TWI423993B - A method for polyesterification by tin catalysts - Google Patents
A method for polyesterification by tin catalysts Download PDFInfo
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本發明係關於一種含錫催化劑用於聚酯化反應之方法，特別是一種改善含錫催化劑之催化效率，以加速聚酯類高分子聚合物生成之方法。The present invention relates to a method for a polyesterification reaction of a tin-containing catalyst, and more particularly to a method for improving the catalytic efficiency of a tin-containing catalyst to accelerate the formation of a polyester-based polymer.
目前工業上操作酯化及聚酯化反應的進行，大多採用含金屬之化合物作為催化劑，如鋁、鈦、鋰或錫等化合物，藉以縮短酯化及聚酯化反應所需耗費的時間。At present, in the industrial operation of the esterification and polyesterification reaction, a metal-containing compound is often used as a catalyst, such as a compound such as aluminum, titanium, lithium or tin, thereby shortening the time required for the esterification and polyesterification reaction.
其中，更以錫化合物較常作為催化劑廣泛使用，該錫化合物包含有異辛酸亞錫、氯化亞錫、硫酸亞錫及二丁基氧化錫等。以該異辛酸亞錫為例，其係能於較少用量下，以高轉化率獲得較高分子量的聚合物。然而，該異辛酸亞錫本身的催化活性較低，必須經由長時間的高溫反應，才能發揮該異辛酸亞錫的完整催化效果，來獲得具有所需高分子量之聚合物，故於該異辛酸亞錫催化聚酯化反應的過程，往往需耗費大量能源與時間，而相對提高後續製成產品的成本負擔。Among them, tin compounds are more widely used as catalysts, and the tin compound includes stannous isooctanoate, stannous chloride, stannous sulfate, dibutyltin oxide, and the like. Taking the stannous isooctylate as an example, it is possible to obtain a higher molecular weight polymer at a high conversion rate with a lower amount. However, the stannous isooctylate itself has a low catalytic activity and must undergo a long-term high-temperature reaction in order to exert the complete catalytic effect of the stannous isooctylate to obtain a polymer having a desired high molecular weight, so the isooctanoic acid The process of stannous catalyzed polyesterification often requires a large amount of energy and time, and relatively increases the cost burden of subsequent finished products.
於此，多數業者係積極開發除了上述錫化合物之外，更能夠足以取代該異辛酸亞錫的催化劑，以期望於該聚酯化反應中獲得較佳的催化效果。Here, most of the companies actively develop a catalyst which is more capable of replacing the stannous isooctylate in addition to the above tin compound, in order to obtain a preferable catalytic effect in the polyesterification reaction.
如中華民國公開第200301273號「用於聚酯化反應之甲基錫觸媒」專利案，其係揭示一種甲基錫化合物，以於高溫酯化及聚酯化反應中作為催化劑，藉由該甲基錫化合物催化所獲得之酯及聚酯係具有極佳的物理/化學性質，以改進該酯及聚酯的色澤及熱穩定性，而適用於多階段聚酯化反應。然而，該習知專利案所揭示的甲基錫化合物，僅能改變後續聚酯化反應所生成之產品的物理及化學性質，甚至須以攝氏200度以上的高溫長時間作用，才能達到聚酯化反應過程的較佳催化效果，故該習知專利案仍舊無法改善如上所述之問題，更因反應溫度的提升相對增加整體聚酯化反應過程所需耗費的成本。For example, the Patent No. 200301273 of the Republic of China, "methyl tin catalyst for polyesterification reaction", discloses a methyl tin compound as a catalyst in high temperature esterification and polyesterification reaction. The methyl tin compound catalyzes the ester and polyester obtained to have excellent physical/chemical properties to improve the color and thermal stability of the ester and polyester, and is suitable for multi-stage polyesterification. However, the methyl tin compound disclosed in the prior patent can only change the physical and chemical properties of the product produced by the subsequent polyesterification reaction, and even must be subjected to a high temperature of 200 degrees Celsius or longer for a long time to reach the polyester. The preferred catalytic effect of the reaction process is still unable to improve the above-mentioned problems, and the increase in the reaction temperature relatively increases the cost of the overall polyesterification reaction process.
此外，儘管如上述習知專利案以其他含金屬之化合物作為聚酯化反應的催化劑，至今仍然無法於催化效率上有明顯的突破。甚至，多數催化劑往往容易於空氣的作用下，先行與空氣中的氧或水氣產生反應，而降低該催化劑的催化效果。不僅沒有如該異辛酸亞錫般具有較低的空氣敏感度，甚至無法於空氣下對未高度純化的酯類化合物進行開環聚合，以致於該些催化劑於進行聚酯化反應的過程係明顯存在有較多的限制。於是，現階段於業界操作聚酯化反應生成聚酯類高分子聚合物的過程，始終係以該異辛酸亞錫等錫化合物為主要催化劑，以至目前為止仍舊無法改善如上所述含錫催化劑催化效率不彰之困擾。Further, although the above-mentioned conventional patents use other metal-containing compounds as catalysts for the polyesterification reaction, there has been no significant breakthrough in catalytic efficiency. Even most catalysts tend to react with air or oxygen in the air under the action of air, thereby reducing the catalytic effect of the catalyst. Not only does it have low air sensitivity like the stannous isooctylate, but it is not even capable of ring-opening polymerization of unpurified ester compounds under air, so that the processes of the catalysts in the polyesterification reaction are obvious. There are more restrictions. Therefore, at this stage, the process of operating the polyesterification reaction to produce a polyester-based polymer in the industry has always been based on a tin compound such as stannous isooctylate as a main catalyst, and so far, it has not been possible to improve the catalysis of the tin-containing catalyst as described above. The efficiency is not plagued.
