TWI394767B

TWI394767B - Honeycomb-like polymeric films base on dendritic side-chain polyurethane

Info

Publication number: TWI394767B
Application number: TW98142748A
Authority: TW
Inventors: Wen Chiung Su; Wei Ho Ting; Chun Ming Yeh; Chia Cheng Chang; Sheng Hong Dai; Ru Jong Jeng
Original assignee: Chung Shan Inst Of Science
Priority date: 2009-12-14
Filing date: 2009-12-14
Publication date: 2013-05-01
Also published as: TW201120078A

Description

樹枝狀高分子、含有側鏈規則樹枝狀高分子之聚胺酯及其製備方法 Dendrimer, polyurethane containing side chain regular dendrimer and preparation thereof method

本發明是合成末端具有疏水官能基的樹枝狀高分子(dendron)，並製備成樹枝狀高分子導入聚胺酯中，其中樹枝狀高分子末端基為烷鏈或者是全氟烷鏈，如C₁₀~C₁₈或是C₄以上全氟烷基乙基化合物之衍生物。 The invention relates to a dendrimer having a hydrophobic functional group at the end, and is prepared as a dendrimer into a polyurethane, wherein the dendrimer terminal group is an alkyl chain or a perfluoroalkyl chain, such as C ₁₀ ~ C ₁₈ or a derivative of a perfluoroalkylethyl compound of C ₄ or more.

近年來關於樹枝狀分子化學的相關文獻數量高達2000篇以上，樹枝狀聚合物(dendrimer)具備高度規則之分枝結構，藉由逐步反應(step reaction)精準控制分子大小及設計多樣化。Buhleier等人於1978年利用丙烯晴(acrylonitrile)加成及還原反應製備出類似樹枝狀聚合物之分枝型胺類化合物，即為超分枝高分子。Tomalia等人於1984年首先發表奈米樹狀體(poly(amidoamine),PAMAM)的樹枝狀聚合物，也締造最早商品化紀錄。樹枝狀聚合物由三個基本結構組合而成，包括：(1)核心(core)(2)重覆接枝單位(repeating unit)(3)外圍官能基(periphery group)。合成路徑依據成長方向分為發散式(divergent type)及收斂式(convergent type)二大類。 In recent years, the number of related literatures on dendritic chemistry has reached more than 2,000. The dendrimer has a highly regular branching structure, and the molecular size and design diversification are precisely controlled by step reaction. In 1978, Buhleier et al. used a acrylonitrile addition and reduction reaction to prepare a branched amine compound similar to a dendrimer, which is a hyperbranched polymer. In 1984, Tomalia et al first published a dendrimer of poly(amidoamine, PAMAM), which also established the earliest commercial record. The dendrimer is composed of three basic structures, including: (1) core (2) repeating unit (repeating unit) (3) peripheral group (periphery group). The synthetic path is divided into two categories: a divergent type and a convergent type according to the growth direction.

為了免除繁瑣保護及去保護步驟、提高產率及有效延伸代數的成長，先前技術中以雙官能基構築單元IDD為基礎，利用異氰酸(isocyanate)的高反應性及azetidine-2,4-dione的反應選擇性，搭配不同的醇類及胺類化合物進行交替性合成反應，發展一系列丙二醯胺(malonamide)及胺甲酸乙酯(urethane)衍生物之規則樹枝狀分子。其流程如以下之示意圖。 In order to avoid the cumbersome protection and deprotection steps, increase the yield and the growth of effective extension algebra, the prior art utilizes the high reactivity of isocyanate and azetidine-2,4-based on the bifunctional building block IDD. Dione reaction Selectively, alternately synthesize reactions with different alcohols and amines to develop a series of regular dendrimers of malonamide and urethane derivatives. The flow is as follows.

