1283689 玖、發明說明： 【發明所屬之技術領域】 錫、鋅或鎂氣化合物， 本發明係關於一種藉添加活性裂解觸媒 以有效提昇聚碳酸酯裂解之方法。 【先前技術】1283689 玖, invention description: TECHNICAL FIELD OF THE INVENTION Tin, zinc or magnesium gas compounds, the present invention relates to a method for effectively increasing the cracking of polycarbonate by adding an active cracking catalyst. [Prior Art]
固體廢棄物處理在垃圾量年年增加而又無法完全有效解決的情 形下，無論是_外，大_了㈣此_難題存在的事實。尤並 量使用塑膠製品的今天，廢棄娜的處置更絲固體廢棄物處理中的 -項重要課題。在這祕無職品巾，除了傳_五大泛用塑膠及 聚對苯二甲酸乙二酉旨(PET)等相關產品佔有相當大的比例之外，以料 酸醋(Pdycarbonate，PC)所製成的相關廢棄產品，也因為被廣泛並大^ 的使用而逐漸佔有-席之地。聚碳酸酯，尤其是常見的2,2_雙(4伽分勤 丙烧聚碳酸轉_咖1八__0她），由於具有多種優點，如土古 衝擊強度及彈性魏、高透明性及自由染色性、耐疲勞性佳、耐候: 佳、電氣特性佳、無味無臭對人體無傷害性和尺寸安定性良好等，過 去已被廣泛應祕賴及遮_、家電和機具外殼、汽車和其 他工業零件、醫療用品等的製造上。近幾年來，聚碳酸自旨被大量用來 生產光學、電子零件和CD、CD_R〇M、CD R、cd rw、dvd、洲⑽ 等各種光㈣。由於當今電子資訊和視聽多雜產品，因為技術進步 且競，烈使產品價格大眾化，已經成為現代人生活的必需品和消費 性產品。再加上產品生命週期短、製作過程容易損壞或因著作權等種 種因素’造成其相關廢棄產物的急遽增加。根據ITIS產業資訊服務網於 =02年5胃月24日所公佈的資料顯示，全球2謝年的產能為⑽萬公嘲， 實際產量為177.4萬公噸，雖然因為全世界經濟不景氣造成需求量略有 下降’但由於專家難市場f求量仍有穩定成長空間，還是有許多家 廠商正在各地新建或彳鍵生產線以增加產量，尤其是在亞洲地區。因 1283689 此 如此 :綠色產品和製程的要求二=:ί:= 動，就如同其他歸—樣，在過錢年間已經賴。廢魏的仃 ^ ^ ^ όί; ih7 ^ ^ ^ ± ^ ^ ^ js ^ 是將回收廢棄塑膠產品上的其它 :万力物理方法 匕材貝为離、去除、洗淨、切成碎片、 t 丁溫炼融，依需要進行以下幾種可能的加 =力=出成型等。以此方式所製成的再製品，大多應用於生 Ϊ#丨=:的產品上，而此法所製成的再製品，品質比較不容易 I此回收之再製料使用於光學、電子零件和各種光碟 片製作上_子。化學方法是—難具=#源化和轉效制做法，常 見的是細b學·綠’將歸騎吻咖_罐為原聚合單 體、碳數較少且_價錢高的錢化合物或職成再生油以做雜 油㈣〇η)之用，所獲得的產品通常具有比較高的利用價值。聚碳咖旨 降解的方式主要有水解(Hydr〇lysis)、醇解(Methan〇lysis)和裂解 (Cracking or pyrolysis)等。其中水解和醇解是分別以水和醇類為溶劑的 液相反應，而裂解為固相反應。過去探討聚碳酸醋的化學回收處 理’在相關文獻與專利資料上並不多見，現有的學術與專利資料多集 中在液相反應的水解和醇解上。在學術f料方面，Tagaya等人於1999 年P^ly. Degmd. Stab.第64卷第289至292頁曾經發表，將聚碳酸酯在 230 C和430°C之間的次臨界(Subcritical)和超臨界(Supercriticai)水狀態 中，探討添加NaCl和NafO3對聚碳酸酯水解產物的影響。結果發現， 聚碳酸酯若不添加水，在3〇〇°C反應24小時並沒有任何前述產物生成； 如果有水的存在，在240°C反應24小時，前述產物可以有35·2%總產率， 右將/JEL度上升至430 C的超臨界狀態只要1小時便有的總產率。若 加入NafO3，在300°C反應24小時，總產率達67%。此實驗顯示聚碳酸 酯在有水的環境下且溫度足夠，水是良好的介質；如果有驗性鹽類加 入’對於其水解也有所助益。Hu專人於1998年Polymer第39卷第3841至 1283689 3845頁冒經發表，聚碳酸g旨在Na〇H的存在下，以甲醇或甲醇與甲苯的 混合液做為溶劑之醇解反應。結果發現，聚碳酸酯以甲醇為溶劑在6〇〇c 下330 mm ’轉化率極低；但是改以甲醇與甲苯混合液為溶劑並在ν&〇η 催化下只要70 min便有96%的轉化率。至於有關聚碳酸酯裂解反應，多 屬於有關裂解產物的分析及反應機制的探討，如·· McNem等人於1989 年Poly. Degrad· Stab.第24卷第59至63 頁、於1991 年Poly· Degrad· Stab.第 31 卷第 163至 180頁和於 1993年Poly· Degrad. Stab.第39卷第 145至 149頁 以及Forti等人於 1983年 j· Pdy· Sci pdym chem Ed，第21 卷第 1567 至 1572頁、Montaudo等人於 1985年 Poly. Degrad· Stab·第26卷第285至 263頁和於1992年Poly· Degrad. Stab.第37卷第91至96頁等。另有Day等人· 於1999年J· Anal. Appl. Pyrolysis第w卷第199至224頁探討電子工業常用， 塑膠（有ABS、P〇M、PC和PVC等）單獨或添加5%Cu，與混合塑膠（前 三種塑膠和PVC等量混合）分別在700〇C和9〇0〇C進行瞬間裂解時，以聚 碳酸酯為例，發現700忙時的裂解轉化率均較900〇c時為低，但混合塑 膠的裂解產率則明顯比預期值還高，顯示pvc的存在有助於聚碳酸酯的 裂解；但添加銅對聚碳酸酯裂解則沒有如PVC明顯，此一現象在其他塑 膠和PVC的混合裂解也有類似的情形發生。 在專利方面，R.J. Evans在美國專利第5,216，149號、第5,300,704 唬、第5,321，174號和第5,359,099號曾揭示有關多種純塑膠及塑膠混合 物之裂解回收，其中亦包含聚碳酸§旨和聚碳酸s旨與ABS或烈混合物:· 裂解回收，該回收法發現前述待裂解物在47〇〜5〇〇〇c間於水蒸汽氣氛 下有CaC〇3、Ca(OH)2或PVC存在時，待裂解物會有極佳之裂解轉化 率及裂解產物回收。Leeetal·在美國專利第5,386,〇55號揭示聚合物可以 姐度380〜450〇C及壓力220〜27〇atm的超臨界水狀態下，加人適當量之 氣化別如·空氣、氧氣或氧氣與鈍氣之混合氣體，可使此聚合物分解， 適用此法的聚合物麵文中雖有提及聚碳_但無侧實施例出現。 Bufch eUL在美國專利第5,266,716號揭示可以將聚碳酸酯溶解於弘以 倍量的溶劑(如:octane、tol職e、xylene等）中，同時加入4〇〇〜3〇〇〇则队 1283689 之咼沸點monohydroxy comp0lmds(如:methanol和ethanol)、觸媒(如:鈉與 鉀的metal oxides、hydroxides、acetates等)和complexing agents(如:crown ether 或polyethylene glyC〇ls)，在蒸德塔中（溫度 7〇〜j 7〇〇c 及壓力 2〇〇 mi>ar〜3 bar)蒸餾四小時，即可在塔頂和塔底處完全回收 carbonate與bisphenol A單體。