200918562 ’ 八、 本案若有化學式時，請揭示最能顯示發明特徵的化學式. 九、 發明說明： 【發明所屬之技術領域】 本發明涉及高分子化合物的製備方法及所用設備’具體爲—種光學級聚甲基丙烯酸 甲酯連續式溶液聚合工藝及所用設備。 【先前技術】 , 聚甲基丙烯酸甲酯’英文名Polymethyl Methacrylate，簡稱pMMA，是有著廣泛應 用領域的剛性透明的熱塑性材料’其聚合製備方法有懸浮法 '乳化法、本體法及溶液法 多種，其中’乳化法的成品透明性差，且成本昂貴’不適用於商業生產。懸浮法製備過 程是.將MMA和共聚物添加引發劑，聚合反應至某一轉化率，再添加大量水及懸浮劑 進一步聚合，PMMA形成珠料懸浮于水中，經過脫水洗滌、乾燥再經過擠出機$_ 〇 在生產過程，7JC及能源消耗極大，同時因屬分批式反應，各段步騾需要許多人工處理， 對大量生產而言，經濟效益不高，同時因含有灰分故不適用於高級光學產品應用。 合法一·般有。單體濃度高，容易產生凝 膠，同時反應速率快，大型規模生產其放熱反應不易控制。80年代美國PTI公司提出溶 液聚合方式雖改進前述問題’美國專利US4,728,701於1988年3月1日公開了—種丙燦 酸酯的聚合方法；美國專利US4,933,400於1990年6月12日公開了一種甲基丙嫌酸醋 的連續式溶液聚合方法，但這些聚合方法使用溶劑比例高達進料60%，反應速率過慢， 反應釜體積顯著比例增大致使投資額高昂，同時該工藝還存在著以下各項缺點：1.聚合 反應溫度低於100°C，使用引發劑，及分子調節齊Ιί的劑量相對增加，影響純度及回收精 製問題。2·採用兩段聚合槽’因爲ΜΜΑ及其共聚物如ΜΑ或ΕΑ的共聚速度比率不同， 致使第一段反應及第二段反應生成聚合物其共聚比例會有遊移差異。3.脫揮工藝不良， 當聚合過程固形物達到40%以上’聚合溶液經齒輪泵輸往殼管式加熱器預熱，其流程爲 由下往上，聚合溶液經過加熱器的加熱管，並於尾端由控制閥控制出口壓力以維持管內 液態狀況，此方式傳熱係數低加熱效果不佳，致使加熱器龐大’聚合溶液在其間滯留時 間長，容易產生低聚物及寡聚物’嚴重影響品質。 200918562 此外，商業用途甲基丙烯酸甲酯一般添加有l〇ppm以上的抑制劑，働□ 6-叔丁基-34-二甲基苯酚（商品名TopanolA)，此抑制劑對產品光學性如透光性，濁度及顏色會有影 響，因此可去除此抑制劑及雜物是必要的考慮。 【發明内容】 爲克服現有技術的不足，提高PMMA的生產效率和產品品質，並降低生產能耗， 本發明公開了一種光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝及所用設備，本發明通 過如下技術方案實現所述目的： 一種光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備，由精製蒸餾裝置、聚 •合反應裝置、兩段脫揮裝置和拉絲造粒襄置串聯組合而成，包括：主原料儲槽(1)、共聚 單體儲槽(2)、溶劑儲槽(3)、回收單體儲槽(4) '預熱器(5)、進料精製塔(6)、再沸器⑺、 聚合反應槽⑻、回收精製塔(9)、添加劑配製槽(1〇)、線上攪拌器(11)、過濾裝置(12)、 模頭(13)、加熱器(14)、力口熱器(15)、脫揮槽(16)、脫揮槽(17)、冷凝器(18)，（19)，(20)，(21)， (22)、貯罐(23)，(24)、泵(25)，(26), (27)，(28)，（29)，（30), (31), (32), (33)、控制閥(35), (36)， (37)和高黏度齒輪泵(38), (39), (40). 