另外，側鏈樹枝狀聚合物(side chain dendritic polymers)可視為線型聚合物和樹枝狀聚合物的「結構共聚物」，始於1987年Tomalia等人的專利中，首次提及以線形聚乙烯亞胺(PEI)為主鏈的樹枝化聚合物。根據文獻可得知側鏈樹枝狀聚合物可應用於自組裝、單分子納米導線、發光材料和催化劑等領域。 In addition, side chain dendritic polymers can be considered as "structural copolymers" of linear polymers and dendrimers, beginning with the patent of Tomalia et al. in 1987, first mentioned in the form of linear polyethylene. A dendrimer of the amine (PEI) as the main chain. It is known from the literature that side chain dendrimers can be used in the fields of self-assembly, single-molecule nanowires, luminescent materials, and catalysts.

本發明導入長烷鏈段及全氟烷鏈於樹枝狀結構中，其分子間具凡得瓦爾力作用；此外，利用樹枝狀高分子結構，將長烷鏈或全氟烷鏈限制、綑綁在一起形成臘狀樹枝狀高分子，結構具備疏水之性質。另一方面，樹枝狀高分子為內部具有強氫鍵之尿素/丙二醯胺(urea/malonamide)結構，且隨著樹枝狀高分子代數之增加，樹枝狀分子內外部之氫鍵及凡得瓦爾力也隨之增加。 The invention introduces a long alkyl chain segment and a perfluoroalkyl chain in a dendritic structure, and has a Valent force effect between the molecules; in addition, the dendritic polymer structure is used to restrict or bind the long alkyl chain or the perfluoroalkyl chain. A waxy dendrimer is formed together, and the structure has a hydrophobic property. On the other hand, dendrimers are urea/malonamide structures with strong hydrogen bonds inside, and as the dendrimers increase, the hydrogen bonds inside and outside the dendrimers Valli also increased.

經開環加成反應後，本發明製備不同代數之樹枝狀高分子，導入於聚胺酯(polyurethane)系統中，形成一系列側鏈規則樹枝狀聚胺酯。由於樹枝狀高分子分子內外部之氫鍵及凡得瓦爾力，側鏈規則樹枝狀聚胺酯可利用Breath-figure法製備出多孔性材料；此外，為增加材料應用可行性，本發明調控側鏈樹枝狀聚胺酯的軟硬鏈段組成，以補強多孔性薄膜之機械性質。 After the ring-opening addition reaction, the present invention prepares dendrimers of different algebras and introduces them into a polyurethane system to form a series of side chain rules. Dendritic polyurethane. Due to the hydrogen bonding between the inner and outer sides of the dendrimer molecule and the van der Waals force, the side chain regular dendritic polyurethane can prepare the porous material by the Breath-figure method; in addition, in order to increase the material application feasibility, the present invention regulates the side chain branch The soft and hard segments of the polyurethane are composed to reinforce the mechanical properties of the porous film.

本發明之一範疇係於聚胺酯的側鏈導入一樹枝狀高分子，其通式如(I)結構所示： One aspect of the invention is the introduction of a dendrimer into the side chain of the polyurethane, the general formula of which is shown in the structure of (I):

其中R₁代表二異氰酸鹽(diisocyanate)，R₂則代表多元醇(polyol)。 Wherein R ₁ represents diisocyanate and R ₂ represents a polyol.

上述二異氰酸鹽(diisocyanate)可為異氰酸亞甲基二對苯酯(Methylene di-p-phenyl diisocyanate,MDI)、1,6-己二異氰酸酯(Hexamethylene diisocyanate,HDI)或異佛爾酮二異氰酸酯(Isophorone diisocyanate,IPDI)；而多元醇(polyol)則可為聚丙二醇(polypropyl glycol,PPG)、聚己內酯多元醇(polycaprolacton,PCL)或聚四氫呋喃(polytetramethylene ether glycol,PTMEG)。 The above diisocyanate may be Methylene di-p-phenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophor. Isophorone diisocyanate (IPDI); and polyol can be polypropyl glycol (PPG), polycaprolacton (PCL) or polytetramethylene ether glycol (PTMEG).