Buysch et.al.後來在美國專利第5,391，802 號和第5,440,066號又分別揭示在前述類似反應裝置和反應條件下，可 以使用不同種類溶劑(如：phenol)或處理對象改為芳香族類聚碳酸酯，都 有良好的單體回收產率。 【發明内容】In the case of solid waste treatment, when the amount of garbage increases year by year and cannot be completely solved effectively, no matter whether it is _ or not, it is a big problem. In particular, the use of plastic products today, Abandoned Na's disposal of more important items in the disposal of solid waste. In this secret unemployed towel, in addition to the _ five major plastics and polyethylene terephthalate (PET) and other related products account for a considerable proportion, made of vinegar (Pyllylate, PC) The related waste products are gradually occupied by the use of a wide range of products. Polycarbonate, especially the common 2,2_double (4 gamma dimethoate, _ _ 1 1 __0 her), due to a variety of advantages, such as the ancient impact strength and elastic Wei, high transparency and Free dyeing, good fatigue resistance, weather resistance: good, good electrical properties, tasteless, odorless, harmless to the human body, good dimensional stability, etc., have been widely used in the past, cover, _, home appliances and machine casings, cars and other Manufacturing of industrial parts, medical supplies, etc. In recent years, polycarbonate has been used in large quantities to produce optical, electronic parts and various light (CD) such as CD, CD_R〇M, CD R, cd rw, dvd, and continent (10). Due to the current electronic information and audio-visual products, because of technological advancement and competition, the price of products has become popular, and it has become a necessity and a consumer product for modern people's lives. Coupled with the short life cycle of the product, the damage to the manufacturing process, or the rapid increase in its related waste products due to various factors such as copyright. According to the information published by the ITIS Industry Information Service Network on the 24th of the stomach on the 24th of the 0th year, the global production capacity of the two years is (10) million, and the actual output is 1.774 million metric tons, although the demand is due to the global economic downturn. A slight decline 'But because the experts are difficult to find the market, there is still room for stable growth, there are still many manufacturers are building new or key production lines to increase production, especially in Asia. Because 1283689 This is the case: Green products and process requirements 2 =: ί: = Action, just like other categorizations, have been in the money years.废魏 ^ ^ ^ όί; ih7 ^ ^ ^ ± ^ ^ ^ js ^ is the rest of the recycled plastic products: Wanli physical method coffin shells for separation, removal, washing, cutting into pieces, t Warm refining, as needed, the following possible additions = force = molding. The re-products produced in this way are mostly applied to the products of Ϊ#丨=:, and the re-products made by this method are not easy to be used. The recycled materials are used for optical and electronic parts and Various CDs are made on the _ sub. The chemical method is - hard to use = #source and transfer system practice, the common is that the fine b · green 'will be