有鑑於此，確實有必要發展一種含錫催化劑用於聚酯化反應之方法，以期望提升該含錫催化劑於該聚酯化反應的催化效率，而解決如上所述的各種問題。In view of the above, it is indeed necessary to develop a method of using a tin-containing catalyst for the polyesterification reaction in order to improve the catalytic efficiency of the tin-containing catalyst in the polyesterification reaction, and to solve various problems as described above.
本發明之主要目的乃改良上述缺點，以提供一種含錫催化劑用於聚酯化反應之方法，其係能夠提高該含錫催化劑的催化活性，以提升該含錫催化劑於該聚酯化反應之催化效率者。The main object of the present invention is to improve the above disadvantages to provide a tin-containing catalyst for a polyesterification reaction, which is capable of increasing the catalytic activity of the tin-containing catalyst to enhance the tin-containing catalyst in the polyesterification reaction. Catalytic efficiency.
本發明之次一目的提供一種含錫催化劑用於聚酯化反應之方法，係能夠維持該含錫催化劑對空氣的低敏感度，以確保該含錫催化劑於該聚酯化反應之催化效果者。A second object of the present invention is to provide a method for the polyesterification reaction of a tin-containing catalyst, which is capable of maintaining the low sensitivity of the tin-containing catalyst to air to ensure the catalytic effect of the tin-containing catalyst in the polyesterification reaction. .
為達到前述發明目的，本發明之含錫催化劑用於聚酯化反應之方法之方法，係包含：一混合步驟，係將一N,N-二烷基甲醯胺二烷基縮醛類試劑混合一含錫催化劑，使該N,N二烷基甲醯胺二烷基縮醛類試劑所鍵結之烷氧基轉移至該含錫催化劑，以獲得一含錫催化劑錯合物；及一聚合步驟，係透過該含錫催化劑錯合物催化一酯類化合物進行開環聚合反應，以生成一聚酯類高分子聚合物；其中，該N,N二烷基甲醯胺二烷基縮醛類試劑係如化學式一所示之化合物，且該化學式一中的R係為烷基。In order to attain the foregoing object, the method for the method for the polyesterification reaction of the tin-containing catalyst of the present invention comprises: a mixing step of a N,N-dialkylformamidine dialkyl acetal reagent Mixing a tin-containing catalyst to transfer the alkoxy group bonded by the N,N-dialkylformamide dialkyl acetal reagent to the tin-containing catalyst to obtain a tin-containing catalyst complex; a polymerization step of catalyzing a ring-opening polymerization of an ester compound by the tin-containing catalyst complex to form a polyester-based polymer; wherein the N,N-dialkylformamide dialkyl is reduced The aldehyde reagent is a compound represented by Chemical Formula 1, and the R system of the Chemical Formula 1 is an alkyl group.
(RO)2 CHNR2 [化學式一](RO) 2 CHNR 2 [Chemical Formula I]
其中，該N,N二烷基甲醯胺二烷基縮醛類試劑係為N,N-二甲基甲醯胺二甲基縮醛或N,N-二甲基甲醯胺二乙基縮醛，該含錫催化劑係為異辛酸亞錫、硫酸亞錫、氯化亞錫或二丁基氧化錫。再者，該含錫催化劑的重量莫耳濃度係為0.0025~0.08M，且該含錫催化劑與該N,N二烷基甲醯胺二烷基縮醛類試劑的混合比例係為1：1。Wherein the N,N dialkylformamidine dialkyl acetal reagent is N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl The acetal, the tin-containing catalyst is stannous isooctylate, stannous sulfate, stannous chloride or dibutyltin oxide. Furthermore, the molar concentration of the tin-containing catalyst is 0.0025 to 0.08 M, and the mixing ratio of the tin-containing catalyst to the N,N-dialkylformamide dialkyl acetal reagent is 1:1. .
為讓本發明之上述及其他目的、特徵及優點能更明顯易懂，下文特舉本發明之較佳實施例，並配合所附圖式，作詳細說明如下：請參照第1圖所示，其係為本發明一較佳實施例，該含錫催化劑用於聚酯化反應之方法，其係包含一混合步驟S1及一聚合步驟S2。The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the appended claims. It is a preferred embodiment of the present invention, and the method for using a tin-containing catalyst for a polyesterification reaction comprises a mixing step S1 and a polymerization step S2.
該混合步驟S1係將一N,N二烷基甲醯胺二烷基縮醛試劑混合一含錫催化劑，使該N,N-二烷基甲醯胺二烷基縮醛類試劑所鍵結之烷氧基轉移至該含錫催化劑，以獲得一含錫催化劑錯合物。其中，該N,N二烷基甲醯胺二烷基縮醛類試劑係如化學式一所示之化合物，且該化學式一中的R係為烷基。The mixing step S1 is to mix a N,N-dialkylformamidine dialkyl acetal reagent with a tin-containing catalyst to bond the N,N-dialkylformamidine dialkyl acetal reagent. The alkoxy group is transferred to the tin-containing catalyst to obtain a tin-containing catalyst complex. Here, the N,N dialkylformamidine dialkyl acetal reagent is a compound represented by Chemical Formula 1, and R in the Chemical Formula 1 is an alkyl group.
