TWI395740B - Imidazolium based polyester - Google Patents
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Description
本發明是有關於一種聚合單體和聚合物，特別是指一種咪唑鹽(imidazolium)聚合單體和具有咪唑鹽的聚酯聚合物。This invention relates to a polymeric monomer and polymer, and more particularly to an imidazolium polymeric monomer and a polyester polymer having an imidazolium salt.
為了增加聚酯(Polyester)類織物纖維的抗靜電性及染色性，通常會在高分子材料中添加具有四級銨鹽結構，或是磺酸鈉鹽結構的化合物，以增加高分子材料的抗靜電性、親水性及染色性。In order to increase the antistatic property and dyeability of polyester (Polyester) fabric fibers, a compound having a quaternary ammonium salt structure or a sodium sulfonate salt structure is usually added to the polymer material to increase the resistance of the polymer material. Electrostatic, hydrophilic and dyeing properties.
然而，一般四級銨鹽或是磺酸鈉鹽化合物為低分子量型添加劑，與高分子材料相容性較差，因此，往往容易在加工過程中損耗，或是於使用過程中遷移(blooming)至高分子表面，而造成抗靜電性能降低及製品表面霧化的問題；而另一方面，由於四級銨鹽的耐熱性較差(小於200℃)，所以無法應用於需要更高溫條件下進行熔融紡絲的聚醯胺或聚酯；而為了改善上述低分子量型添加劑的缺點，因此，也有利用含功能性基團的共聚合單體與聚合單體進行共聚(co-polymerization)，例如，使用對苯二甲酸磺酸鈉鹽為共聚合單體與乙二醇及對苯二甲酸聚合單體進行共聚合反應，形成共聚合高分子(co-polymer)，得到具有抗靜電性之聚酯，而可避免因掺雜低分子量型添加劑與高分子材料間的相容性問題，但是，要得到具有高分子量的聚酯時，其應用於聚合之單體的羧基及醇基的比例需要更精確的控制在約1：1，因此，當以上述方式進行共聚所得到的高分子，容易因添加的 共聚合單體數量、種類的影響，而使得聚合系統的複雜性增加。However, generally the quaternary ammonium salt or the sodium sulfonate compound is a low molecular weight type additive, which is inferior in compatibility with the polymer material, and therefore tends to be easily lost during processing or migrated to high during use. Molecular surface, which causes problems of antistatic performance and atomization of the surface of the product; on the other hand, since the quaternary ammonium salt has poor heat resistance (less than 200 ° C), it cannot be used for melt spinning requiring higher temperature conditions. Polyamide or polyester; and in order to improve the disadvantages of the above-mentioned low molecular weight type additives, there is also a co-polymerization using a copolymerizable monomer containing a functional group, for example, using benzene. The sodium diformate sulfonate is a copolymerization monomer and a copolymerization reaction of ethylene glycol and a terephthalic acid polymerization monomer to form a copolymerized polymer (co-polymer) to obtain an antistatic polyester. Avoid compatibility problems between doped low molecular weight additives and polymer materials, but when obtaining a polyester having a high molecular weight, it is applied to the carboxyl group and the alcohol group of the polymerized monomer. The ratio needs to be more precisely controlled at about 1:1, so that the polymer obtained by copolymerization in the above manner is easily added The effect of the number and type of monomers is aggregated, which increases the complexity of the polymerization system.
因此，如何尋求一可同時具有高熱穩定性、高抗靜電性能、高染色性能且聚合製程簡單容易控制的聚酯，以更適合提供產業應用，實為目前相關業者亟欲改良的重要目標之一。Therefore, how to find a polyester which can simultaneously have high thermal stability, high antistatic property, high dyeing property and simple and easy control of the polymerization process, is more suitable for providing industrial applications, and is one of the important goals of the current industry. .
因此，本發明的目的，即在提供一種咪唑鹽聚合單體。Accordingly, it is an object of the present invention to provide an imidazoline polymerizable monomer.