married to the kiss coffee _ cans as the original polymerization monomer, carbon number is less and _ high price of money compounds or The use of reclaimed oil for the use of miscellaneous oil (four) 〇η), the products obtained usually have a relatively high value. Polycarbonate degradation methods mainly include hydrolytic hydrolysis, Methan〇lysis, and cracking or pyrolysis. Wherein hydrolysis and alcoholysis are liquid phase reactions in which water and an alcohol are respectively used as a solvent, and are cleaved into a solid phase reaction. In the past, the chemical recovery of polycarbonate was investigated. 'There are few related literatures and patents. The existing academic and patent data are concentrated in the hydrolysis and alcoholysis of liquid phase reactions. In terms of academic materials, Tagaya et al., 1999, P^ly. Degmd. Stab., Vol. 64, pp. 289-292, published Subcritical, a polycarbonate between 230 C and 430 °C. In the supercriticai water state, the effect of adding NaCl and NafO3 on the polycarbonate hydrolysate was investigated. As a result, it was found that if the polycarbonate is not added with water, it is reacted at 3 ° C for 24 hours without any of the aforementioned products; if there is water, it can be reacted at 240 ° C for 24 hours, and the aforementioned product may have a total of 35.2%. The yield, the right/JEL degree rises to a supercritical state of 430 C as long as the total yield is 1 hour. When NafO3 was added, the reaction was carried out at 300 ° C for 24 hours, and the total yield was 67%. This experiment shows that polycarbonate is in a watery environment at a sufficient temperature and water is a good medium; it can also be beneficial if it is added to the test salt. Hu was published in the 1998 Polymer Volume 39, No. 3841 to 1283689, page 3845. Polycarbonate g is aimed at the alcoholysis reaction of methanol or a mixture of methanol and toluene in the presence of Na〇H. It was found that polycarbonate has a very low conversion rate of 330 mm at 6 〇〇c with methanol as solvent; however, it is changed to a mixture of methanol and toluene as solvent and catalyzed by ν & ηη as long as 70 min. Conversion rates. As for the polycarbonate cracking reaction, it is mostly related to the analysis of the cracking products and the reaction mechanism, as in McNem et al., 1989, Poly. Degrad· Stab. Vol. 24, pp. 59-63, Poly. Degrad· Stab. Vol. 31, pp. 163-180 and Poly· Degrad. Stab., Vol. 39, pp. 145-149, 1993, and Forti et al., 1983, j. Pdy Sci pdym chem Ed, Volume 21 1567 to 1572, Montaudo et al., 1985 Poly. Degrad Stab, Vol. 26, pp. 285-263 and 1992, Poly Degra. Stab., Vol. 37, pp. 91-96. Also, Day et al., 1999, J. Anal. Appl. Pyrolysis, Vol. w, pp. 199-224, discusses the common use in the electronics industry. Plastics (with ABS, P〇M, PC, PVC, etc.) alone or with 5% Cu, When the mixed plastic (mixed with the first three plastics and PVC) was subjected to instantaneous cracking at 700 °C and 9〇0〇C, respectively, taking polycarbonate as an example, it was found that the cracking conversion rate at 700 busy was higher than 900〇c. Low, but the cracking yield of the mixed plastic is significantly higher than expected, indicating that the presence