(RO)2 CHNR2 [化學式一](RO) 2 CHNR 2 [Chemical Formula 1]
更詳言之，該N,N二烷基甲醯胺二烷基縮醛類試劑與該含錫催化劑混合後，係生成該含錫催化劑錯合物，該含錫催化劑錯合物係容易釋出類似聚合起始劑的物質，而不需額外添加苯甲醇等聚合起始劑，即可將該含錫催化劑錯合物應用於後續之聚合步驟S2，以進行一酯類化合物的開環聚合反應。其中，該含錫催化劑係可以選擇為異辛酸亞錫、氯化亞錫、硫酸亞錫及二丁基氧化錫等，且該N,N二烷基甲醯胺二烷基縮醛類試劑係可以選擇為N,N-二甲基甲醯胺二甲基縮醛(DMF-DMA)或N,N-二甲基甲醯胺二乙基縮醛(DMF-DEA)等。More specifically, the N,N-dialkylformamidine dialkyl acetal reagent is mixed with the tin-containing catalyst to form the tin-containing catalyst complex, and the tin-containing catalyst complex is easily released. A substance similar to a polymerization initiator can be applied to the subsequent polymerization step S2 to carry out ring-opening polymerization of an ester compound without additionally adding a polymerization initiator such as benzyl alcohol. reaction. Wherein, the tin-containing catalyst may be selected from stannous isooctanoate, stannous chloride, stannous sulfate, dibutyltin oxide, etc., and the N,N-dialkylformamidine dialkyl acetal reagent system It may be selected from N,N-dimethylformamide dimethyl acetal (DMF-DMA) or N,N-dimethylformamide diethyl acetal (DMF-DEA).
本實施例較佳係選擇為N,N-二甲基甲醯胺二甲基縮醛，使得該N,N-二甲基甲醯胺二甲基縮醛上的甲氧基更可以輕易轉移至該含錫催化劑上，以形成結構較為穩定之含錫催化劑錯合物。又，由於該酯類化合物的開環聚合反應主要係以甲氧基為聚合起始端，故鍵結於該含錫催化劑錯合物末端的甲氧基係可以作為聚合起始劑，而於後續之聚合步驟S2中發揮較佳的酯類化合物開環聚合之效果。This embodiment is preferably selected as N,N-dimethylformamide dimethyl acetal, so that the methoxy group on the N,N-dimethylformamide dimethyl acetal can be easily transferred. To the tin-containing catalyst, a tin-containing catalyst complex having a relatively stable structure is formed. Moreover, since the ring-opening polymerization reaction of the ester compound mainly uses a methoxy group as a polymerization starting end, the methoxy group bonded to the terminal of the tin-containing catalyst complex can be used as a polymerization initiator, and In the polymerization step S2, a preferred effect of ring-opening polymerization of the ester compound is exhibited.
本發明係以DMF-DMA作為該N,N-二甲基甲醯胺二甲基縮醛於下述內容中的簡稱。舉例而言，本實施例係先以1:1之比例，將該DMF-DMA試劑與異辛酸亞錫於甲苯溶劑中混合，且逐漸加熱至攝氏100度反應半小時，待真空抽乾反應後的揮發性物質後，加入正己烷洗去反應後的有機溶劑層，以生成油狀的該異辛酸亞錫錯合物。以此進行光譜分析，其結果係如第2a~2b圖所示，將該異辛酸亞錫錯合物(C)與該異辛酸亞錫(B)、DMF-DMA試劑(A)之光譜進行比較，明顯看出原本存在於(A)光譜中的a及c訊號皆於(C)光譜中消失，僅保留有該DMF-DMA試劑中的甲氧基訊號(如(C)圖所示之b訊號)，以及(B)光譜的異辛酸亞錫訊號。其中，該DMF-DMA試劑(A)之光譜所顯現之a、b及c訊號，係詳見於第2b圖所示，a代表氮基上鍵結之碳原子所鍵結之氫；b代表氧基上鍵結之碳原子所鍵結之氫；c代表主結構碳原子所鍵結之氫。The present invention uses DMF-DMA as an abbreviation for the N,N-dimethylformamide dimethyl acetal in the following. For example, in this embodiment, the DMF-DMA reagent is first mixed with stannous isooctylate in a toluene solvent at a ratio of 1:1, and gradually heated to a temperature of 100 ° C for half an hour, after being vacuum-dried. After the volatile matter, the organic solvent layer after the reaction is washed away by adding n-hexane to form the stannous isooctanoate complex in the form of an oil. Spectral analysis was carried out as a result, and the spectrum of the stannous isooctylate (C) and the stannous isooctanoate (B) and DMF-DMA reagent (A) was carried out as shown in Figures 2a to 2b. In comparison, it is apparent that the a and c signals originally present in the (A) spectrum disappear in the (C) spectrum, and only the methoxy signal in the DMF-DMA reagent remains (as shown in (C) b signal), and (B) spectrum of stannous isooctanoate signal. Wherein, the a, b and c signals appearing in the spectrum of the DMF-DMA reagent (A) are shown in Figure 2b, where a represents hydrogen bonded to the carbon atom bonded to the nitrogen group; b represents The hydrogen bonded to the carbon atom bonded to the oxy group; c represents the hydrogen bonded to the carbon atom of the main structure.