根據一具體實施例，當上述R1使用MDI，R2使用PPG 時，該式(I)化合物之之結構式可為： According to a specific embodiment, when the above R1 uses MDI and R2 uses PPG, the structural formula of the compound of the formula (I) can be:

根據另一具體實施例，當上述R1使用HDI，R2使用PPG時，該式(I)化合物之結構式可為： According to another specific embodiment, when the above R1 uses HDI and R2 uses PPG, the structural formula of the compound of the formula (I) may be:

根據另一具體實施例，當上述R1使用MDI，R2使用PCL時，該式(I)化合物之結構式可為： According to another specific embodiment, when the above R1 uses MDI and R2 uses PCL, the structural formula of the compound of the formula (I) may be:

根據另一具體實施例，當上述R1使用MDI，R2使用PTMEG時，該式(I)化合物之結構式可為： According to another specific embodiment, when the above R1 uses MDI and R2 uses PTMEG, the structural formula of the compound of the formula (I) can be:

以上所形成之膜材係利用breath figure的方式製備出蜂窩狀孔洞之薄膜，根據粗糙度的增加，可達到疏水甚至是超疏水的特性。 The film formed above is prepared by using a breath figure to form a film of honeycomb holes, which can achieve hydrophobic or even superhydrophobic properties according to the increase in roughness.

關於本發明之優點與精神可以藉由以下的發明詳述及所附圖式得到進一步的瞭解。 The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

根據一具體實施例，本發明之聚胺酯的側鏈導入一樹枝狀高分子，其通式如(I)結構所示： According to a specific embodiment, the side chain of the polyurethane of the present invention is introduced into a dendrimer having the general formula of (I):

其中R₁代表二異氰酸鹽(diisocyanate)，R₂則代表多元醇 (polyol)。 Wherein R ₁ represents diisocyanate and R ₂ represents a polyol.

上述於聚胺酯的側鏈導入一樹枝狀高分子之流程，可以流程圖一表示，並且此流程將以下列之具體實施例詳細說明。 The above procedure for introducing a dendrimer into the side chain of the polyurethane can be represented by the flow chart 1, and the flow will be described in detail in the following specific examples.

於具體實施例中，具有反應選擇性的單體IDD其反應流程如流程圖二所示： In a specific embodiment, the reaction process of the monomer IDD has a reaction scheme as shown in the second scheme:

利用IDD和硬脂醇(stearyl alcohol)進行反應，爾後再利用一級胺對azetidine-2,4-dione做開環反應，此逐步的合成步驟可合成出不同代數的樹枝狀高分子，其反應流程如流程圖三所示： The IDD and stearyl alcohol are used for the reaction, and then the azetidine-2,4-dione is subjected to a ring-opening reaction using a primary amine. This stepwise synthesis step can synthesize dendrimers of different algebras. As shown in flowchart three:

上述樹枝狀高分子可以下述步驟製備而成：首先，將一雙官能基構築單元(IDD)以四氫呋喃(tetrahydrofuran,THF)溶解形成第一溶液，再將一醇類加入第一溶液中並通氮氣於70℃下反應4小時，待反應結束後滴入甲醇中以沉澱析出，並在70℃下持續攪拌6小時，抽氣過濾收集一第一產物，烘乾該第一產物得到第一中間體[G-0.5]。 The dendrimer can be prepared by first dissolving a difunctional building block (IDD) in tetrahydrofuran (THF) to form a first solution, and then adding an alcohol to the first solution. Nitrogen gas was reacted at 70 ° C for 4 hours. After the reaction was completed, it was added dropwise to methanol to precipitate, and stirring was continued at 70 ° C for 6 hours. A first product was collected by suction filtration, and the first product was dried to obtain a first intermediate. Body [G-0.5].

接著，取第一中間體[G-0.5]於反應瓶內，以適量除水的四氫呋喃溶解於以形成一第二溶液，通氮氣並於70℃下攪拌該第二溶液並緩慢地加入二次乙基三胺(Diethylenetriamine,DETA)，待一第二產物析出後持續反應3小時，之後冷卻至室溫，以大量的四氫呋喃清洗該第二產品並抽氣過濾烘乾，以得到第一樹枝狀分子[G-1]。 Next, the first intermediate [G-0.5] was taken in a reaction flask, and an appropriate amount of water-depleted tetrahydrofuran was dissolved to form a second solution, and the second solution was stirred at 70 ° C and slowly added twice. Diethylenetriamine (DETA), after a second product is precipitated, the reaction is continued for 3 hours, then cooled to room temperature, and the second product is washed with a large amount of tetrahydrofuran and suction-dried to obtain the first dendrimer. Molecule [G-1].