of pvc contributes to the cracking of the polycarbonate; however, the addition of copper to polycarbonate cracking is not as obvious as PVC, this phenomenon is in other A similar situation occurs in the mixed cracking of plastic and PVC. In the patents, RJ Evans, in U.S. Patent Nos. 5,216,149, 5,300,704, 5,321,174 and 5,359,099, disclose the recovery of various pure plastics and plastic mixtures, including polycarbonate and poly The carbonic acid s is intended to be combined with ABS or a strong mixture: · cracking recovery. The recovery method finds that the above-mentioned lysate is in the presence of CaC〇3, Ca(OH)2 or PVC under a steam atmosphere between 47〇5〇〇〇5〇〇〇c. The lysate will have excellent cracking conversion rate and recovery of the cleavage product. Lee et al., in U.S. Patent No. 5,386, 〇55, discloses that the polymer can be in a supercritical water state of 380 to 450 〇C and a pressure of 220 to 27 〇 atm, and an appropriate amount of gasification is added, such as air or oxygen. A mixture of oxygen and a gas can decompose the polymer. The polymer surface to which this method is applied is referred to as polycarbon—but no side examples are present. Bufch eUL, U.S. Patent No. 5,266,716, discloses that the polycarbonate can be dissolved in a multi-volume solvent (e.g., octane, tol, e, xylene, etc.) while adding 4〇〇~3〇〇〇 to the team 1283689.咼 boiling point monohydroxy comp0lmds (such as: methanol and ethanol), catalysts (such as sodium and potassium metal oxides, hydroxides, acetates, etc.) and complexing agents (such as: crown ether or polyethylene glyC〇ls), in the steam tower ( The temperature of 7〇~j 7〇〇c and the pressure of 2〇〇mi>ar~3 bar) are distilled for four hours, and the carbonate and bisphenol A monomers can be completely recovered at the top of the column and at the bottom of the column. In U.S. Patent Nos. 5,391,802 and 5,440,066, respectively, it is disclosed that different types of solvents (e.g., phenol) or treated objects can be changed to aromatic polycarbonates under the aforementioned similar reaction apparatus and reaction conditions. Esters have good monomer recovery yields. [Summary of the Invention]
本發明之發明人發現在聚碳酸酯的裂解反應中，添加錫、鋅或鎂 化合物觸媒，可以非常有效的提昇聚碳酸酯裂解轉化率。 本發明亦發現在聚碳酸酯的裂解反應中，添加錫、辞或鎂化合物 觸媒，還可以非常有效的降低聚碳酸酯裂解溫度、縮短裂解時間、減 少觸媒用量和提昇液體油在產物中之選擇率。 依照本發明之方法，除了可應用於常見的2,2_雙(4-羥酚基)丙烷聚 破酸醋裂解外，也可以適麟任何以多祕化合物與碳酸為單體所聚 合而成的塑膠。此外，其他可以適用的聚酯類還包含聚鄰苯二甲酸乙 二醋、聚間苯二憎乙二醋、聚己讀乙二§旨、聚對苯二甲酸丁二醋、 及其他雙醇飽和或非飽和聚酯等，皆可達到增加裂解效率之目的。 依照本發明之方法，尚可應用於含上述聚酯類於加工過程中所產% 生之廢料以及以其所製成的產品經消費者使用過後所棄置之物品並已 將其他材質完全分離者。 本發明之方法運用錫、鋅或鎂化合物為觸媒，使用的化合物可為 醋酸化合物、魏化合物、輕化合物、氣化合物及械錯合物，复 中以氣化合物為最佳。 /、 依照本發明之方法，在聚碳酸酯的裂解反應中，運用錫、鋅或 鎂化合物觸媒，增加聚碳酸酯的裂解效率。裂解反應的操作溫度可在 1283689 300°C至550°C之範圍，其中以350°C至450cC之溫度範圍較佳。觸媒和聚 碳酸酯重量比值應介於0.01至0.33之間，其中以0.04至〇·2〇之範圍幹佳K 依照本發明之方法，觸媒和聚碳酸酯混合的方式可以為乾式^直接 混合法、濕式臨濕含浸法或其他能有效混合二者的方法。^果觸媒、舌 性佳，不論使用何種混合方式，聚碳酸酯皆有相近裂解轉化率；若觸 媒活性較差，則以濕式臨濕含浸法較佳。 為使本發明之目的、方法及優點能更明顯地說明，以下特舉實施 例作具體之陳述，但不以其内容限制本發明之範圍。 【實施方式】 f施例一：以氯化錫催化聚碳酸酯裂解反應 聚碳酸酯的裂解反應是在一個批式反應器内於常壓下進行。所用 聚碳酸醋原料之粒徑大小為〇_5〇〜0.71 mm、極限黏度為0.493，反靡用 量為1·00克；將聚碳酸酯重量1/1〇之帶二結晶水氯化錫(SnCl2.2H2〇)觸 媒以濕式臨濕含浸法和聚碳酸酯均勻混合，在8〇°c循環烘箱内乾燥12 小時後放入反應管内。裂解溫度為4〇(TC，裂解時間為1小日夺。裂解後有 殘留固體、液體與氣體產物，其中聚碳酸酯裂解轉化率是以聚碳酸酯 裂解過程中所損失的重量與原始重量比值表示之。液體油之選擇率是 裂解後所收集液體重量與殘留固體、液體與氣體產物總重(即聚碳酸酯 原始重量)之比值。 