為更了解該DMF-DMA試劑係如何改變該含錫催化劑的結構，請再參再照第2a及2c圖所示，另以二氯化錫混合DMF-DMA進行光譜之分析(D)，明顯看出(D)光譜中僅顯現二組甲氧基d、e的訊號，可能係由其一甲氧基參與架橋鍵結(如第2c圖所示之e部分)，而以另一甲氧基懸掛鍵結於該二氯化錫之錫元素上(如第2c圖所示之d部分)；且，再輔以Sn119 NMR光譜圖得知，混合該DMF-DMA試劑後所生成之異辛酸亞錫錯合物，相較於該異辛酸亞錫於該NMR光譜圖上的偏移變化不大，故該異辛酸亞錫錯合物中的錫元素依然維持二價狀態，證實該異辛酸亞錫錯合物僅係以該DMF-DMA試劑所鍵結的甲氧基，與該異辛酸亞錫所鍵結的異辛酸基相互替換所形成之寡聚物，其化學反應式詳見第3圖所示。藉此，經由該DMF-DMA試劑的作用，係可以將該異辛酸亞錫合成為富含有甲氧基的該異辛酸亞錫錯合物，以提升該異辛酸亞錫本身的催化活性。In order to better understand how the DMF-DMA reagent system changes the structure of the tin-containing catalyst, please refer to the second and second graphs, and analyze the spectrum (D) with tin dichloride mixed with DMF-DMA. It can be seen that only the signals of the two groups of methoxy d, e appear in the (D) spectrum, possibly by the one-methoxy group participating in the bridging bond (such as the e part shown in Fig. 2c), and the other methoxy group. The base dangling is bonded to the tin element of the tin dichloride (as part d shown in Fig. 2c); and, by the Sn 119 NMR spectrum, the difference between the DMF-DMA reagents is obtained. The stannous octoate complex has little change in the shift on the NMR spectrum compared to the stannous isooctylate, so the tin element in the stannous isooctylate complex still maintains a divalent state, confirming the difference The stannous octoate complex is only formed by the methoxy group bonded by the DMF-DMA reagent and the oligomer formed by the substitution of the isooctanoic acid group bonded by the stannous isooctylate. Figure 3 shows. Thereby, the stannous isooctylate can be synthesized into the stannous isooctanoate complex rich in methoxy group by the action of the DMF-DMA reagent to enhance the catalytic activity of the stannous isooctanoate itself.
該聚合步驟S2係透過該含錫催化劑錯合物催化該酯類化合物進行開環聚合反應，以生成一聚酯類高分子聚合物。更詳言之，該含錫催化劑錯合物係具有烷氧基端，以透過該烷氧基端為該酯類化合物的聚合起始點，將該酯類化合物開環，以改變該酯類化合物的鍵連接順序，而可以由原本的環狀單體轉變為線性單體，且逐步聚合成高分子量的該聚酯類高分子聚合物。The polymerization step S2 catalyzes the ring-opening polymerization of the ester compound through the tin-containing catalyst complex to form a polyester-based polymer. More specifically, the tin-containing catalyst complex has an alkoxy end to permeate the alkoxy end to the polymerization starting point of the ester compound, and the ester compound is opened to change the ester. The bond sequence of the compound can be converted from a cyclic monomer to a linear monomer, and gradually polymerized into a high molecular weight polymer.
舉例而言，本實施例係將該混合步驟S1所生成之異辛酸亞錫錯合物混合25倍的環己內酯，使得該環己內酯能夠於足量的該異辛酸亞錫錯合物催化下，打開該環己內酯的環狀結構，以使該環己內酯的各元素、離子或分子間產生新的鍵連接順序，並轉變為線狀的環己內酯單體，再透過該異辛酸亞錫錯合物所富含的甲氧基為聚合起始劑，開始進行連續且逐步性的聚合反應，以此達到加速該環己內酯開環聚合生成高分子量之聚環己內酯的較佳效果。另外，更於該混合步驟S1中以該DMF-DMA試劑混合不同的該含錫催化劑，以生成各種該含錫催化劑錯合物，以對該環己內酯及乳酸交酯進行聚酯化反應，其化學反應式詳見於第4圖之(A)及(B)，其中(A)係指該環己內酯的聚酯化反應，而(B)係指該乳酸交酯的聚酯化反應。此外，該聚合步驟S2較佳係於一溶劑中進行反應，該溶劑特別係選擇為甲苯(toluene)，藉以達到較佳的酯類化合物聚合效果。For example, in this embodiment, the stannous isooctanoate complex formed by the mixing step S1 is mixed with 25 times of cyclocaprolactone, so that the cyclocaprolactone can be mixed in a sufficient amount of the stannous isooctanoate. Under the catalysis of the catalyst, the ring structure of the cyclocaprolactone is opened to generate a new bond connection sequence between the elements, ions or molecules of the cyclohexanolide, and is converted into a linear cyclocaprolactone monomer. Further, the methoxy group rich in the stannous isooctylate complex is used as a polymerization initiator to start a continuous and stepwise polymerization reaction, thereby accelerating the ring-opening polymerization of the cyclocaprolactone to form a high molecular weight polycondensation. The preferred effect of cyclocaprolactone. Further, in the mixing step S1, the tin-containing catalyst is mixed with the DMF-DMA reagent to form various tin-containing catalyst complexes to polyesterize the cyclocaprolactone and lactide. The chemical reaction formula is detailed in (A) and (B) of Fig. 4, wherein (A) refers to the polyesterification reaction of the cyclocaprolactone, and (B) refers to the polyester of the lactide. Reaction. Further, the polymerization step S2 is preferably carried out by reacting in a solvent, which is selected in particular as toluene, whereby a preferred polymerization effect of the ester compound is achieved.