此外，本發明的另一目的，即在提供一種具有咪唑鹽的聚酯聚合物。Further, another object of the present invention is to provide a polyester polymer having an imidazolium salt.
於是，本發明一種咪唑鹽聚合單體其結構如式(I)所示：
其中，R1 、R2 、R3 各自獨立地為氫，或烷基，R4 、R5 是各自獨立地為C1 ~C10 的烷基、R6 是選自氫或C1 ~C10 的烷基，Z- 是選自鹵素離子、PF6 - 、BF4 - 、N(SO2 CF3 )2 - ，或N(SO2 CF2 CF3 )2 - 。Wherein R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group, R 4 and R 5 are each independently a C 1 -C 10 alkyl group, and R 6 is selected from hydrogen or C 1 -C The alkyl group of 10 , Z - is selected from the group consisting of a halogen ion, PF 6 - , BF 4 - , N(SO 2 CF 3 ) 2 - , or N(SO 2 CF 2 CF 3 ) 2 - .
再者，本發明一種具有咪唑鹽的聚酯聚合物是包含上述式(I)所示之咪唑鹽聚合單體聚合而得。Further, a polyester polymer having an imidazole salt of the present invention is obtained by polymerizing an imidazolium salt-polymerizable monomer represented by the above formula (I).
本發明之功效在於：利用咪唑鹽單體的結構設計，得到在單一咪唑鹽分子結構中即同時具有羧基及羥基的新穎型咪唑鹽聚合單體，而可以自聚合方式得到聚酯聚合物，不僅製 程簡便，且可得到一同時具有抗靜電性及染色性佳的聚酯聚合物。The invention has the advantages that: by using the structural design of the imidazole salt monomer, a novel imidazolium salt-polymerizable monomer having a carboxyl group and a hydroxyl group in a single imidazolium salt molecular structure can be obtained, and the polyester polymer can be obtained from a polymerization method. system The process is simple, and a polyester polymer having both antistatic properties and good dyeability can be obtained.
有關本發明之前述及其他技術內容、特點與功效，在以下配合參考圖式之一個較佳實施例的詳細說明中，將可清楚的呈現。The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.
本發明具有咪唑鹽的聚酯聚合物的一較佳實施例是包含由下述式(I)所示的咪唑鹽聚合單體聚合而得，可直接聚合後而可得到具有抗靜電性及高染色性的聚酯纖維、或是添加在各式高分子材料中，以提昇一般高分子材料的抗靜電性及高染色性；惟本發明之應用並不以此為限。A preferred embodiment of the polyester polymer having an imidazolium salt of the present invention comprises polymerization of an imidazolium salt-polymerizable monomer represented by the following formula (I), which can be directly polymerized to obtain antistatic properties and high The dyed polyester fiber is added to various polymer materials to improve the antistatic property and high dyeability of the general polymer material; however, the application of the present invention is not limited thereto.
本發明一種具有咪唑鹽的聚酯聚合物的該較佳實施例是包含由下列式(I)所示之咪唑鹽共聚合單體聚合而得：
其中，R1 、R2 、R3 各自獨立地為氫，或烷基，R4 、R5 是各自獨立地為C1 ~C10 的烷基、R6 是選自氫或C1 ~C10 的烷基，Z- 是選自鹵素離子、PF6 - 、BF4 - ，或N(SO2 CF3 )2 - 。Wherein R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group, R 4 and R 5 are each independently a C 1 -C 10 alkyl group, and R 6 is selected from hydrogen or C 1 -C The alkyl group of 10 , Z - is selected from the group consisting of a halogen ion, PF 6 - , BF 4 - , or N(SO 2 CF 3 ) 2 - .
