TWI460206B - Method of preparing a heat-resistant polyamide - Google Patents
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本發明有關於一種聚醯胺的製造方法，特別是有關於一種較為經濟之耐熱性聚醯胺的製造方法，其中，作為原料之單體係可以簡單且便宜地被製備，且本發明不需去除溶劑的步驟，以致聚合反應時間縮短。The invention relates to a method for producing polyamide, in particular to a method for producing a relatively economical heat-resistant polyamide, wherein a single system as a raw material can be prepared simply and inexpensively, and the invention does not need The step of removing the solvent causes the polymerization reaction time to be shortened.
以尼龍6(nylon 6)與尼龍66(nylon 66)為代表的聚醯胺，由於其優越的機械特性與耐化學性，因而被廣泛地應用於纖維、薄膜、片狀物、射出成型製品及其類似物。然而，由於尼龍6與尼龍66的熔解溫度分別為230℃與260℃，因此尼龍6與尼龍66存在有因其耐熱性不足而使其無法應用於半導體加工設備、電路板、汽車與飛機零件及其類似物的問題。Polyamide, represented by nylon 6 (nylon 6) and nylon 66 (nylon 66), is widely used in fibers, films, sheets, and injection molded articles due to its superior mechanical properties and chemical resistance. Its analogues. However, since the melting temperatures of nylon 6 and nylon 66 are 230 ° C and 260 ° C, respectively, nylon 6 and nylon 66 are not suitable for use in semiconductor processing equipment, circuit boards, automotive and aircraft parts due to insufficient heat resistance. The problem with its analogues.
為了解決耐熱性不足的問題，以丁二胺與己二酸反應而製備出的尼龍46(nylon 46)，具有相對較高的熔解溫度290℃。但是，由於尼龍46的高密度醯胺鍵導致其具有吸濕特性，因而使其在應用上受到限制，並且由於透過使用芳香族二羧酸與芳香族二胺，來取代脂肪族二羧酸或脂肪族二胺所獲得之芳香族聚醯胺的單體價格昂貴，因此亦使得尼龍46無法被廣泛地使用。In order to solve the problem of insufficient heat resistance, nylon 46 (nylon 46) prepared by reacting butanediamine with adipic acid has a relatively high melting temperature of 290 °C. However, since the high-density guanamine bond of nylon 46 causes its hygroscopic property, it is limited in application and is substituted for the aliphatic dicarboxylic acid or by using an aromatic dicarboxylic acid and an aromatic diamine. The monomer of the aromatic polyamine obtained from the aliphatic diamine is expensive, and thus the nylon 46 cannot be widely used.
另外，雖然聚亞醯胺、聚醚酮、芳香族聚醯胺、聚苯硫醚及其類似物都屬於高耐熱性樹脂，然而他們都具有價格昂貴以及製造方法複雜的缺失。In addition, although polyamines, polyether ketones, aromatic polyamines, polyphenylene sulfides, and the like are all high heat resistant resins, they are both expensive and complicated in manufacturing methods.
換言之，由於製造聚醯胺的習知方法是透過在二乙醇中製備二羧酸與二胺的鹽、將鹽自前述溶液中分離、將分離出的鹽溶解於大量溶劑中(例如大量的水)、在高溫下藉由壓力與真空之條件來除水等步驟，是故習知的製造方法非常繁瑣。此外，由於習知的製造方法會消耗大量的水，且需要大量的能源來除水，因此亦不符合經濟效益。In other words, since a conventional method for producing polyamines is to prepare a salt of a dicarboxylic acid and a diamine in diethanol, separate the salt from the aforementioned solution, and dissolve the separated salt in a large amount of solvent (for example, a large amount of water). It is a conventional manufacturing method that is very complicated by the steps of removing water by pressure and vacuum at a high temperature. In addition, since the conventional manufacturing method consumes a large amount of water and requires a large amount of energy to remove water, it is not economical.
為解決上述習知技術的問題，本發明之一目的係提供一種耐熱性聚醯胺的製造方法，其中，作為原料之單體係可以簡單且便宜地被製備。In order to solve the above problems of the prior art, it is an object of the present invention to provide a method for producing a heat-resistant polyamide which can be prepared simply and inexpensively as a single material.