由上述得知，本發明之含錫催化劑用於聚酯化反應之方法，係可以藉由該N,N-二烷基甲醯胺二烷基縮醛類試劑與該含錫催化劑的先行反應，而生成具有新鍵結結構的該含錫催化劑錯合物，且該含錫催化劑錯合物係具有足以啟動該酯類化合物進行開環聚合的烷氧基端，藉此大幅提升該含錫催化劑的催化活性，而可以在不添加聚合起始劑的情況下，快速進行該酯類化合物的聚酯化反應，以便於較低溫環境下，生成高分子量的聚酯類高分子聚合物，達到提升該聚酯化反應效率之功效。It is known from the above that the method for the polyesterification reaction of the tin-containing catalyst of the present invention can be preceded by the reaction of the N,N-dialkylformamidine dialkyl acetal reagent with the tin-containing catalyst. And forming the tin-containing catalyst complex having a new bonding structure, and the tin-containing catalyst complex has an alkoxy end sufficient to initiate ring-opening polymerization of the ester compound, thereby greatly increasing the tin-containing Catalyst activity of the catalyst, and the polyesterification reaction of the ester compound can be rapidly carried out without adding a polymerization initiator, so as to generate a high molecular weight polyester polymer at a lower temperature, Improve the efficiency of the polyesterification reaction.
再且，該N,N二烷基甲醯胺二烷基縮醛類試劑的添加僅具有鍵結結構的改變，而能維持該含錫催化劑本身錫元素的二價態樣，也不會影響該含錫催化劑對空氣的敏感度，故本發明混合該N,N-二烷基甲醯胺二烷基縮醛類試劑與含錫催化劑所生成的該含錫催化劑錯合物，係能保有該含錫催化劑較佳的物理及化學性質，以確保該含錫催化劑錯合物仍然具有較低的空氣敏感度，而可以暴露於空氣下，進行酯類化合物的聚酯化反應，而不至於在聚酯化反應的進行過程存在過多的限制。Furthermore, the addition of the N,N dialkylformamidine dialkyl acetal reagent only has a change in the bonding structure, and the divalent state of the tin element of the tin-containing catalyst itself can be maintained without affecting The sensitivity of the tin-containing catalyst to air, so that the N,N-dialkylformamide dialkyl acetal reagent and the tin-containing catalyst complex formed by the tin catalyst can be retained in the present invention. The tin-containing catalyst preferably has physical and chemical properties to ensure that the tin-containing catalyst complex still has low air sensitivity, and can be exposed to air to carry out polyesterification reaction of the ester compound without There are excessive limitations in the progress of the polyesterification reaction.
為了證實本發明之含錫催化劑用於聚酯化反應之方法，確實可以提高該含錫催化劑的活性，而於短時間內以較佳的催化效率，加速該酯類化合物的開環聚合反應，以於較低溫的反應過程，獲得高分子量的聚酯類高分子聚合物。In order to confirm the method for the polyesterification reaction of the tin-containing catalyst of the present invention, the activity of the tin-containing catalyst can be improved, and the ring-opening polymerization reaction of the ester compound is accelerated in a short time with a preferred catalytic efficiency. For the lower temperature reaction process, a high molecular weight polyester polymer is obtained.
本發明係針對環己內酯及乳酸交酯的聚合情形，個別進行下述實驗及分析，藉此觀察該含錫催化劑的催化反應時間(分)及轉化率(%)，且透過凝膠滲透層析法(GPC)分析該聚酯類高分子聚合物的分子量及分子量分佈度(PDI)。The present invention is directed to the polymerization of cyclocaprolactone and lactide, and the following experiments and analyses are separately performed, thereby observing the catalytic reaction time (minutes) and conversion rate (%) of the tin-containing catalyst, and permeating through the gel. The molecular weight and molecular weight distribution (PDI) of the polyester polymer were analyzed by chromatography (GPC).
請參照表1-1所示，其係為含錫催化劑催化環己內酯生成聚合物之情形，本實施例之N,N二烷基甲醯胺二烷基縮醛類試劑係選擇為N,N-二甲基甲醯胺二甲基縮醛(DMF-DMA)；該含錫催化劑係包含異辛酸亞錫、硫酸亞錫、氯化亞錫及二丁基氧化錫，且該含錫催化劑之重量莫耳濃度較佳係為0.08M。於此，依照不同比例將該DMF-DMA試劑個別與該些含錫催化劑混合後，再選擇性添加苯甲醇(benzyl alcohol,BnOH)作為聚合起始劑，來與未添加DMF-DMA的反應作比較，且於攝氏100度的環境下，同時添加10毫升的甲苯(toluene)作為溶劑，以進行環己內酯(ε-caprolactone,CL)的開環聚合反應。其中，該環己內酯的重量莫耳濃度較佳係選擇為2M。Referring to Table 1-1, it is a case where a tin-containing catalyst catalyzes the formation of a polymer of cyclocaprolactone, and the N,N-dialkylformamide dialkyl acetal reagent of the present embodiment is selected as N. N-dimethylformamide dimethyl acetal (DMF-DMA); the tin-containing catalyst comprises stannous isooctylate, stannous sulfate, stannous chloride and dibutyltin oxide, and the tin is contained The molar concentration of the catalyst is preferably 0.08 M. Herein, the DMF-DMA reagent is separately mixed with the tin-containing catalysts in different proportions, and then benzyl alcohol (BnOH) is selectively added as a polymerization initiator to react with the unadded DMF-DMA. For comparison, 10 ml of toluene was added as a solvent in an environment of 100 ° C to carry out ring-opening polymerization of cyclohexylide (ε-caprolactone, CL). Among them, the weight molar concentration of the cyclocaprolactone is preferably selected to be 2M.