之後，取第一樹枝狀分子[G-1]混合除水的四氫呋喃以形成一第三溶液，通氮氣於75℃下攪拌該第三溶液，待第一樹枝狀分子[G-1]完全溶解後加入該雙官能基構築單元IDD並反應4小時，之後將部分的四氫呋喃抽掉，並滴入甲醇中沉澱析出，經抽氣過濾烘乾得到一第二中間體[G-1.5]。 Thereafter, the first dendrimer [G-1] is mixed with dehydrogenated tetrahydrofuran to form a third solution, and the third solution is stirred by nitrogen at 75 ° C until the first dendrimer [G-1] is completely dissolved. Thereafter, the bifunctional building block IDD was added and reacted for 4 hours, after which part of the tetrahydrofuran was taken out, precipitated by dropping into methanol, and dried by suction filtration to obtain a second intermediate [G-1.5].

之後，重複上述步驟，製備出第三中間體[G-2.5]以及第四中間體[G-3.5]。最後，以除水的四氫呋喃溶解該第一中間體[G-0.5]、該第二中間體[G-1.5]、該第三中間體[G-2.5]以及該第四中間體[G-3.5]並混合N-(3-胺丙基)二乙醇胺(N-(3-aminopropyl)diethanolamine,APDEA)以形成一第三溶液，將該第三溶液通氮氣於75℃下反應48小時，待該第二中間體[G-1.5]完全反應後以甲醇析出並洗掉未反應完的APDEA，接著攪拌6小時後抽氣過濾並烘乾得到樹枝狀高分子。 Thereafter, the above procedure was repeated to prepare a third intermediate [G-2.5] and a fourth intermediate [G-3.5]. Finally, the first intermediate [G-0.5], the second intermediate [G-1.5], the third intermediate [G-2.5], and the fourth intermediate [G-3.5] are dissolved in water-depleted tetrahydrofuran. And mixing N-(3-aminopropyl)diethanolamine (APDEA) to form a third solution, and reacting the third solution with nitrogen at 75 ° C for 48 hours, After the second intermediate [G-1.5] was completely reacted, methanol was precipitated and the unreacted APREA was washed away, followed by stirring for 6 hours, followed by suction filtration and drying to obtain a dendrimer.

為了將樹枝狀高分子導入於聚胺酯的系統當中，必須將其透過化學改質。於本具體實施例中可利用APDEA之一級胺和azetidine-2,4-dione進行開環反應，合成出具有二元醇官能基的中間體[G-1.5]-二元醇，使之能在聚胺酯系統中做鏈延長劑使用。上述流程如流程圖四所示： In order to introduce a dendrimer into a system of polyurethane, it must be chemically modified. In this embodiment, a ring-opening reaction can be carried out using a single amine of ADPEA and azetidine-2,4-dione to synthesize an intermediate [G-1.5]-diol having a glycol functional group, so that Used as a chain extender in the polyurethane system. The above process is shown in flowchart four:

與烷鏈系列的樹枝狀高分子合成方式相似，導入全氟烷基乙基醇相關衍生物使末端帶全氟辛基乙基，由於具有低表面能的關係，因此有機會使膜材達到超疏水的特性；其樹枝狀高分子示意圖一如下： Similar to the synthesis of dendrimers in the alkyl chain series, the introduction of perfluoroalkylethyl alcohol-related derivatives leads to a perfluorooctylethyl group at the end, which has a low surface energy relationship, so that the organic film will reach the super Hydrophobic property; its dendritic polymer schematic is as follows:

依照軟硬鏈段的比例取各原物料的克數；MDI在50℃下加熱融熔，取上層的澄清液部分，PPG以真空烘箱除水，並加熱至80℃及抽氣6小時；接著以二甲基甲醯胺(DMF)做為溶劑，將MDI和PPG溶解，於60℃下通氮氣反應半小時，隨後加入樹枝狀高分子[G-1.5]-二元醇並以二月桂酸二丁錫(Dibutyltin dilaurate)做為催化劑，升溫至80℃，繼續反應3.5小時，反應結束後將此溶液倒入鐵氟龍盤中置入烘箱中去除溶劑成膜。 According to the ratio of soft and hard segments, the grams of each raw material are taken; MDI is heated and melted at 50 ° C, the supernatant portion of the upper layer is taken, the PPG is dehydrated in a vacuum oven, and heated to 80 ° C and pumped for 6 hours; Dissolve MDI and PPG with dimethylformamide (DMF) as solvent, react with nitrogen at 60 ° C for half an hour, then add dendrimer [G-1.5]-diol and dilaurate Dibutyltin dilaurate was used as a catalyst, and the temperature was raised to 80 ° C. The reaction was continued for 3.5 hours. After the reaction was completed, the solution was poured into a Teflon tray and placed in an oven to remove the solvent to form a film.

依照軟硬鏈段的比例取各原物料的克數；HDI不經純化直接使用，PPG以真空烘箱除水，並加熱至80℃及抽氣6小時；接著以二甲基甲醯胺(DMF)做為溶劑，將HDI和PPG溶解，於60℃下通氮氣反應半小時，隨後加入樹枝狀高分子[G-1.5]- 二元醇並以二月桂酸二丁錫(Dibutyltin dilaurate)做為催化劑，升溫至80℃，繼續反應3.5小時，反應結束後將此溶液倒入鐵氟龍盤中置入烘箱中去除溶劑成膜。 The grams of each raw material were taken according to the ratio of soft and hard segments; HDI was used without purification, PPG was dehydrated in a vacuum oven, and heated to 80 ° C and pumped for 6 hours; followed by dimethylformamide (DMF) As a solvent, dissolve HDI and PPG, react with nitrogen at 60 ° C for half an hour, and then add dendrimer [G-1.5]- The diol is dibutyltin dilaurate as a catalyst, and the temperature is raised to 80 ° C. The reaction is continued for 3.5 hours. After the reaction is completed, the solution is poured into a Teflon tray and placed in an oven to remove the solvent to form a film. .

依照軟硬鏈段的比例取各原物料的克數；IPDI不經純化直接使用，PPG以真空烘箱除水，並加熱至80℃及抽氣6小時；接著以二甲基甲醯胺(DMF)做為溶劑，將IPDI和PPG溶解，於60℃下通氮氣反應半小時，隨後加入樹枝狀高分子[G-1.5]-二元醇並以二月桂酸二丁錫(Dibutyltin dilaurate)做為催化劑，升溫至80℃，繼續反應3.5小時，反應結束後將此溶液倒入鐵氟龍盤中置入烘箱中去除溶劑成膜。 The grams of each raw material were taken according to the ratio of soft and hard segments; IPDI was used without purification, PPG was dewatered in a vacuum oven, and heated to 80 ° C and pumped for 6 hours; followed by dimethylformamide (DMF) As a solvent, IPDI and PPG were dissolved, and reacted with nitrogen at 60 ° C for half an hour, followed by addition of dendrimer [G-1.5]-diol and dibutyltin dilaurate. The catalyst was heated to 80 ° C and the reaction was continued for 3.5 hours. After the reaction was completed, the solution was poured into a Teflon tray and placed in an oven to remove the solvent to form a film.