為了達成此技術層面，本發明提供一種耐熱性聚醯胺的製造方法，該聚醯胺具有如化學式3所表示之重複單元，其係透過包含有如化學式1所表示之二酯化合物以及如化學式2所表示之二胺化合物的單體混合物，進行縮合聚合反應所完成者：In order to attain the technical level, the present invention provides a method for producing a heat-resistant polyamine having a repeating unit represented by Chemical Formula 3, which is passed through a diester compound represented by Chemical Formula 1 and a chemical formula 2 The monomer mixture of the represented diamine compound is subjected to a condensation polymerization reaction:
其中，R1 為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴；Wherein R 1 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms;
化學式2Chemical formula 2
H2 N-R2 -NH2 H 2 NR 2 -NH 2
其中，R2 為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴；Wherein R 2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms;
其中，R2 為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴。Wherein R 2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.
在此，以化學式2所表示的二胺化合物可為己二胺(hexamethylene diamine,HMDA)或2-甲基-1,5-戊二胺(2-methyl-1,5-pentane diamine,MPDA)。Here, the diamine compound represented by Chemical Formula 2 may be hexamethylene diamine (HMDA) or 2-methyl-1,5-pentane diamine (MPDA). .
更且，該單體混合物可進一步包含有如下列化學式4所表示的二羧酸：Furthermore, the monomer mixture may further comprise a dicarboxylic acid represented by the following Chemical Formula 4:
其中，R3為碳數2至20的脂肪族烴或者是碳數6至20的芳香族烴。Wherein R3 is an aliphatic hydrocarbon having 2 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms.
以下將更詳細敘述本發明。The invention will be described in more detail below.
依據本發明一實施例所製備的耐熱性聚醯胺，其可藉由聚合化學式1所表示的二酯化合物與化學式2所表示的二胺化合物予以製備，其中，係可透過氫化反應來還原芳香族二酯化合物的芳香環從而獲得該二酯化合物。The heat-resistant polyamine prepared according to one embodiment of the present invention can be prepared by polymerizing a diester compound represented by Chemical Formula 1 and a diamine compound represented by Chemical Formula 2, wherein a hydrogenation reaction is carried out to reduce aroma. The aromatic ring of the diester compound thereby obtains the diester compound.
由於芳香族二酯化合物的價格低廉，且其亦為用於合成製造習知聚醯胺用之1,4-環己烷二羧酸(1,4-cyclohexane dicarboxylic acid)的中間產物，因此相較於習知技術，本發明具有可經由縮減反應步驟從而以低成本來製造聚醯胺的優勢。Since the aromatic diester compound is inexpensive, and it is also an intermediate product for the synthesis and production of 1,4-cyclohexane dicarboxylic acid for the conventional polyamine, it is compared with The prior art has the advantage that the polyamine can be produced at a low cost via a reduction reaction step.
除此之外，由於化學式1所表示的二酯化合物極易溶解於化學式2所表示的二胺化合物中，且本發明不需去除溶劑的步驟，所以本發明亦具有反應簡單且反應速率快的優勢。因此，本發明不需要將鹽自反應溶液中分離、將分離的鹽溶解於包括水的溶劑中、以及在高溫下以真空條件除水等步驟，是故本發明具有可減少用於去除溶劑而耗損之大量能源的優勢。此外，由於用來進行製程的設備簡易，因而可簡化製程，所以本發明還具有能夠大幅地降低最終產物-耐熱性聚醯胺之製造成本的優勢。In addition, since the diester compound represented by Chemical Formula 1 is extremely soluble in the diamine compound represented by Chemical Formula 2, and the present invention does not require a solvent removal step, the present invention also has a simple reaction and a fast reaction rate. Advantage. Therefore, the present invention does not require the steps of separating the salt from the reaction solution, dissolving the separated salt in a solvent including water, and removing water under vacuum conditions at a high temperature, so that the present invention can be reduced for solvent removal. The advantage of a large amount of energy consumed. Further, since the apparatus for carrying out the process is simple, the process can be simplified, and therefore the present invention has an advantage of being able to greatly reduce the manufacturing cost of the final product-heat resistant polyamide.