表1-1：含錫催化劑催化環己內酯生成聚合物之情形。Table 1-1: The case where the tin-containing catalyst catalyzes the formation of a polymer from cyclocaprolactone.
由表1-1之結果得知，無論選擇之含錫催化劑係為上述何者，於該環己內酯開環聚合之過程中添加有該DMF-DMA試劑之組別(A1、B1、C1及D1)，相較於僅添加有該苯甲醇作為聚合起始劑未添加有該DMF-DMA試劑之組別(A2、B2、C2及D2)，於相同時間下，該環己內酯的轉化率係具有顯著性的提升，藉以證明該DMF-DMA試劑的添加，係能夠大幅增強該含錫催化劑本身的活性。且僅於攝氏100度的低溫，即可達到加速該環己內酯開環聚合生成聚環己內酯之功效。From the results of Table 1-1, no matter which of the selected tin-containing catalysts is selected, the group of DMF-DMA reagents (A1, B1, C1, and the like) are added during the ring-opening polymerization of the cyclocaprolactone. D1), the conversion of the cyclohexanolide at the same time compared to the group (A2, B2, C2, and D2) to which the DMF-DMA reagent was not added with the addition of the benzyl alcohol as a polymerization initiator The rate is markedly improved, thereby demonstrating that the addition of the DMF-DMA reagent can greatly enhance the activity of the tin-containing catalyst itself. And only at a low temperature of 100 degrees Celsius, the effect of accelerating the ring-opening polymerization of the cyclocaprolactone to form polycyclocaprolactone can be achieved.
此外，請參照表1-2所示，其係為含錫催化劑催化環己內酯生成高分子量聚合物之情形，本實施例係選擇以異辛酸亞錫作為催化劑，於攝氏140度之環境下，加入2500倍的環己內酯，且選擇性混合該DMF-DMA試劑，以進行該環己內酯的開環聚合反應。其中，該異辛酸亞錫的重量莫耳濃度較佳係為0.01M，且該環己內酯的重量莫耳濃度較佳係為25M。本實施例係於混合有該DMF-DMA試劑之情況下，添加20毫升之二甲苯，且於未混合該DMF-DMA試劑之情況下，添加5毫升之二甲苯，以同時反應1.2小時。In addition, please refer to Table 1-2, which is a case where a tin-containing catalyst catalyzes the formation of a high molecular weight polymer by cyclohexanolide. In this embodiment, stannous isooctylate is selected as a catalyst at a temperature of 140 degrees Celsius. 2500 times of cyclocaprolactone was added, and the DMF-DMA reagent was selectively mixed to carry out ring-opening polymerization of the cyclocaprolactone. Wherein, the weight molar concentration of the stannous isooctylate is preferably 0.01 M, and the weight molar concentration of the cyclocaprolactone is preferably 25 M. In the present embodiment, 20 ml of xylene was added in the case where the DMF-DMA reagent was mixed, and 5 ml of xylene was added without mixing the DMF-DMA reagent to simultaneously react for 1.2 hours.
表1-2：含錫催化劑催化環己內酯生成高分子量聚合物之情形。Table 1-2: The case where the tin-containing catalyst catalyzes the formation of a high molecular weight polymer by cyclocaprolactone.
由表1-2之結果得知，以該DMF-DMA試劑混合該含錫催化劑所生成之含錫催化劑錯合物，係可以對2500倍的環己內酯進行開環聚合反應，於相同時間下，相較於僅添加該含錫催化劑，而未混合有該DMF-DMA試劑時，該環己內酯的轉化率明顯自23%提升至76%，且其生成聚環己內酯後的分子量更可以高達74000，分子量分佈度為3.7。於此，證實本發明以該N,N-二烷基甲醯胺二烷基縮醛類試劑先行與該含錫催化劑作用後，的確可以獲得具有高催化活性的該含錫催化劑錯合物，以提升該含錫催化劑之催化效率，而於攝氏140度的低溫下，達到快速合成高分子量聚環己內酯之功效。As is apparent from the results of Table 1-2, by mixing the tin-containing catalyst complex formed by the tin-containing catalyst with the DMF-DMA reagent, ring-opening polymerization of 2,500-fold of cyclocaprolactone can be carried out at the same time. When the DMF-DMA reagent is not mixed, the conversion of the cyclocaprolactone is obviously increased from 23% to 76%, and the polycyclohexanolide is formed. The molecular weight can be as high as 74,000 and the molecular weight distribution is 3.7. Herein, it is confirmed that the N,N-dialkylformamidine dialkyl acetal reagent is first reacted with the tin-containing catalyst to obtain a tin-containing catalyst complex having high catalytic activity. In order to improve the catalytic efficiency of the tin-containing catalyst, the effect of rapidly synthesizing the high molecular weight polycyclocaprolactone is achieved at a low temperature of 140 degrees Celsius.