依照軟硬鏈段的比例取各原物料的克數；MDI在50℃下加熱融熔，取上層的澄清液部分，PCL以真空烘箱除水，並加熱至80℃及抽氣6小時；接著以二甲基甲醯胺(DMF)做為溶劑，將MDI和PCL溶解，於60℃下通氮氣反應半小時，隨後加入樹枝狀高分子[G-1.5]-二元醇並以二月桂酸二丁錫(Dibutyltin dilaurate)做為催化劑，升溫至80℃，繼續反應3.5小時，反應結束後將此溶液倒入鐵氟龍盤中置入烘箱中去除溶劑成膜。 According to the ratio of soft and hard segments, the grams of each raw material are taken; MDI is heated and melted at 50 ° C, the supernatant portion of the upper layer is taken, the PCL is dehydrated in a vacuum oven, and heated to 80 ° C and pumped for 6 hours; Dissolve MDI and PCL with dimethylformamide (DMF) as solvent, react with nitrogen at 60 ° C for half an hour, then add dendrimer [G-1.5]-diol and dilaurate Dibutyltin dilaurate was used as a catalyst, and the temperature was raised to 80 ° C. The reaction was continued for 3.5 hours. After the reaction was completed, the solution was poured into a Teflon tray and placed in an oven to remove the solvent to form a film.

依照軟硬鏈段的比例取各原物料的克數；MDI在50℃下加熱融熔，取上層的澄清液部分，PTMEG以真空烘箱除水，並加熱至80℃及抽氣6小時；接著以二甲基甲醯胺(DMF)做為溶劑，將MDI和PTMEG溶解，於60℃下通氮氣反應半小時，隨後加入樹枝狀高分子[G-1.5]-二元醇並以二月桂酸二丁錫(Dibutyltin dilaurate)做為催化劑，升溫至80℃，繼續反應3.5小時，反應結束後將此溶液倒入鐵氟龍盤中置入烘箱中去除溶劑成膜。 According to the ratio of soft and hard segments, the grams of each raw material are taken; MDI is heated and melted at 50 ° C, the supernatant portion of the upper layer is taken, PTMEG is dehydrated in a vacuum oven, and heated to 80 ° C and pumped for 6 hours; Dissolve MDI and PTMEG with dimethylformamide (DMF) as solvent, and react with nitrogen at 60 ° C for half an hour. Subsequently, a dendrimer [G-1.5]-diol was added and Dibutyltin dilaurate was used as a catalyst, and the temperature was raised to 80 ° C, and the reaction was continued for 3.5 hours. After the reaction, the solution was poured into iron. The solvent is placed in an oven to remove the solvent to form a film.

藉由以上較佳具體實施例之詳述，係希望能更加清楚描述本發明之特徵與精神，而並非以上述所揭露的較佳具體實施例來對本發明之範疇加以限制。相反地，其目的是希望能涵蓋各種改變及具相等性的安排於本發明所欲申請之專利範圍的範疇內。因此，本發明所申請之專利範圍的範疇應該根據上述的說明作最寬廣的解釋，以致使其涵蓋所有可能的改變以及具相等性的安排。 The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. Therefore, the scope of the patented scope of the invention should be construed as broadly construed in the

圖一係繪示化合物A的¹H NMR光譜圖。 Figure 1 is a chart showing the ¹ H NMR spectrum of Compound A.

圖二係繪示化合物B的¹H NMR光譜圖。 Figure 2 is a chart showing the ¹ H NMR spectrum of Compound B.

圖三係繪示I-A所形成孔洞膜材之AFM示意圖。 Figure 3 is a schematic diagram showing the AFM of the hole film formed by I-A.

圖四係繪示I-B所形成孔洞膜材之AFM示意圖。 Figure 4 is a schematic view showing the AFM of the hole film formed by I-B.

Claims

一種含有側鏈規則樹枝狀高分子之聚胺酯，具有如通式(I)之結構：，其中，R1為二異氰酸鹽(diisocyanates)，R2為多元醇(polyols)，以及該聚胺酯之末端為全氟烷鏈。 A polyurethane containing a side chain regular dendrimer having a structure of the formula (I): Wherein R1 is diisocyanates, R2 is a polyol, and the end of the polyurethane is a perfluoroalkyl chain.