較佳地，該R1 、R2 、R3 各自獨立地為氫，或C1 ~C5 的烷基，R4 、R5 是各自獨立地為C1 ~C5 的烷基、R6 是選自C1 ~C5 的烷基，Z- 是Cl- 、Br- 、I- 、PF6 - 、BF4 - 、N(SO2 CF3 )2 - ，或N(SO2 CF2 CF3 )2 - 。Preferably, each of R 1 , R 2 and R 3 is independently hydrogen or a C 1 -C 5 alkyl group, and R 4 and R 5 are each independently a C 1 -C 5 alkyl group, R 6 Is an alkyl group selected from C 1 to C 5 , Z - is Cl - , Br - , I - , PF 6 - , BF 4 - , N(SO 2 CF 3 ) 2 - , or N(SO 2 CF 2 CF 3 ) 2 - .
要說明的是，本發明的咪唑鹽聚合單體利用結構設計，讓咪唑鹽聚合單體於同一分子同時具有羧基及羥基的反應官能基，因此，不僅可藉由自聚合反應後即可得到具有咪唑鹽的聚酯聚合物，且由於該咪唑鹽聚合單體於同一分子同時具有1：1的羧基及羥基的反應官能基，因此，當添加應用於一般聚酯的聚合系統時，其不同的添加量都不會影響原聚合系統中羧基及羥基的比例，因此可更有效簡化製程，而得到具有抗靜電性及染色性佳的具有咪唑鹽的聚酯聚合物。It is to be noted that the imidazolium salt-polymerizable monomer of the present invention utilizes a structural design such that the imidazolium salt-polymerizable monomer has a reactive functional group of a carboxyl group and a hydroxyl group in the same molecule, and therefore, not only can be obtained by self-polymerization reaction. a polyester polymer of an imidazolium salt, and since the imidazolium salt-polymerizable monomer has a reactive functional group of a 1:1 carboxyl group and a hydroxyl group in the same molecule, when added to a polymerization system of a general polyester, the difference is different. The addition amount does not affect the ratio of the carboxyl group and the hydroxyl group in the original polymerization system, so that the process can be more effectively simplified, and a polyester polymer having an imidazole salt having excellent antistatic property and dyeability can be obtained.
上述具有咪唑鹽的聚酯聚合物，藉由以下該較佳實施例的製備方法說明後當可更清楚明白。The above polyester polymer having an imidazolium salt can be more clearly understood by the following description of the preparation method of the preferred embodiment.
首先將咪唑(imidazolium)與丙烯酸類(acrylate type)化合物，在鹼性條件下進行反應後，接著再與不同碳鏈長度之鹵烷醇類化合物反應，即可合成咪唑鹽聚合單體。First, an imidazolium polymerizable monomer can be synthesized by reacting imidazolium with an acrylate type compound under basic conditions and then reacting with a haloalkanol compound having a different carbon chain length.
較佳地該丙烯酸類是選自丙烯酸甲酯、甲基丙烯酸甲酯、乙基丙烯酸甲酯，該鹵烷醇類化合物是選自碳數為1~5之含鹵素的醇類化合物。Preferably, the acrylic acid is selected from the group consisting of methyl acrylate, methyl methacrylate, and ethyl methacrylate, and the halogenated alkanol compound is a halogen-containing alcohol compound having a carbon number of 1 to 5.
於本實施例中，該丙烯酸類(acrylate type)化合物是選自丙烯酸甲酯，該含鹵素的醇類化合物是選自碳數為1~5溴烷醇類化合物。In the present embodiment, the acrylate type compound is selected from methyl acrylate, and the halogen-containing alcohol compound is selected from the group consisting of brominated alkanol compounds having a carbon number of 1 to 5.