實施例二：以氣化鋅催化聚碏S參酯裂解反應 在反應中加入重量為聚碳酸酯1/1〇之無水氣化鋅(ZnCl2)觸媒， 其他反應條件同實施例一。 實施例三：以氣化鎮催化聚硝酿酯裂解反應 在反應中加入重量為聚碳酸酯1/1〇之帶六結晶水氣化鎂 (MgCl2.6H2〇)觸媒，其他反應條件同實施例一。 比較例一：無觸媒催化之聚碳gy旨裂解反應 在反應中不添加任何觸媒，其他反應條件同實施例一。 1283689 边較例士i每經遂盤也之廢聚碳酸酯裂解反應 反應中所用廢聚碳酸酯是指以聚碳酸酯原料製成的光碟片而尚未 在其表面塗上漆層之裸片，固有黏度為0 368，其他反應條件同比較例 〇 边較例兰」鋼催化聚碳酸酯裂解反應 在反應中添加重量為聚碳酸酯1/10之不具裂解活性帶二結晶水氯化 銅(CuC12.2H20)觸媒，其他反應條件同實施例一。 實施_魁垔....：不同氯化錫用詈之聚碳酸酯裂解反應 在反應中加入重量為聚碳酸酯丨/200、1/1〇〇、1/20或1/5之帶二結晶 水氣化錫觸媒，其他反應條件同實施例一。 實施:_不同氣化鋅用量之聚碳酸酯裂解反應 在反應中加入重量為聚碳酸酯1/2〇〇、1/1〇〇、1/20或1/5之氣化辞觸 媒’其他反應條件同實施例一。 實綠魁古：_不同氯化鎂用量之聚碳酸酯裂解反應 在反應中加入重量為聚碳酸酯1/200、1/100、1/20或1/5之帶六結晶 水氯化鎖觸媒’其他反應條件同實施例一。 實施例七：以乾式物理混合法利用氣化錫催化聚碏酸酯裂解反應 以乾式物理混合法使帶二結晶水氣化錫與聚碳酸酯原料直接均勻 混合後反應，其他反應條件同實施例一。 實施例八：以乾式物理混合法利用氩化鋅催化聚破酸酯裂解反應 以乾式物理混合法使氣化鋅與聚碳酸酯原料直接均勻混合後反 應’其他反應條件同實施例一。 實綠丄列九：以乾式物理混合法利用氣化鎂催化聚碳酸酯裂解反應 以乾式物理混合法使帶六結晶水氣化鎮與聚碳酸酯原料直接均勻 混合後反應，其他反應條件同實施例一。 1283689 . t 施例十：以氛化錫催化廢聚碳酸酯之裂解反應 反應中所用廢聚碳酸酯同比較例二，其他反應條件同實施例一。 复遮迦土一 ：以氪化锌俏化廢聚碳酸酯之裂解反應 反應中所用廢聚碳酸酯同比較例二，其他反應條件同實施例二。 复毯:以氣化鎂俏化廢聚碳酸酯之裂解反應 反應中所用廢聚碳酸酯同比較例二，其他反應條件同實施例三。 查玉同溫度以氯化錫催化聚碳酸酯裂解反應 裂解溫度改為300°c、325°c、350°C、450°C、475°C、500°C和550°C， 其他反應條件同實施例一。 达毯例四：在Μ遥度無觸媒催化聚瑞醯酯裂解反應 在反應中不添加任何觸媒，其他反應條件同實施例九。 ：H_例十四：在_王既時間以氣化錫催化聚碳酸酯裂解反應 將裂解時間改為1分鐘、3分鐘、7分鐘、15分鐘、3〇分鐘、3、5和8 小時，其他反應條件同實施例一。 生毯倒1 ·· 蜀媒催化聚破醯酯裂解及龐 將裂解時間改為3〇分鐘、3、5、小時，其他反應條件同比較例 —〇 一 一 ^施例—至三及比較例一至三的聚碳酸酯裂解轉化率列於表 。實施例-至二及比較例—之聚魏g旨裂解油選擇率列二 施例四至六之聚碳酸§旨裂解轉化率列於表三。實施例十 _裂解轉化率列於表…實施例十三及比較例四之聚碳 化率列於表四。實旆你丨, ± 久反日衣解轉 7； M、fZ 十 較例五之聚魏6旨裂解轉化率列於表 ^。。由上述的結果可知，本發明成功發現運用錫、 為觸媒’可_著提料碳_旨轉鱗魏。 ，、减5物 1283689 表一聚碳酸酯裂解轉化率 試例 裂解轉化率 實施例一 83.2 實施例二 81.6 實施例三 68.5 比較例一 8.5 比較例二 5.7 比較例三 6.7 實施例七 83.3 實施例八 80.9 實施例九 64.0 實施例十 83.5 實施例十一 81.5 實施例十二 67.8The inventors of the present invention have found that the addition of a tin, zinc or magnesium compound catalyst in the cracking reaction of polycarbonate can very effectively increase the cracking conversion rate of polycarbonate. The invention also finds that in the cracking reaction of polycarbonate, the addition of tin, rhenium or magnesium compound catalyst can also effectively reduce the cracking temperature of the polycarbonate, shorten the cracking time, reduce the amount of catalyst and enhance the liquid oil in the product. The selection rate. According to the method of the present invention, in addition to being applicable to the common 2,2-bis(4-hydroxyphenol)propane cleavage, it can also be polymerized by any of the secret compounds and carbonic acid as monomers. Plastic. In addition, other applicable polyesters include poly(ethylene phthalate), poly(m-phenylene terephthalate), poly(ethylene bromide), polybutylene terephthalate, and other diols. Saturated or unsaturated polyesters, etc., can achieve the purpose of increasing the efficiency of cracking. According to the method of the present invention, it can be applied to the waste material which is produced by the above-mentioned polyester in the processing process, and the product which is made after being used by the consumer and has completely separated other materials. . The method of the present invention utilizes a tin, zinc or magnesium compound as a catalyst, and the compound used may be an acetic acid compound, a Wei compound, a light compound, a gas compound and an mechanical complex, and a gas compound is