如申請專利範圍第1項所述之聚胺酯，其中R1包含異氰酸亞甲基二對苯酯(Methylene di-p-phenyl diisocyanate,MDI)、1,6-己二異氰酸酯(Hexamethylene diisocyanate,HDI)以及異佛爾酮二異氰酸酯(Isophorone diisocyanate,IPDI)所組成群組中之一，並且R2包含聚丙二醇(polypropyl glycol,PPG)、聚己內酯多元醇(polycaprolacton,PCL)以及聚四氫呋喃(polytetramethylene ether glycol,PTMEG)所組成群組中之一。 The polyurethane according to claim 1, wherein R1 comprises Methylene di-p-phenyl diisocyanate (MDI), Hexamethylene diisocyanate (HDI) And one of the group consisting of Isophorone diisocyanate (IPDI), and R2 comprises polypropyl glycol (PPG), polycaprolacton (PCL), and polytetramethylene ether (polytetramethylene ether) Glycol, PTMEG) One of the groups.

一種製備含有側鏈規則樹枝狀高分子之聚胺酯之方法，用以製備含有側鏈規則樹枝狀高分子以及其末端為全氟烷鏈之一聚胺酯，該聚胺酯具有如通式(I)之結構：，該方法包含下列步驟：(a)於一第一階段的反應中，將純化過的二異氰酸鹽(diisocyanate)以及除水過的多元醇(polyols)於圓底燒瓶中於60℃通氮氣下形成一反應系統，該反應系統迴流反應半個小時；以及(b)於一第二階段的反應中，加入做為鏈延長劑之樹枝狀高分子(Dendron)以及做為催化劑之二月桂酸二丁錫(Dibutyltin dilaurate)於該反應系統，接著將該反應系統升溫至80℃並持續反應3.5小時，待反應結束後，將該反應系統中之溶液倒入鐵氟龍盤中並置於烘箱內以除去溶劑，進而獲得該聚胺酯。 A method for preparing a polyurethane containing a side chain regular dendrimer for preparing a dendrimer having a side chain and a polyurethane having a terminal end of a perfluoroalkyl chain having a structure of the formula (I): The method comprises the steps of: (a) purifying the diisocyanate and the dehydrated polyol in a round-bottomed flask at 60 ° C in a first-stage reaction Forming a reaction system under nitrogen, the reaction system is refluxed for half an hour; and (b) adding a dendrimer as a chain extender (Dendron) as a catalyst and a second laurel as a catalyst in a second stage reaction Dibutyltin dilaurate is applied to the reaction system, and then the reaction system is heated to 80 ° C and the reaction is continued for 3.5 hours. After the reaction is completed, the solution in the reaction system is poured into a Teflon tray and placed in an oven. The solvent was removed to obtain the polyurethane.

一種做為聚胺酯(polyurethane)之鏈延長劑之樹枝狀高分子(Dendron)，具有如通式(A)之結構：，其中，R為C₄以上之全氟烷基乙基衍生物。 A dendrimer (Dendron) which is a chain extender of polyurethane and has a structure of the general formula (A): Wherein R is a perfluoroalkylethyl derivative of C ₄ or more.

如申請專利範圍第4項所述之樹枝狀高分子，其中R包含C₄F₉CH₂CH₂-、C₆F₁₃CH₂CH₂-、C₈F₁₇CH₂CH₂-、C₁₀F₂₁CH₂CH₂-以及C₁₂F₂₅CH₂CH₂-所組成群組中之一。 The dendrimer according to claim 4, wherein R comprises C ₄ F ₉ CH ₂ CH ₂ -, C ₆ F ₁₃ CH ₂ CH ₂ -, C ₈ F ₁₇ CH ₂ CH ₂ -, C ₁₀ One of the group consisting of F ₂₁ CH ₂ CH ₂ - and C ₁₂ F ₂₅ CH ₂ CH ₂ -.