在依據本發明一實施例之耐熱性聚醯胺的製造方法中，耐熱性聚醯胺可透過化學式1所表示之二酯化合物與化學式2所表示之二胺化合物，進行如下列反應方程式1所示之縮合聚合反應製備而得：In the method for producing a heat-resistant polyamide according to an embodiment of the present invention, the heat-resistant polyamide can be subjected to a diester compound represented by Chemical Formula 1 and a diamine compound represented by Chemical Formula 2, and is subjected to the following Reaction Formula 1 The condensation polymerization is shown to be obtained:
其中，R1 與R2 可為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴，且R1 與R2 較佳可為碳數1至14的脂肪族烴或者是碳數6至14的芳香族烴。更佳者為，化學式1中的R1 可為碳數1至6的烷基。最佳者為，化學式1所表示的化合物可為1,4-環己烷二羧酸二甲酯(1,4-cyclohexane dicarboxylic acid dimethylester)(或者是二甲基環己烷-1,4-二羧酸酯(dimethyl cyclohexane-1,4-dicarboxylate))，亦即，化學式1中的R1 為甲基。Wherein R 1 and R 2 may be an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 1 and R 2 may preferably be an aliphatic hydrocarbon having 1 to 14 carbon atoms or It is an aromatic hydrocarbon having 6 to 14 carbon atoms. More preferably those of Chemical Formula 1, R 1 may be an alkyl group having 1 to 6 carbon atoms. Preferably, the compound represented by Chemical Formula 1 may be 1,4-cyclohexane dicarboxylic acid dimethylester (or dimethylcyclohexane-1,4- Dimethyl cyclohexane-1,4-dicarboxylate, that is, R 1 in Chemical Formula 1 is a methyl group.
除此之外，化學式2中的R2 較佳為碳數1至10之線型或支鏈的烯烴基。更佳者為，化學式2所表示的化合物可為己二胺(HMDA)或2-甲基-1,5-戊二胺(MPDA)。In addition, R in the formula 22 is preferably an olefin-based linear or branched chain of 1 to 10 carbon atoms. More preferably, the compound represented by Chemical Formula 2 may be hexamethylenediamine (HMDA) or 2-methyl-1,5-pentanediamine (MPDA).
另外，化學式1所表示的二酯化合物，係可透過如下列反應方程式2所示之芳香族二酯化合物的氫還原反應製備而得：Further, the diester compound represented by Chemical Formula 1 can be obtained by a hydrogen reduction reaction of an aromatic diester compound represented by the following Reaction Formula 2:
其中，R1 可為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴，且R1 較佳可為碳數1至14的脂肪族烴或者是碳數6至14的芳香族烴。Wherein R 1 may be an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 1 may preferably be an aliphatic hydrocarbon having 1 to 14 carbon atoms or a carbon number of 6 to 14 Aromatic hydrocarbons.
芳香族二酯化合物可為二烷基對苯二甲酸酯(dialkyl terephthalate)或者是二芳基對苯二甲酸酯(diaryl terephthalate)。當芳香族二酯化合物為二烷基對苯二甲酸酯時，R1 最佳可為如上述之碳數1至6的烷基。The aromatic diester compound may be a dialkyl terephthalate or a diaryl terephthalate. When the aromatic diester compound is a dialkyl terephthalate, R 1 may preferably be an alkyl group having 1 to 6 carbon atoms as described above.
依據習知技術，1,4-環己烷二羧酸(CHA)係用於耐熱性聚醯胺的製造方法中，且該1,4-環己烷二羧酸係由對苯二甲酸酯製備而得，特別是由二烷基對苯二甲酸酯製備而得。本發明中所使用之該芳香族二酯化合物，係為用於合成習知技術中所使用之該1,4-環己烷二羧酸的中間產物。因此，本發明藉由縮減製造聚醯胺的整個反應步驟，而可更經濟且快速地製造出耐熱性聚醯胺。According to a conventional technique, 1,4-cyclohexanedicarboxylic acid (CHA) is used in a method for producing a heat-resistant polydecylamine, and the 1,4-cyclohexanedicarboxylic acid is derived from terephthalic acid. The ester is prepared, in particular from the preparation of dialkyl terephthalate. The aromatic diester compound used in the present invention is an intermediate product for synthesizing the 1,4-cyclohexanedicarboxylic acid used in the prior art. Therefore, the present invention can produce a heat-resistant polyamide amine more economically and rapidly by reducing the entire reaction step of producing polyamine.