請參照表2-1所示，其係為含錫催化劑催化乳酸交酯生成聚合物之情形，本實施例之N,N二烷基甲醯胺二烷基縮醛類試劑係選擇為N,N-二甲基甲醯胺二甲基縮醛(DMF-DMA)；該含錫催化劑係包含異辛酸亞錫、硫酸亞錫、氯化亞錫及二丁基氧化錫，且該含錫催化劑之重量莫耳濃度較佳係為0.01M。於此，依照不同比例將該DMF-DMA試劑個別與該些含錫催化劑混合後，再選擇性添加苯甲醇(benzyl alcohol,BnOH)作為聚合起始劑，來與未添加DMF-MDA的反應作比較，且於攝氏100度的環境下，同時添加10毫升的甲苯(toluene)作為溶劑，以進行乳酸交酯(L-lactide,LA)的開環聚合反應。其中，該乳酸交酯的重量莫耳濃度較佳係選擇為0.5M。Referring to Table 2-1, it is a case where a tin-containing catalyst catalyzes the formation of a polymer of lactide, and the N,N-dialkylformamide dialkyl acetal reagent of the present embodiment is selected to be N. N-dimethylformamide dimethyl acetal (DMF-DMA); the tin-containing catalyst comprises stannous isooctylate, stannous sulfate, stannous chloride and dibutyltin oxide, and the tin-containing catalyst The weight molar concentration is preferably 0.01M. Herein, the DMF-DMA reagent is separately mixed with the tin-containing catalysts according to different ratios, and then benzyl alcohol (BnOH) is selectively added as a polymerization initiator to react with the unadded DMF-MDA. For comparison, 10 ml of toluene was added as a solvent in an environment of 100 ° C to carry out ring-opening polymerization of lactide (L-lactide, LA). Among them, the weight molar concentration of the lactide is preferably selected to be 0.5M.
表2-1：含錫催化劑催化乳酸交酯生成聚合物之情形。Table 2-1: The case where the tin-containing catalyst catalyzes the lactide to form a polymer.
由表2-1之結果得知，無論選擇之含錫催化劑係為上述何者，於該乳酸交酯開環聚合之過程中添加有該DMF-DMA試劑之組別(a1、b1、c1及d1)，相較於僅添加有該苯甲醇作為聚合起始劑未添加有該DMF-DMA試劑之組別(a2、b2、c21及d2)，於相同時間下，該乳酸交酯的轉化率係具有顯著性的提升，藉以證明該DMF-DMA試劑的添加，係能夠大幅增強該含錫催化劑本身的活性，同樣於攝氏100度的低溫下，達到加速該乳酸交酯開環聚合生成聚乳酸交酯之功效。As is apparent from the results of Table 2-1, regardless of which of the selected tin-containing catalysts, the group of the DMF-DMA reagents (a1, b1, c1, and d1) were added during the ring-opening polymerization of the lactide. The conversion ratio of the lactide at the same time is compared to the group (a2, b2, c21, and d2) to which the benzyl alcohol is added as a polymerization initiator without adding the DMF-DMA reagent. Significantly improved, thereby demonstrating that the addition of the DMF-DMA reagent can greatly enhance the activity of the tin-containing catalyst itself, and at the low temperature of 100 degrees Celsius, accelerate the ring-opening polymerization of the lactide to form polylactic acid. The effect of the ester.
此外，請參照表2-2所示，其係為含錫催化劑催化乳酸交酯生成高分子量聚合物之情形，本實施例係選擇以異辛酸亞錫作為催化劑，於攝氏140度之環境下，加入4000倍的乳酸交酯，且選擇性混合該DMF-DMA試劑，以進行該乳酸交酯的開環聚合反應。其中，該異辛酸亞錫的重量莫耳濃度較佳係為0.0025M，且該乳酸交酯的重量莫耳濃度較佳係為10M。本實施例係於混合有該DMF-DMA試劑之情況下，添加40毫升之二甲苯，且於未混合該DMF-DMA試劑之情況下，添加20毫升之二甲苯，以同時反應2.8小時。In addition, please refer to Table 2-2, which is a case where a tin-containing catalyst catalyzes the formation of a high molecular weight polymer by lactide. In this embodiment, stannous isooctylate is selected as a catalyst at an environment of 140 degrees Celsius. 4000 times of lactide was added, and the DMF-DMA reagent was selectively mixed to carry out ring-opening polymerization of the lactide. Wherein, the weight molar concentration of the stannous isooctylate is preferably 0.0025 M, and the weight molar concentration of the lactide is preferably 10 M. In the present embodiment, 40 ml of xylene was added in the case where the DMF-DMA reagent was mixed, and 20 ml of xylene was added without mixing the DMF-DMA reagent to simultaneously react for 2.8 hours.
表2-2：含錫催化劑催化乳酸交酯生成高分子量聚合物之情形。Table 2-2: The case where the tin-containing catalyst catalyzes the lactide to form a high molecular weight polymer.