具體的說，該咪唑鹽聚合單體的製備是將咪唑(imidazole)加入至碳酸鉀(K2 CO3 )與丙酮的混合溶液中，於室溫下反應20分鍾後加入與咪唑相同當量的丙烯酸甲酯，接著於70℃反應三天，將反應溶液過濾、濃縮後加入乙酸乙酯，再將有機層以去離子水(100mlx3)清洗、濃縮後可獲得咪唑鹽 中間物。Specifically, the imidazolium salt-polymerizable monomer is prepared by adding imidazole to a mixed solution of potassium carbonate (K 2 CO 3 ) and acetone, and reacting at room temperature for 20 minutes, and then adding the same equivalent amount of acrylic acid as the imidazole. The methyl ester was reacted at 70 ° C for three days. The reaction solution was filtered, concentrated, and then ethyl acetate was added. The organic layer was washed with deionized water (100 ml×3) and concentrated to obtain an imidazole salt intermediate.
接著，再將上述製得的咪唑鹽中間物加入含有與前述之咪唑鹽當量相同的溴烷醇類化合物與甲苯的混合溶液中，於70℃下反應40小時，接著以乙酸乙酯(50ml x 4)清洗，經濃縮、乾燥後即可製得同時具有羧基及醇基的咪唑鹽聚合單體，其反應流程如下所示：
參閱表一，茲將製得之咪唑鹽聚合單體整理如表一所示。Referring to Table 1, the prepared imidazole salt polymerized monomers are shown in Table 1.
參閱圖1，圖1是上述該咪唑鹽中間物3的核磁共振光譜圖(1 H NMR/Bruker Avancetm DPX-200型，CDCl3 )。Referring to Figure 1, 1 is the above-described intermediate imidazolium salt thereof NMR spectrum of FIG. 3 (1 H NMR / Bruker Avancetm DPX -200 type, CDCl 3).
由圖1中可得到：δ 7.47(s,1H),7.00(s,1H),6.89(s,1H),4.23(t,J =6.6Hz,2H),3.66(s,3H),2.75(t,J =6.6Hz,2H)From Figure 1, we can get: δ 7.47 (s, 1H), 7.00 (s, 1H), 6.89 (s, 1H), 4.23 (t, J = 6.6 Hz, 2H), 3.66 (s, 3H), 2.75 ( t, J = 6.6 Hz, 2H)
參閱圖2，圖2是該咪唑鹽聚合單體4-1的核磁共振光 譜圖(1 H NMR/Bruker Avancetm DPX-200型，D2 O)光譜圖。Referring to FIG. 2, FIG. 2 is a polymerizable monomer imidazolium salt NMR spectrum shown in Figure 4-1 (1 H NMR / Bruker Avancetm DPX -200 type, D 2 O) spectrum of FIG.
由圖2中可得到：δ 8.94(s,1H),7.61~7.58(m,2H),4.56(t,J =6.3Hz,2H),4.37(t,J =5.0Hz,2H),3.96(t,J=5.0Hz,2H),3.73(s,3H),3.08(t,J =6.3Hz,2H)，因此可確認該咪唑鹽聚合單體4-1的結構式為：3-(2-hydroxyethyl)-1-methoxycarbonylethylimidazoliumbromide)。From Figure 2, we can get: δ 8.94 (s, 1H), 7.61~7.58 (m, 2H), 4.56 (t, J = 6.3 Hz, 2H), 4.37 (t, J = 5.0 Hz, 2H), 3.96 ( t, J = 5.0 Hz, 2H), 3.73 (s, 3H), 3.08 (t, J = 6.3 Hz, 2H), so that the structural formula of the imidazolium salt-polymerizable monomer 4-1 was confirmed to be: 3-(2) -hydroxyethyl)-1-methoxycarbonylethylimidazoliumbromide).
參閱圖3，圖3是該咪唑鹽聚合單體4-2的核磁共振光譜圖(1 H NMR/Bruker Avancetm DPX-200型，D2 O)光譜圖。Referring to FIG. 3, FIG. 3 is a polymerizable monomer imidazolium salt of the NMR spectrum of Figure 4-2 (1 H NMR / Bruker Avancetm DPX -200 type, D 2 O) spectrum of FIG.