其中’主原料儲槽(1)、共聚單體儲槽(2)、溶劑儲槽(3)和回收單體儲槽(4)分別從位 於各自底部的出料口通過泵(25)，泵(26)、泵(27)和泵(28)及輸送管道連接至預熱器(5)的進 料口，預熱器(5)的出料口通過輸送管道連接至進料精製塔(6)下部的進料口，進料精製 塔⑹進料口的下方安裝有再沸器，進料精製塔(6)頂部的1號出料口通過輸送管道連接 '" 至冷凝器(18)的1號進料口，進料精製塔(6)底部的2號出料口通過泵(29)及輸送管道連 接至塔內中部的2號排放口，貯罐(23)的1號出料口通過泵(30)及輸送管道連接至在進 料精製塔(6)內部上方的1號入口，在輸送管道進入1號入口之前安裝有控制閥(35).聚 合反應槽(8)的進料口通過輸送管道和泵(30)與控制閥(35)之間的輸送管道相連通，聚合 反應槽(8)爲單一聚合槽，內有攪拌設施，貯罐(23)的2號出料口通過輸送管道連接至冷 凝器(18)的2號出料口，貯罐(23)的3號出料口是一排水泄閥，聚合反應槽(8)上部的1 號出料口通過管道連接至冷凝器(19)的進料口，冷凝器(19)內夾套迴圈冷水，冷凝器(19) 的出料口和冷凝器(18)的出料口都通過輸送管道和連接冷凝器(20)與冷凝器(21)之間的2 條輸送管道中的1號輸送管道相連通，連接在冷凝器(19)出口的輸送管道上安裝有控制 閥(36) 氣輸送管道上安裝有控制閥(37)，聚合反應槽(8)下部的2號出料口通過高黏 200918562 度齒輪泵(38)及輸送管道連接至加熱器(1.4)的進料口，脫揮槽(16)安裝在加熱器(14)的下 方並和加熱器(14)的出料口直接連接，脫揮槽(16)上方的一號出料口通過輸送管道連接 至回收精製塔⑼的進料口，脫揮槽(16)下方的二號出料口通過高黏度齒輪泵(39)及輸送 管道連接至加熱器(15)的進料口，脫揮槽(17)安裝在加熱器(15)的下方並和加熱器(15)的 出料口直接連接，脫揮槽(Π)上方的一號出料口通過輸送管道連接至冷凝器(22)的進料 口，脫揮槽(17)下方的二號出料口通過高黏度齒輪泵(40)及輸送管道連接至線上攪拌器 (11)的進料口，添加劑配製槽(1〇)的出料口通過輸送管道和連接脫揮槽(Π)出料口與線上 攪拌器(11)進料口之間的輸送管道相連通，線上攪拌器(11)的進料口通過輸送管道連接至 過濾裝置(12)的進料口，過濾裝置(12)的出料口通過輸送管道連接至模頭(13)，冷凝器(22) • 的1號出料口通過輸送管道連接至貯罐(24)的進料口，冷凝器(22)的2號出口連接至真 空泵(32)和排放管道，貯罐(24)的1號出料口通過輸送管道和連接冷凝器(20)與冷凝器(21) 之間的2條輸送管道中的2號輸送管道相連通，貯罐(24)的2號出料口通過泵(33)及輸 送管道連接至回收精製塔⑼內部上方的1號入口，回收精製塔(9)頂部的1號出料口通過 輸送管道連接至冷凝器(20)的進料口，回收精製塔(9)底部的2號出料口通過泵(34)及輸 送管道連接至塔內中部的2號入口，冷凝器(21)的出料口連接有真空泵(31)和排放管道’ 回收單體儲槽⑷的另一個入料口通過輸送管道和泵(33)與回收精製塔(9)內部上方的1號 排放口之間的輸送管道相連通。 一種光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝，將單體、共聚物、穩定劑、分 子量調節齊1、引發劑、溶劑按①精製蒸餾、②聚合反應、③閃蒸脫揮和④拉絲造粒四步 驟操作完成’全部反應都在如權利要求1或2所述的光學級聚甲基丙烯酸甲酯連續式溶 液聚合工藝所用設備內完成，其特徵在於： ① 精製蒸餾：從主原料儲槽(1)、共聚單體儲槽(2)、溶劑儲槽(3)、回收單體儲槽(句 中輸送出的單體、共聚物、溶劑先經預熱器⑶加熱至6〇°C〜12〇。