preferred. /, according to the method of the present invention, in the cracking reaction of polycarbonate, a catalyst of tin, zinc or magnesium compound is used to increase the cracking efficiency of the polycarbonate. The operating temperature of the cleavage reaction may range from 1283689 to 300 ° C to 550 ° C, with a temperature range of from 350 ° C to 450 c C being preferred. The catalyst and polycarbonate weight ratio should be between 0.01 and 0.33, wherein the range of 0.04 to 〇·2 干 is good. According to the method of the present invention, the catalyst and the polycarbonate can be mixed in a dry manner. Mixed methods, wet wet impregnation methods or other methods that can effectively mix the two. ^The fruit catalyst and the tongue are good. Regardless of the mixing method, the polycarbonate has a similar cracking conversion rate; if the catalyst activity is poor, the wet type wet impregnation method is preferred. The following detailed description of the preferred embodiments of the present invention is intended to [Embodiment] f Example 1: Catalytic cracking reaction of polycarbonate with tin chloride The cracking reaction of polycarbonate is carried out in a batch reactor under normal pressure. The polycarbonate raw material used has a particle size of 〇_5〇~0.71 mm, an ultimate viscosity of 0.493, a ruthenium amount of 1.00 g, and a polycarbonate of 1/1 〇 of dicrystalline water of tin chloride ( The SnCl2.2H2(R) catalyst was uniformly mixed with a wet wet impregnation method and polycarbonate, and dried in a circulating oven at 8 ° C for 12 hours before being placed in a reaction tube. The pyrolysis temperature is 4 〇 (TC, the lysis time is 1 sec. There are residual solids, liquids and gaseous products after cleavage, wherein the polycarbonate cracking conversion rate is the weight-to-origin weight ratio lost during the polycarbonate cracking process. The liquid oil selectivity is the ratio of the weight of the liquid collected after cracking to the total weight of the residual solids, liquid and gas products (ie, the original weight of the polycarbonate). Example 2: Catalytic polymerization of poly(S) sulphate with zinc hydride In the cleavage reaction, an anhydrous zinc hydride (ZnCl2) catalyst having a weight of polycarbonate 1/1 〇 is added to the reaction, and other reaction conditions are the same as in the first embodiment. Example 3: catalyzing the cracking reaction of the polynitrocellulose ester by gasification A catalyst containing six crystal water of magnesium carbonate (MgCl2.6H2〇) having a weight of polycarbonate 1/1 〇 was added to the reaction, and other reaction conditions were the same as in Example 1. Comparative Example 1: Non-catalytic catalyzed poly carbon gy The cleavage reaction does not add any catalyst in the reaction, and the other reaction conditions are the same as in the first embodiment. 1283689 The waste polycarbonate used in the cracking reaction of the waste polycarbonate is also referred to as polycarbonate. Light made from raw materials A piece of die that has not been painted on its surface, has an intrinsic viscosity of 0 368, and other reaction conditions are the same as those of the comparative example. The steel is catalyzed by a polycarbonate cracking reaction. 