本發明亦提供一種如化學式5所表示的共聚物以及該共聚物的製造方法。化學式5所表示之共聚物係由化學式4所表示之脂肪族或芳香族二羧酸與化學式1所表示之二酯化合物以及化學式2所表示之二胺化合物，進行縮合聚合反應製備而得者：The present invention also provides a copolymer represented by Chemical Formula 5 and a method for producing the copolymer. The copolymer represented by Chemical Formula 5 is prepared by a condensation polymerization reaction of an aliphatic or aromatic dicarboxylic acid represented by Chemical Formula 4 with a diester compound represented by Chemical Formula 1 and a diamine compound represented by Chemical Formula 2:
其中，R2 為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴，且R2 較佳為碳數1至14的脂肪族烴或者是碳數6至14的芳香族烴；R3 為碳數2至20的脂肪族烴或者是碳數6至20的芳香族烴；n為1至999的自然數；以及m為1至999的自然數。Wherein R 2 is an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 2 is preferably an aliphatic hydrocarbon having 1 to 14 carbon atoms or an aromatic having 6 to 14 carbon atoms. a hydrocarbon; R 3 is an aliphatic hydrocarbon having 2 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms; n is a natural number of 1 to 999; and m is a natural number of 1 to 999.
最佳者為，R2 可為碳數1至10之線型或支鏈的烯烴基，以及R3 可為碳數2至6的烯烴基或者是伸苯基。Most preferably, R 2 may be a linear or branched olefinic group having 1 to 10 carbon atoms, and R 3 may be an alkene group having 2 to 6 carbon atoms or a phenyl group.
具體而言，化學式4所表示之二羧酸較佳可為選自下列所構成之群組中的至少一種化合物：己二酸(adipic acid)、琥珀酸(succinic acid)、對苯二甲酸(terephthalic acid)、間苯二甲酸(isophthalic acid)、鄰苯二甲酸(phthalic acid)以及鄰苯二甲酸酐(phthalic anhydride)。Specifically, the dicarboxylic acid represented by Chemical Formula 4 may preferably be at least one compound selected from the group consisting of adipic acid, succinic acid, and terephthalic acid ( Terephthalic acid), isophthalic acid, phthalic acid, and phthalic anhydride.
如下列反應方程式3所示，化學式5之共聚物可透過將包含有化學式4所表示之脂肪族或芳香族二羧酸的單體混合物，添加至包含有化學式1所表示之二酯化合物與化學式2所表示之二胺化合物的混合物中，再進行縮合聚合反應製備而得。如上所述，當藉由將化學式4所表示之二羧酸，添加至化學式1所表示之二酯化合物與化學式2所表示之二胺化合物中來進行縮合聚合反應時，係存在有可透過適當地控制二羧酸的添加莫耳比，來輕易操控耐熱性聚醯胺之熔解溫度的優勢。As shown in the following reaction formula 3, the copolymer of Chemical Formula 5 can be added to a diester compound represented by Chemical Formula 1 and a chemical formula by a monomer mixture containing the aliphatic or aromatic dicarboxylic acid represented by Chemical Formula 4. The mixture of the diamine compounds represented by 2 is further prepared by a condensation polymerization reaction. As described above, when the dicarboxylic acid represented by Chemical Formula 4 is added to the diester compound represented by Chemical Formula 1 and the diamine compound represented by Chemical Formula 2 to carry out a condensation polymerization reaction, it is suitably permeable. The molar ratio of the dicarboxylic acid to the molar ratio of the dicarboxylic acid is controlled to easily control the melting temperature of the heat resistant polyamide.
其中中，R1 與R2 可為碳數1至20的脂肪族烴或者是碳數6至20的芳香族烴，且R1 與R2 較佳可為碳數1至14的脂肪族烴或者是碳數6至14的芳香族烴；以及R3 可為碳數2至20的脂肪族烴或者是碳數6至20的芳香族烴，且R3 較佳可為碳數2至6的烯烴基或者是伸苯基。Wherein R 1 and R 2 may be an aliphatic hydrocarbon having 1 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 1 and R 2 may preferably be an aliphatic hydrocarbon having 1 to 14 carbon atoms. Or an aromatic hydrocarbon having 6 to 14 carbon atoms; and R 3 may be an aliphatic hydrocarbon having 2 to 20 carbon atoms or an aromatic hydrocarbon having 6 to 20 carbon atoms, and R 3 may preferably be a carbon number of 2 to 6 The olefin group is either a phenyl group.
透過上述反應所製備之耐熱性聚醯胺之縮合聚合反應的具體方法係如下所述。The specific method of the condensation polymerization of the heat resistant polyamine prepared by the above reaction is as follows.
首先，將二酯化合物與二胺化合物導入配備有攪拌裝置與回流裝置之高壓反應器中。如果是製備化學式5所示之共聚物，再進一步將脂肪族或芳香族二羧酸導入前述高壓反應器中。First, a diester compound and a diamine compound are introduced into a high pressure reactor equipped with a stirring device and a reflux device. If the copolymer of Chemical Formula 5 is prepared, an aliphatic or aromatic dicarboxylic acid is further introduced into the aforementioned high pressure reactor.