由圖3中可得到：δ 8.94(s,1H),7.60~7.57(m,2H),4.57(t,J =6.3Hz,2H),4.37(t,J =7.1Hz,2H),3.71(s,3H),3.68(t,J =6.0Hz,2H),3.10(t,J =6.3Hz,2H),2.23~2.10(m,2H)，因此可確認該咪唑鹽聚合單體4-1的結構式為：3-(3-hydroxypropyl)-1-methoxycarbonylethylimidazoliumbromide)。From Figure 3, we can get: δ 8.94 (s, 1H), 7.60~7.57 (m, 2H), 4.57 (t, J = 6.3 Hz, 2H), 4.37 (t, J = 7.1 Hz, 2H), 3.71 ( s, 3H), 3.68 (t, J = 6.0 Hz, 2H), 3.10 (t, J = 6.3 Hz, 2H), 2.23 to 2.10 (m, 2H), so it can be confirmed that the imidazolium salt polymerization monomer 4-1 The structural formula is: 3-(3-hydroxypropyl)-1-methoxycarbonylethylimidazoliumbromide).
接著，將前述製得的咪唑鹽聚合單體在鈦觸媒的催化下，進行縮合聚合反應得到聚離子高分子後即可製備出不同的咪唑鹽聚酯聚合物，由於該聚合方法為本技術領域業者所周知，且非為本發明之重點，因此不再多加贅述，其整體的反應流程如下所示：
值得一提的是，該經聚合反應製得的具有咪唑鹽的聚酯聚合物可再藉由陰離子交換反應而製得具有不同陰離子的咪唑鹽的聚酯聚合物，而改變該具有咪唑鹽的聚酯聚合物的熱穩定性及在不同極性中之溶解度，其結果整理如下表二所示；由於前述之陰離子交換反應的製程方法為本技術領域業者所周知且非為本發明之技術重點，因此不再多加贅述，較佳地，該陰離子是鹵素離子、PF6 - 、BF4 - 、N(SO2 CF3 )2 - ，或N(SO2 CF2 CF3 )2 - ，更佳地，該陰離子是Cl- 、Br- 、I- 、PF6 - 、BF4 - ，或N(SO2 CF3 )2 - 。It is worth mentioning that the polyester polymer having an imidazolium salt obtained by the polymerization reaction can further produce a polyester polymer having an imidazole salt of a different anion by an anion exchange reaction, and changing the imidazolium salt. The thermal stability of the polyester polymer and the solubility in different polarities, the results of which are shown in Table 2 below; since the above-mentioned anion exchange reaction process is well known to those skilled in the art and is not the technical focus of the present invention, Therefore, the description will not be repeated. Preferably, the anion is a halogen ion, PF 6 - , BF 4 - , N(SO 2 CF 3 ) 2 - , or N(SO 2 CF 2 CF 3 ) 2 - , more preferably The anion is Cl - , Br - , I - , PF 6 - , BF 4 - , or N(SO 2 CF 3 ) 2 - .
接著將上述製得之具有咪唑鹽的聚酯聚合物6-1~6-6以熱重分析儀(TGA)進行耐熱性質量測。Next, the polyester polymers 6-1 to 6-6 having the imidazolium salt prepared above were subjected to heat resistance measurement by a thermogravimetric analyzer (TGA).
TGA規格/廠牌：TGA-50/Shimadzu,JapanTGA specifications / label: TGA-50/Shimadzu, Japan
升溫速率：10℃/分鐘Heating rate: 10 ° C / min
最終溫度：500℃Final temperature: 500 ° C
參閱圖5、圖6，圖5~6分別是6-1~6-6的TGA量測結果，由圖中可知，咪唑鹽聚酯聚合物其耐熱性會隨著陰離子的不同而有所差異，且當陰離子為NTf2 - 時均具有較佳之熱安定性，由圖中結果可看出最高之熱裂解溫度約可達到370℃，而此類耐高溫之咪唑鹽聚酯聚合物更適用於一般須耐高溫之製程或高溫操作條件下使用，例如可應用在高溫溶劑、汽相層析管柱的靜相材料等。Referring to Fig. 5 and Fig. 6, Fig. 5~6 are the TGA measurement results of 6-1~6-6 respectively. It can be seen from the figure that the heat resistance of the imidazolium polyester polymer varies with the anion. And when the anion is NTf 2 - , it has better thermal stability. It can be seen from the results that the highest thermal cracking temperature can reach 370 ° C, and such high temperature imidazole salt polyester polymer is more suitable for Generally used in high temperature resistant processes or high temperature operating conditions, such as static phase materials for high temperature solvents and vapor chromatography columns.
