各自獨立地為
Figure 03_image023
或
Figure 03_image025
， 式II-1及式III-1中，X 1為氫或甲基，X 2及X 3各自獨立地為伸乙基或伸丙基，Z 3為
Figure 03_image023
或
Figure 03_image025
，Q 1為
Figure 03_image027
或
Figure 03_image029
，Q 2為
Figure 03_image031
。 A method for preparing an anti-biological mucosal membrane according to claim 1, comprising the following steps: (a) providing an amphiphilic compound having a structure of formula I-1, and a hydrophobic polymer or a hydrophobic membrane; (b) using The vinyl group of the amphiphilic compound undergoes radical addition polymerization with the zwitterionic compound represented by formula II-1 or formula III-1 to generate the anti-biological adhesion copolymer represented by formula I; and one step (I) or a step (II), wherein the step (I) is to adsorb the phenyl group of the amphiphilic compound to the hydrophobic polymer or the hydrophobic membrane before the step (b); the Step (II) is to make the phenyl group of the anti-bioadhesive copolymer adsorb to the hydrophobic polymer or the hydrophobic membrane after the step (b); [Formula I-1]
Figure 03_image007
[Formula II-1]
Figure 03_image009
[Formula III-1]
Figure 03_image011
In formula I-1, one of Y 3 and Y 4 is
Figure 03_image017
, The other is
Figure 03_image033
, Where R 1 is hydrogen or methyl, R 2 is methyl or ethyl, R 3 is a single bond or
Figure 03_image021
, Where o is an integer from 1 to 3, and Z 1 and Z 2 are each independently
Figure 03_image023
or
Figure 03_image025
, In formula II-1 and formula III-1, X 1 is hydrogen or methyl, X 2 and X 3 are each independently ethylene or propylene, and Z 3 is
Figure 03_image023
or
Figure 03_image025
，Q 1 is
Figure 03_image027
or
Figure 03_image029
, Q 2 is
Figure 03_image031
. 如請求項6所述的抗生物沾黏膜的製法，其中，在該步驟(a)中，是使具有式IV結構的化合物與具有式V結構的化合物進行開環反應，得到該兩親性化合物， [式IV]
Figure 03_image013
[式V]
Figure 03_image015
式IV中，m為1至5的整數，n為15至25的整數， 式V中，R 1為氫或甲基，R 2為伸甲基或伸乙基，R 3為單鍵或
Figure 03_image021
，其中，o為1至3的整數， Z 2為
Figure 03_image023
或
Figure 03_image025
，Z 4為
Figure 03_image035
或
Figure 03_image037
。 The method for preparing an anti-biological adhesion film according to claim 6, wherein, in this step (a), the compound having the structure of formula IV and the compound having the structure of formula V are subjected to a ring-opening reaction to obtain the amphiphilic compound , [Formula IV]
Figure 03_image013
[Formula V]
Figure 03_image015
In formula IV, m is an integer from 1 to 5, n is an integer from 15 to 25. In formula V, R 1 is hydrogen or methyl, R 2 is ethylene or ethylene, and R 3 is a single bond or
Figure 03_image021
, Where o is an integer from 1 to 3, and Z 2 is
Figure 03_image023
or
Figure 03_image025
, Z 4 is
Figure 03_image035
or
Figure 03_image037
. 如請求項6所述的抗生物沾黏膜的製法，其中，在該步驟(I)中，該兩親性化合物的苯基是吸附於該疏水性膜體。The method for preparing an anti-biological adhesion membrane according to claim 6, wherein, in the step (I), the phenyl group of the amphiphilic compound is adsorbed on the hydrophobic membrane. 如請求項6所述的抗生物沾黏膜的製法，其中，在該步驟(I)中， 該兩親性化合物的苯基是吸附於該疏水性聚合物，且該步驟(I)還包括以下子步驟： (I-1)使包括該疏水性聚合物及該兩親性化合物的混合物進行一成膜程序。 The method for preparing an anti-biological mucosal membrane according to claim 6, wherein, in the step (I), the phenyl group of the amphiphilic compound is adsorbed on the hydrophobic polymer, and the step (I) further includes the following Substep: (I-1) A film forming process is performed on the mixture including the hydrophobic polymer and the amphiphilic compound. 如請求項6所述的抗生物沾黏膜的製法，其中，在該步驟(a)中，該疏水性聚合物是選自於聚偏二氟乙烯，該疏水性膜體是選自於聚偏二氟乙烯。The method for preparing an anti-biological adhesion membrane according to claim 6, wherein in the step (a), the hydrophobic polymer is selected from polyvinylidene fluoride, and the hydrophobic membrane is selected from polyvinylidene fluoride. Difluoroethylene.
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