10 does not have cracking activity with two crystal water copper chloride (CuC12.2H20) catalyst, other reaction conditions are the same as in the first example. Implementation _ burst ....: different tin chloride with ruthenium polycarbonate cracking reaction A hydrogenated tin catalyst with a weight of polycarbonate 丨/200, 1/1 〇〇, 1/20 or 1/5 was added to the reaction, and other reaction conditions were the same as in Example 1. Implementation: _ different gasification The amount of zinc in the polycarbonate cracking reaction is added to the reaction by adding a gasification catalyst of 1/2 〇〇, 1/1 〇〇, 1/20 or 1/5 of polycarbonate. Other reaction conditions are the same as in the first embodiment.实绿魁古: _ different magnesium chloride dosage of polycarbonate cracking reaction in the reaction to add weight of polycarbonate 1 / 200, 1 / 100, 1 / 20 or 1 / 5 with six crystal water chlorination lock catalyst 'Other reaction conditions are the same as in the first embodiment. Example 7: Using a dry physical mixing method to catalyze the polyphthalate cleavage reaction using a gasification tin The dry physical mixing method is carried out by directly mixing the dicrystalline water vaporized tin with the polycarbonate raw material, and the other reaction conditions are the same as those in the first embodiment. Example 8: Catalytic polymerization of the polyesterate by using zinc argon by dry physical mixing The reaction is carried out by dry physical mixing method to directly and uniformly mix the zinc oxide and the polycarbonate raw material. The other reaction conditions are the same as in the first embodiment. The green enthalpy is as follows: the cleavage reaction of the polycarbonate is catalyzed by magnesium hydride by dry physical mixing method. The gasification of the six-crystal water gasification town and the polycarbonate raw material are directly and uniformly mixed by the dry physical mixing method, and the other reaction conditions are the same as those in the first embodiment. 1283689 . t Example 10: Catalytic cracking of the waste polycarbonate by the tin-concentrating tin The waste polycarbonate used in the reaction was the same as in Comparative Example 2, and the other reaction conditions were the same as in Example 1. Fujijia soil 1: The cracking reaction used in the cracking reaction of zinc trioxide is the same as in the second comparative example. The other reaction conditions are the same as those in the second embodiment. The blanket: the waste polycarbonate used in the cracking reaction of the vaporized magnesium oxide polycarbonate was the same as in the second comparative example, and the other reaction conditions were the same as those in the third embodiment. Chayutong temperature is catalyzed by tin chloride catalyzed polycarbonate cracking reaction cracking temperature changed to 300 °c, 325 °c, 350 °C, 450 °C, 475 °C, 500 °C and 550 °C, other reaction conditions are the same Embodiment 1. Example 4: In the case of liberation, no catalyst-catalyzed ruthenium ester cleavage reaction. No catalyst was added in the reaction, and other reaction conditions were the same as in Example 9. :H_Example 14: At the