由上述結果可知，本發明利用結構設計出一同時具有羧基及羥基的反應官能基，因此，不僅可藉由自聚合反應後即可得到具有咪唑鹽的聚酯聚合物，且由於該咪唑鹽聚合單體於同一分子同時具有1：1的羧基及羥基的反應官能基，因此，當添加應用於一般聚酯的聚合系統時，其不同的添加量都不會影響原聚合系統中羧基及醇基的比例，因此可更有效簡化製程，而得到具有咪唑鹽的聚酯聚合物，故確實能達成本發明之目的。From the above results, the present invention utilizes a structure to design a reactive functional group having both a carboxyl group and a hydroxyl group. Therefore, not only a polyester polymer having an imidazolium salt but also a polymerization of the imidazolium salt can be obtained by self-polymerization. The monomer has a reactive functional group of 1:1 carboxyl group and hydroxyl group in the same molecule. Therefore, when added to a polymerization system of a general polyester, the different addition amount does not affect the carboxyl group and the alcohol group in the original polymerization system. The ratio of the present invention is therefore more effective in simplifying the process to obtain a polyester polymer having an imidazolium salt, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
圖1是一NMR圖，說明咪唑鹽中間物的核磁共振光譜結果；圖2是一NMR圖，說明咪唑鹽聚合單體4-1的核磁共振光譜結果； 圖3是一NMR圖，說明咪唑鹽聚合單體4-2的核磁共振光譜結果；圖4是一TGA圖，說明本發明具有咪唑鹽聚酯聚合物該較佳實施例6-1~6-3的熱重分析結果；及圖5是一TGA圖，說明本發明具有咪唑鹽聚酯聚合物該較佳實施例6-4~6-6的熱重分析結果。1 is an NMR chart illustrating the results of nuclear magnetic resonance spectroscopy of an imidazolium salt intermediate; FIG. 2 is an NMR chart illustrating the results of nuclear magnetic resonance spectroscopy of an imidazolium salt-polymerizable monomer 4-1; Figure 3 is an NMR chart illustrating the results of nuclear magnetic resonance spectroscopy of the imidazolium salt-polymerizable monomer 4-2; Figure 4 is a TGA diagram illustrating the preferred embodiment 6-1 to 6- of the present invention having an imidazolium salt polyester polymer. The thermogravimetric analysis result of 3; and FIG. 5 is a TGA diagram illustrating the thermogravimetric analysis results of the preferred embodiment 6-4 to 6-6 of the present invention having an imidazolium salt polyester polymer.
Claims (2)
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| TW98141818A TWI395740B (en) | 2009-12-08 | 2009-12-08 | Imidazolium based polyester |
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| TW98141818A TWI395740B (en) | 2009-12-08 | 2009-12-08 | Imidazolium based polyester |
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| TW201120011A TW201120011A (en) | 2011-06-16 |
| TWI395740B true TWI395740B (en) | 2013-05-11 |
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| US20060149074A1 (en) * | 2003-07-21 | 2006-07-06 | Basf Aktiengesellschaft | Method for the production of purified 1,3-substituted imidazolium salts |
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| US20060149074A1 (en) * | 2003-07-21 | 2006-07-06 | Basf Aktiengesellschaft | Method for the production of purified 1,3-substituted imidazolium salts |
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