導入反應物後，該高壓反應器隨即伴隨著逐漸增高的溫度開始攪拌。當該反應器內部的溫度升高至65℃或更高時，醇類就會被蒸餾出來並被收集於冷凝器中。After introduction of the reactants, the high pressure reactor is then agitated with increasing temperature. When the temperature inside the reactor is raised to 65 ° C or higher, the alcohol is distilled off and collected in a condenser.
當醇類被收集至理論收集量的一半時，將該反應器中的空氣置換成諸如氮氣、氬氣及其類似物的惰性氣體，並將該反應器密封以提高反應器的內部壓力。When the alcohol is collected to half of the theoretical collection amount, the air in the reactor is replaced with an inert gas such as nitrogen, argon, and the like, and the reactor is sealed to increase the internal pressure of the reactor.
反應的進行，是透過將反應溫度提升至300至400℃，以及攪拌反應物1小時至3小時，較佳為攪拌1小時45分鐘至2小時15分鐘，以及更佳為攪拌2小時來完成者。於此同時，透過使用閥門來控制該反應器的內部壓力不超過20kgf/cm2 。The reaction is carried out by raising the reaction temperature to 300 to 400 ° C, and stirring the reactant for 1 hour to 3 hours, preferably for 1 hour 45 minutes to 2 hours 15 minutes, and more preferably for 2 hours. . At the same time, the internal pressure of the reactor was controlled to not exceed 20 kgf/cm 2 by using a valve.
藉由緩慢地開啟閥門使該反應器的內部壓力成為大氣壓力以後，使用真空幫浦進一步將該反應器的內部壓力降至1torr或更低，並持續攪拌2至4小時，較佳為攪拌2小時30分鐘至3小時30分鐘，更佳為攪拌約3小時。After the internal pressure of the reactor is brought to atmospheric pressure by slowly opening the valve, the internal pressure of the reactor is further reduced to 1 torr or lower using a vacuum pump, and stirring is continued for 2 to 4 hours, preferably with stirring 2 30 minutes to 3 hours and 30 minutes, more preferably about 3 hours.
當透過量測攪拌裝置的轉力矩或是即時負載得知反應物的黏度達到要求值時，將諸如氮氣、氬氣及其類似物的惰性氣體導入該反應器中以釋放真空，並使用惰性氣體的注入壓力以卸出產物。When the viscosity of the reactant is measured by the torque of the stirring device or the instantaneous load to obtain the desired value, an inert gas such as nitrogen, argon or the like is introduced into the reactor to release the vacuum, and an inert gas is used. The injection pressure is to discharge the product.
視需求而定，係可進行額外的固態聚合反應。該固態聚合反應可透過將特定尺寸的聚合切片(polymerized chips)導入配備有攪拌裝置的反應器中、將溫度升高至超過該聚合切片的玻璃轉移溫度、以及將氮氣或氬氣導入該反應器中或者是使該反應器成為真空等步驟來完成。Additional solid state polymerization can be carried out depending on the needs. The solid state polymerization can be carried out by introducing a specific size of polymerized chips into a reactor equipped with a stirring device, raising the temperature to exceed the glass transition temperature of the polymerized slice, and introducing nitrogen or argon into the reactor. The process is completed by making the reactor vacuum.
如上所述，本發明之耐熱性聚醯胺的製造方法係使用可簡單經由氫化反應而製得之價格低廉的單體，且不需進行將鹽自反應溶液中分離、使用大量的水作為溶劑以溶解分離的鹽、以及除水等繁瑣且需消耗大量能源的複雜過程。因此，由於本發明之聚合反應的步驟簡短，且可大幅地縮減能源耗損，是故本發明可提供一種簡便且符合經濟效益之耐熱性聚醯胺的製造方法。As described above, the method for producing the heat-resistant polydecylamine of the present invention uses an inexpensive monomer which can be easily produced by a hydrogenation reaction, and does not require separation of the salt from the reaction solution, and uses a large amount of water as a solvent. In order to dissolve the separated salts, and complicated processes such as water removal, which consume a lot of energy. Therefore, since the steps of the polymerization reaction of the present invention are short and the energy consumption can be greatly reduced, the present invention can provide a simple and economical method for producing heat-resistant polyamide.