time of _ Wang, the cracking time was changed to 1 minute, 3 minutes, 7 minutes, 15 minutes, 3 minutes, 3, 5 and 8 hours by gasification of tin-catalyzed polycarbonate cracking reaction. Other reaction conditions are the same as in the first embodiment. The raw carpet is poured 1 ·· The catalyzed catalyzed cracking of the ruthenium ester and the cleavage time is changed to 3 〇 minutes, 3, 5 hours, and the other reaction conditions are the same as the comparative example—〇一一^例—至三和比较One to three polycarbonate cracking conversion rates are listed in the table. Examples - to the second and comparative examples - the selection rate of the pyrolysis oil of the poly-weig is shown in Table 2. The cracking conversion rates of the four to six polycarbonates are shown in Table 3. Example 10 The cracking conversion rate is shown in Table 4. The carbonization rates of Example 13 and Comparative Example 4 are shown in Table 4. Actually, you are 丨, ± 久反反衣解转转; 7; M, fZ 十 The comparison of the cracking conversion rate of the sample 5 of the fifth example is listed in Table ^. . As is apparent from the above results, the present inventors have succeeded in finding that the use of tin and the catalyst can be used to extract carbon. , minus 5 1283689 Table 1 Polycarbonate Cracking Conversion Rate Trial Cracking Conversion Example 1 83.2 Example 2 81.6 Example 3 68.5 Comparative Example 1 8.5 Comparative Example 2 5.7 Comparative Example 3 6.7 Example 7 83.3 Example 8 80.9 Example 9 64.0 Example 10 83.5 Example 11 81.5 Example 12 67.8
表二聚碳酸酯裂解油之選擇率 試例 裂解油選擇率 實施例一 59.5 實施例二 51.7 實施例三 59.4 比較例一 1.2Table 2 Selection rate of polycarbonate cracking oil Test example Cracking oil selectivity Example 1 59.5 Example 2 51.7 Example 3 59.4 Comparative Example 1 1.2
12 1283689 表三不同觸媒用量之聚碳酸酯裂解轉化率 觸媒與聚碳 酸S旨重量比 裂解轉化率 實施例四 實施例五 實施例六 1/200 57.8 69.9 50.7 1/100 63.5 75.5 52.4 1/20 79.4 78.8 62.6 1/10 83.2 81.6 68.5 1/5 88.6 81.7 69.4 表四不同裂解溫度之聚碳酸酯裂解轉化率 裂解轉化率 裂解溫度 比較例四 實施例十三 300°C - 10.6 325°C - 73.1 350°C 0.5 77.7 400°C 8.5 83.2 450°C 64.6 82.1 475°C 71.4 79.2 500°C 73.8 78.6 550°C 75.9 80.2 13 1283689 表五不同裂解時間之聚碳酸酯裂解轉化率 裂解轉化率 裂解時間 比較例五 實施例十四 〆分鐘 一 64.3 三分鐘 麵 81.4 七分鐘 两 82.1 十五分鐘 - 82.4 三十分鐘 4.6 83.5 一小時 8.5 83.2 三小時 37.2 82.1 五小時 46.3 82.6 八小時 59.6 83.0 十一小時 63.5 1412 1283689 Table 3 Polycarbonate cracking conversion rate of different catalyst amount of catalyst and polycarbonate S weight ratio cracking conversion rate Example 4 Example 5 Example 61/200 57.8 69.9 50.7 1/100 63.5 75.5 52.4 1/ 20 79.4 78.8 62.6 1/10 83.2 81.6 68.5 1/5 88.6 81.7 69.4 Table 4 Polycarbonate cracking conversion rate of different cracking temperatures Cracking conversion rate Cracking temperature comparison Example 4 Example 13 300 ° C - 10.6 325 ° C - 73.1 350 ° C 0.5 77.7 400 ° C 8.5 83.2 450 ° C 64.6 82.1 475 ° C 71.4 79.2 500 ° C 73.8 78.6 550 ° C 75.9 80.2 13 1283689 Table 5 different cracking time of polycarbonate cracking conversion rate cracking conversion rate cracking time comparison Example 5 Example Fourteen minutes minute 64.3 three minutes face 81.4 seven minutes two 82.1 15 minutes - 82.4 thirty minutes 4.6 83.5 one hour 8.5 83.2 three hours 37.2 82.1 five hours 46.3 82.6 eight hours 59.6 83.0 eleven hours 63.5 14