由表2-2之結果得知，以該DMF-DMA試劑混合該異辛酸亞錫所生成之異辛酸亞錫錯合物，係可以對4000倍的乳酸交酯進行開環聚合反應，於相同時間下，相較於僅添加該含錫催化劑，而未混合有該DMF-DMA試劑時，經由該異辛酸亞錫錯合物催化之乳酸交酯係聚合為塊狀，且其生成聚乳酸交酯後的分子量更可以高達405000，分子量分佈度為2.87。於此，證實本發明以該N,N二烷基甲醯胺二烷基縮醛類試劑先行與該含錫催化劑作用後，的確可以獲得具有高催化活性的該含錫催化劑錯合物，以提升該含錫催化劑之催化效率，而於攝氏140度的低溫下，達到快速合成高分子量聚乳酸交酯之功效。It is known from the results of Table 2-2 that the stannous isooctylate complex formed by mixing the stannous isooctylate with the DMF-DMA reagent can perform ring-opening polymerization on 4000 times of lactide. At the time, when the DMF-DMA reagent is not mixed with the addition of the tin-containing catalyst, the lactide-based polymerization catalyzed by the stannous isooctylate complex is agglomerated, and the polylactic acid is formed. The molecular weight after the ester can be as high as 405,000 and the molecular weight distribution is 2.87. Herein, it is confirmed that the N,N-dialkylformamide dialkyl acetal reagent is first reacted with the tin-containing catalyst to obtain a tin-containing catalyst complex having high catalytic activity. The catalytic efficiency of the tin-containing catalyst is improved, and the high-molecular-weight polylactide is rapidly synthesized at a low temperature of 140 degrees Celsius.
本發明之含錫催化劑用於聚酯化反應之方法，其係能夠提高該含錫催化劑的催化活性，以提升該含錫催化劑於該聚酯化反應的催化效率，以達到該酯類化合物快速聚合之功效。The method for the polyesterification reaction of the tin-containing catalyst of the present invention is capable of improving the catalytic activity of the tin-containing catalyst to improve the catalytic efficiency of the tin-containing catalyst in the polyesterification reaction, so as to achieve the ester compound rapidly The effect of polymerization.
本發明之含錫催化劑用於聚酯化反應之方法，係能夠維持該含錫催化劑對空氣的低敏感度，以確保該含錫催化劑於該聚酯化反應的催化效果，達到生成高分子量酯類聚合物之功效。The method for the polyesterification reaction of the tin-containing catalyst of the invention is capable of maintaining the low sensitivity of the tin-containing catalyst to air to ensure the catalytic effect of the tin-containing catalyst in the polyesterification reaction, and to form a high molecular weight ester. The efficacy of polymers.
雖然本發明已利用上述較佳實施例揭示，然其並非用以限定本發明，任何熟習此技藝者在不脫離本發明之精神和範圍之內，相對上述實施例進行各種更動與修改仍屬本發明所保護之技術範疇，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.
[本發明][this invention]
S1．．．混合步驟S1. . . Mixing step
S2．．．聚合步驟S2. . . Aggregation step
第1圖：本發明之操作流程圖。Figure 1: Flow chart of the operation of the present invention.
第2a圖：本發明之光譜分析圖。Figure 2a: Spectral analysis of the invention.
第2b~2c圖：本發明之化學結構示意圖。2b~2c: Schematic diagram of the chemical structure of the present invention.
第3圖：本發明之化學結構反應式一。Figure 3: Reaction Scheme 1 of the chemical structure of the present invention.
第4圖：本發明之化學結構反應式又一。Figure 4: The chemical structure of the present invention is further.
Claims (9)
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| US9839906B1 (en) | 2016-12-07 | 2017-12-12 | Industrial Technology Research Institute | Catalyst and method for synthesizing cyclic carbonate by the same |
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|---|---|---|---|---|
| US4439597A (en) * | 1980-08-25 | 1984-03-27 | Celanese Corporation | Process for the preparation of polybutylene terephthalate |
| EP0634435A1 (en) * | 1993-07-12 | 1995-01-18 | General Electric Company | Improved polyesterification catalyst |
| CN1129478C (en) * | 1999-05-25 | 2003-12-03 | Acma有限公司 | Esterification catalysts |
| CN1610580A (en) * | 2000-11-21 | 2005-04-27 | 帝国化学工业公司 | Esterification catalyst, polyester process and polyester article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4439597A (en) * | 1980-08-25 | 1984-03-27 | Celanese Corporation | Process for the preparation of polybutylene terephthalate |
| EP0634435A1 (en) * | 1993-07-12 | 1995-01-18 | General Electric Company | Improved polyesterification catalyst |
| CN1129478C (en) * | 1999-05-25 | 2003-12-03 | Acma有限公司 | Esterification catalysts |
| CN1610580A (en) * | 2000-11-21 | 2005-04-27 | 帝国化学工业公司 | Esterification catalyst, polyester process and polyester article |
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| US9839906B1 (en) | 2016-12-07 | 2017-12-12 | Industrial Technology Research Institute | Catalyst and method for synthesizing cyclic carbonate by the same |
| CN108160116A (en) * | 2016-12-07 | 2018-06-15 | 财团法人工业技术研究院 | Catalyst and method for synthesizing cyclic carbonate by using same |
| CN108160116B (en) * | 2016-12-07 | 2020-11-10 | 财团法人工业技术研究院 | Catalyst and method for synthesizing cyclic carbonate by using same |
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