以下透過較佳範例與比較範例從而更加了解本發明。然而，下列範例與比較範例僅用以敘述本發明，且本發明之範疇並不受限於下列所述者。The invention will be better understood by the following examples and comparative examples. However, the following examples and comparative examples are merely illustrative of the invention, and the scope of the invention is not limited by the following.
範例1Example 1
將200克(1當量)的1,4-環己烷二羧酸二甲酯(1,4-cyclohexane dicarboxylic acid dimethylester)(Aldrich公司供售，順式結構與反式結構的混合物)以及233克(2當量)的己二胺(hexamethylene diamine)(Aldrich公司供售)導入一高壓反應器中，攪拌並混合之。待溫度升高至75℃後，蒸發的甲醇即可經由冷凝而透過冷凝器予以收集。當蒸餾出32克的甲醇時，將氮氣導入該反應器中以除去氧氣，而在關閉閥門後將溫度升高至400℃，之後攪拌混合物2小時。藉由緩慢地開啟閥門使該反應器的內部壓力降至大氣壓力，並藉由使該反應器成為真空致使該反應器的內部壓力變為1torr或更低以聚合該混合物3小時。其後，在開啟閥門後藉由導入氮氣以釋放真空，並經由該反應器的底部卸料裝置(lower discharging device)卸出耐熱性聚醯胺，並且，卸出的聚醯胺在水中冷卻後，使用裁切裝置將其裁切成特定尺寸的切片。200 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid dimethylester (available from Aldrich, a mixture of cis and trans structures) and 233 g (2 equivalents) of hexamethylene diamine (available from Aldrich) was introduced into a high pressure reactor, stirred and mixed. After the temperature is raised to 75 ° C, the evaporated methanol can be collected by condensation through a condenser. When 32 g of methanol was distilled off, nitrogen gas was introduced into the reactor to remove oxygen, and after the valve was closed, the temperature was raised to 400 ° C, after which the mixture was stirred for 2 hours. The internal pressure of the reactor was lowered to atmospheric pressure by slowly opening the valve, and the internal pressure of the reactor was changed to 1 torr or lower by subjecting the reactor to a vacuum to polymerize the mixture for 3 hours. Thereafter, after the valve is opened, nitrogen is introduced to release the vacuum, and the heat-resistant polyamide is discharged through the lower discharging device of the reactor, and the discharged polyamine is cooled in water. Cut it into slices of a specific size using a cutting device.
範例2Example 2
除了使用2-甲基-1,5-戊二胺(2-methyl-1,5-pentane diamine)來取代己二胺之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to using 2-methyl-1,5-pentane diamine to replace hexamethylenediamine, heat-resistant polyfluorene was produced in substantially the same manner as in Example 1. amine.
範例3Example 3
除了使用228克(1當量)的1,4-環己烷二羧酸二乙酯(1,4-cyclohexane dicarboxylic acid diethylester)(或者是二乙基環己烷-1,4-二羧酸酯(diethyl cyclohexane-1,4-dicarboxylate))來取代200克(1當量)的1,4-環己烷二羧酸二甲酯之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to 228 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid diethylester (or diethylcyclohexane-1,4-dicarboxylate) (diethyl cyclohexane-1,4-dicarboxylate)), in place of 200 g (1 equivalent) of dimethyl 1,4-cyclohexanedicarboxylate, the heat resistance was generally produced in the same manner as in Example 1. Polyamide.
此時，該1,4-環己烷二羧酸二乙酯係透過進行如下列所述方法的轉酯化反應予以合成者：將1當量的1,4-環己烷二羧酸二甲酯與2當量的乙醇溶解於二甲苯中，並使用迪安-史塔克裝置(dean-stark device)在回流前述反應物的同時去除甲醇。At this time, the diethyl 1,4-cyclohexanedicarboxylate was synthesized by performing a transesterification reaction as described below: 1 equivalent of 1,4-cyclohexanedicarboxylic acid dimethyl The ester was dissolved in xylene with 2 equivalents of ethanol and the methanol was removed while refluxing the aforementioned reactants using a dean-stark apparatus.