一種製備樹枝狀高分子(Dendron)之方法，用以製備做為一聚胺酯(polyurethane)之鏈延長劑之一樹枝狀高分子(Dendron)，該樹枝狀高分子具有如通式(A)之結構：其中，R為C₄以上之全氟烷基乙基衍生物，該方法包含下列步驟： (a)於一第一階段的反應中，將一雙官能基構築單元(IDD)以四氫呋喃(tetrahydrofuran,THF)溶解形成一第一溶液，再將一醇類加入該第一溶液中並通氮氣於70℃下反應4小時，待反應結束後滴入甲醇中以沉澱析出，並在70℃下持續攪拌6小時，抽氣過濾收集一第一產物，烘乾該第一產物得到一第一中間體[G-0.5]；(b)於一第二階段的反應中，取該第一中間體[G-0.5]於反應瓶內，以適量除水的四氫呋喃溶解於以形成一第二溶液，通氮氣並於70℃下攪拌該第二溶液並緩慢地加入二次乙基三胺(Diethylenetriamine,DETA)，待一第二產物析出後持續反應3小時，之後冷卻至室溫，以大量的四氫呋喃清洗該第二產品並抽氣過濾烘乾，以得到一第一樹枝狀分子[G-1]；(c)於一第三階段的反應中，取該第一樹枝狀分子[G-1]混合除水的四氫呋喃以形成一第三溶液，通氮氣於75℃下攪拌該第三溶液，待該第一樹枝狀分子[G-1]完全溶解後加入該雙官能基構築單元IDD並反應4小時，之後將部分的四氫呋喃抽掉，並滴入甲醇中沉澱析出，經抽氣過濾烘乾得到一第二中間體[G-1.5]；(d)重複上述步驟，製備出一第三中間體[G-2.5]以及一第四中間體[G-3.5]；以及(e)以除水的四氫呋喃溶解該第一中間體[G-0.5]、該第二中間體[G-1.5]、該第三中間體[G-2.5]以及該第四中間體 [G-3.5]並混合N-(3-胺丙基)二乙醇胺(N-(3-aminopropyl)diethanolamine,APDEA)以形成一第三溶液，將該第三溶液通氮氣於75℃下反應48小時，待該第二中間體[G-1.5]完全反應後以甲醇析出並洗掉未反應完的APDEA，接著攪拌6小時後抽氣過濾並烘乾得到該樹枝狀高分子。 A method for preparing a dendrimer (Dendron) for preparing a dendrimer (Dendron) which is a chain extender of polyurethane having a structure of the general formula (A) : Wherein R is a C ₄ or higher perfluoroalkylethyl derivative, the method comprising the steps of: (a) in a first stage reaction, a bifunctional building block (IDD) is tetrahydrofuran (tetrahydrofuran, THF) dissolves to form a first solution, and then an alcohol is added to the first solution and reacted at 70 ° C for 4 hours through nitrogen gas. After the reaction is completed, it is added dropwise to methanol to precipitate and continuously stir at 70 ° C. After 6 hours, a first product is collected by suction filtration, and the first product is dried to obtain a first intermediate [G-0.5]; (b) in a second stage reaction, the first intermediate is taken [G -0.5] In a reaction flask, an appropriate amount of water-depleted tetrahydrofuran was dissolved to form a second solution, and the second solution was stirred by nitrogen gas at 70 ° C and slowly added with diethylethylene triamine (DETA). After a second product is precipitated, the reaction is continued for 3 hours, then cooled to room temperature, and the second product is washed with a large amount of tetrahydrofuran and suction-dried to obtain a first dendrimer [G-1]; c) in the third stage of the reaction, the first dendrimer [G-1] mixed water removal Tetrahydrofuran to form a third solution, the third solution is stirred at 75 ° C by nitrogen, and after the first dendrimer [G-1] is completely dissolved, the bifunctional building block IDD is added and reacted for 4 hours, after which Part of the tetrahydrofuran is taken out, and precipitated by dropping into methanol, and dried by suction filtration to obtain a second intermediate [G-1.5]; (d) repeating the above steps to prepare a third intermediate [G-2.5 And a fourth intermediate [G-3.5]; and (e) dissolving the first intermediate [G-0.5], the second intermediate [G-1.5], the third intermediate, with water-depleted tetrahydrofuran [G-2.5] and the fourth intermediate [G-3.5] and mixing N-(3-aminopropyl)diethanolamine (APDEA) to form a third solution, The third solution was reacted with nitrogen at 75 ° C for 48 hours. After the second intermediate [G-1.5] was completely reacted, methanol was precipitated and the unreacted APREA was washed off, followed by stirring for 6 hours, followed by suction filtration and drying. The dendrimer was obtained.