範例4Example 4
除了使用256克(1當量)的1,4-環己烷二羧酸二丙酯(1,4-cyclohexane dicarboxylic acid dipropylester)(或者是二丙基環己烷-1,4-二羧酸酯(dipropyl cyclohexane-1,4-dicarboxylate))來取代200克(1當量)的1,4-環己烷二羧酸二甲酯之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to 256 grams (1 equivalent) of 1,4-cyclohexane dicarboxylic acid dipropylester (or dipropylcyclohexane-1,4-dicarboxylate) (dipropyl cyclohexane-1,4-dicarboxylate) was prepared in the same manner as in Example 1 except that 200 g (1 equivalent) of dimethyl 1,4-cyclohexanedicarboxylate was replaced. Polyamide.
此時，該1,4-環己烷二羧酸二丙酯係透過進行如下列所述方法的轉酯化反應予以合成者：將1當量的1,4-環己烷二羧酸二甲酯與2當量的丙醇溶解於二甲苯中，並使用迪安-史塔克裝置(dean-stark device)在回流前述反應物的同時去除甲醇。At this time, the dipropyl 1,4-cyclohexanedicarboxylate is synthesized by performing a transesterification reaction as described below: 1 equivalent of 1,4-cyclohexanedicarboxylic acid dimethyl The ester was dissolved in xylene with 2 equivalents of propanol and the methanol was removed while refluxing the aforementioned reactants using a dean-stark apparatus.
範例5Example 5
除了使用284克(1當量)的1,4-環己烷二羧酸二丁酯(1,4-cyclohexane dicarboxylic acid dibutylester)(或者是二丁基環己烷-1,4-二羧酸酯(dibutyl cyclohexane-1,4-dicarboxylate))來取代200克(1當量)的1,4-環己烷二羧酸二甲酯之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to 284 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid dibutylester (or dibutylcyclohexane-1,4-dicarboxylate) (dibutyl cyclohexane-1,4-dicarboxylate) was substituted for 200 g (1 equivalent) of dimethyl 1,4-cyclohexanedicarboxylate, and heat resistance was produced in substantially the same manner as in Example 1. Polyamide.
此時，該1,4-環己烷二羧酸二丁酯係透過進行如下列所述方法的轉酯化反應予以合成者：將1當量的1,4-環己烷二羧酸二甲酯與2當量的丁醇溶解於二甲苯中，並使用迪安-史塔克裝置(dean-stark device)在回流前述反應物的同時去除甲醇。At this time, the dibutyl 1,4-cyclohexanedicarboxylate is synthesized by performing a transesterification reaction as described below: 1 equivalent of 1,4-cyclohexanedicarboxylic acid dimethyl The ester was dissolved in xylene with 2 equivalents of butanol and the methanol was removed while refluxing the reactants using a dean-stark apparatus.
範例6Example 6
除了使用324克(1當量)的1,4-環己烷二羧酸二苯酯(1,4-cyclohexane dicarboxylic acid diphenylester)(或者是二苯基環己烷-1,4-二羧酸酯(diphenyl cyclohexane-1,4-dicarboxylate))來取代200克(1當量)的1,4-環己烷二羧酸二甲酯之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to using 324 g (1 equivalent) of 1,4-cyclohexane dicarboxylic acid diphenylester (or diphenylcyclohexane-1,4-dicarboxylate) (diphenyl cyclohexane-1,4-dicarboxylate)), in place of 200 g (1 equivalent) of dimethyl 1,4-cyclohexanedicarboxylate, the heat resistance was substantially produced in the same manner as in Example 1. Polyamide.
此時，該1,4-環己烷二羧酸二苯酯係透過進行如下列所述方法的轉酯化反應予以合成者：將1當量的1,4-環己烷二羧酸二甲酯與2當量的苯酚溶解於二甲苯中，並使用迪安-史塔克裝置(dean-stark device)在回流前述反應物的同時去除甲醇。At this time, the diphenyl 1,4-cyclohexanedicarboxylate is synthesized by performing a transesterification reaction as described below: 1 equivalent of 1,4-cyclohexanedicarboxylic acid dimethyl The ester was dissolved in xylene with 2 equivalents of phenol, and methanol was removed while refluxing the aforementioned reactants using a dean-stark apparatus.
範例1至6之詳細的反應物組成及依其所製得之聚醯胺的物理性質係表列於下表1。The detailed reactant compositions of Examples 1 through 6 and the physical properties of the polyamines prepared therefrom are listed in Table 1 below.
比較範例1至6Comparison examples 1 to 6
除了使用表列於下表2之1當量的二羧酸來取代1當量的1,4-環己烷二羧酸二甲酯，以及使用表列於下表2之2當量的二胺來取代2當量的己二胺之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。Instead of using one equivalent of dicarboxylic acid listed in Table 2 below, one equivalent of dimethyl 1,4-cyclohexanedicarboxylate was used, and two equivalents of diamines listed in Table 2 below were used instead. The heat resistant polyamine was produced in substantially the same manner as in Example 1 except for 2 equivalents of hexamethylenediamine.
範例7至36Examples 7 to 36
除了使用表列於下表3之1,4-環己烷二羧酸二甲酯(CHDR)與二羧酸並依表3之使用莫耳比來取代1當量的1,4-環己烷二羧酸二甲酯，以及使用表列於下表3之2當量的己二胺(HMDA)或者是2當量的2-甲基-1,5-戊二胺(MPDA)來取代2當量的己二胺之外，其餘大體上依據與範例1相同的方法來製造耐熱性聚醯胺。In addition to using the dimethyl 1,4-cyclohexanedicarboxylate (CHDR) listed below in Table 3 and the dicarboxylic acid and using the molar ratio of Table 3 to replace 1 equivalent of 1,4-cyclohexane Dimethyl dicarboxylate, and replace 2 equivalents with 2 equivalents of hexamethylenediamine (HMDA) listed in Table 3 below or 2 equivalents of 2-methyl-1,5-pentanediamine (MPDA) The heat resistant polyamine was produced in substantially the same manner as in Example 1 except for hexamethylenediamine.
【實驗例】[Experimental example]
上述範例與比較範例所製造之耐熱性聚醯胺的性質係透過下列方法予以量測，且所得之測試結果表列於上表1至表3中。The properties of the heat-resistant polyamide produced by the above examples and comparative examples were measured by the following methods, and the test results obtained are shown in Tables 1 to 3 above.
黏度Viscosity
待藉由上述方法所製造之耐熱性聚醯胺溶解於間甲苯酚後，於35℃時使用奧斯特瓦爾德黏度計(Ostwald Viscosimeter)來測量該耐熱性聚醯胺的黏度。After the heat-resistant polyamine produced by the above method was dissolved in m-cresol, the viscosity of the heat-resistant polyamide was measured at 35 ° C using an Ostwald Viscometer.
熔點Melting point
使用掃描式熱差分析儀(differential scanning calorimeter,DSC)以每分鐘10℃的掃描速度，來測量藉由上述方法所製造之耐熱性聚醯胺的熔點。The melting point of the heat-resistant polyamide compound produced by the above method was measured using a scanning scanning calorimeter (DSC) at a scanning speed of 10 ° C per minute.
如表1所示，依據範例1至6之方法所製造之聚醯胺顯示出適合耐熱性聚醯胺的熔點，然而必須承認的是，透過使用比較範例1至6所揭露的材料，依據本發明之簡單方法所製出的聚合物亦具有良好的耐熱性，但是它們的聚合度並不高。更具體而言，為了獲得聚合度高的聚合物，因此比較範例製得之聚合物必須額外進行諸如增加反應時間或者是施行固態聚合反應等工序，是故比較範例製得之聚合物並不適當。不過，必須承認的是，雖然僅經由簡單的過程就能夠獲得依據本發明範例而聚合的聚合物，但是該聚合物卻具有良好的耐熱性以及適當的聚合度。As shown in Table 1, the polyamines produced according to the methods of Examples 1 to 6 showed a melting point suitable for heat-resistant polyamide, but it must be recognized that by using the materials disclosed in Comparative Examples 1 to 6, according to the present The polymers produced by the simple method of the invention also have good heat resistance, but their degree of polymerization is not high. More specifically, in order to obtain a polymer having a high degree of polymerization, the polymer obtained by the comparative example must be additionally subjected to a process such as increasing the reaction time or performing a solid state polymerization reaction, so that the polymer obtained by the comparative example is not appropriate. . However, it must be admitted that although a polymer polymerized according to an example of the present invention can be obtained only by a simple process, the polymer has good heat resistance and a suitable degree of polymerization.
另外，透過範例7至36可確認本發明之聚醯胺的製造方法，能夠藉由控制導入二羧酸的添加莫耳比以及進行縮合聚合反應，從而簡單地控制最終製得之耐熱性聚醯胺的熔解溫度。Further, the production method of the polyamine of the present invention can be confirmed by the examples 7 to 36, and the heat-resistant polyfluorene finally obtained can be simply controlled by controlling the addition of the molar ratio of the introduced dicarboxylic acid and performing the condensation polymerization reaction. The melting temperature of the amine.
Claims (6)
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