(：，然後送入進料精製 塔⑹精製蒸餾’進料精製塔內氣壓在4xl03Pa〜4.7xl04Pa，除去內含的抑制劑和殘留雜 物； ② 聚合反應：將經第①步精製蒸餾後的反應物輸送入聚合反應槽⑻發生沸騰式聚 合反應，聚合反應溫度控制在130°C〜160°C ; ③ 閃蒸脫揮：脫揮採用兩段脫揮，第一段脫揮裝置包括：加熱器(14)、脫揮槽(16) 及回收精製塔(9)，第二段脫揮裝置包括：力口熱器(15)及脫揮槽(17) ’ 200918562 '將第②步反應聚合的生成物用高黏度齒輪泵(38)輸送至加熱器(14)加熱至22〇t>c〜 260T：，再輸送至脫揮槽(16)，脫揮槽(16)內氣壓在4xl〇Jpa〜4.7xl〇4pa ’未反應單體在 脫揮槽(16)的真空中蒸發並輸送至回收精製塔(9)精製蒸餾’回收精製塔(9)塔頂溫度在30 。(:〜80t，塔內氣壓在4x1.〜4.7Xl〇4Pa，未反應單體在@收精製塔⑼內經真空蒸餾 後輸送至冷凝器(20)和冷凝器(21)冷凝，冷凝後輸送至貯罐(24)貯存， 經第一段脫揮精製的生成物用高黏度齒輪栗(3 9)輸送至加熱器(15)加熱至220°C〜 26(TC，再輸送至脫揮槽(17) ’脫揮槽(17)內氣壓低於Ux10% ’未反應單體在脫揮槽(17) 的真空中蒸發並輸送至冷凝器(22)冷凝，冷胃存； ④拉絲造粒:將經第③步閃蒸脫揮精製的生成物用高黏度齒輪泵(40)輸送至線上攪 ， 拌器(11)，添加紫外線防止劑、潤滑劑、離型劑並混合後輸送至過濾裝置(12)過濾，去 除雜物，再經模頭(13)擠出切粒，乾燥包裝。 所述的光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝，用於聚合反應的單體是甲基 丙烯酸甲酯和苯乙烯中的任意一種，共聚物是丙烯酸甲酯、丙烯酸乙酯，苯乙烯，丙烯 腈和馬林酐中的任意一種；用於聚合反應的溶劑選用甲苯或乙苯，加入量爲反應物總重 量5%〜30% ;第③步拉絲造粒時，過據裝置去除的雜物粒徑大於80μηι。 本發明的所公開技術方案’聚合反應時共聚單體、回收單體由各貯槽按一定比例及 數量匯流並經加熱進入進料精製塔蒸餾精製’此蒸餾精製的目的是去除單體的抑制劑及 殘留不純物及水份，同時去除回收料的寡聚物及雜物。®是光學級生產的第一胃#。 '蒸餾精製的原料混合一定比例的引發劑，分子調節劑及其它添加副料以一定速率均句穩 " 定地進入聚合反應槽。聚合反應槽具有承受壓力結構’夾套以熱媒，蒸氣，或冷熱水迴 圈利用環流（REFLUX)控制聚合反應的放熱，以控制聚合反應的溫度。爲達到最佳聚 合分子結構及經濟效益性，反應溫度控制於130至160°C爲佳。聚合反應槽具有良好攪 拌混合效果，同時利用攪拌以避免槽壁累積聚合物結垢等問題。爲避免聚合物產生於槽 頂冷凝器及槽壁，添加適當比例的溶劑.，溶劑的添加量爲反應物總重量的5%至3〇%， 其重點是稀釋揮發有機蒸氣單體濃度’含溶劑的冷凝液同時具有刷洗避免聚合物生成的 功能。 聚合反應後固形物占總重量的比例在50%以上，經泵傳送到加熱器a預熱至22(rc 〜260。(：，此加熱器的設計及操作條件是脫揮工藝的要件，約50%固形物的聚合物溶液 經第一段般揮後其固形物占總重量的比例達98至99%。脫揮槽(16)是真空控制，氣壓約 200918562 在4xl03Pa至4.7xl04Pa，未參與反應單體及溶劑貝恠脫揮槽(16冲揮發進入配套的一回 收精製塔(9)處理。利用脫揮過程中必需的加熱’此部份回收蒸氣熱量轉爲精製蒸餾所 需，這樣就大大利用了餘熱達到節能效果。在脫揮槽(16)的聚合物輸送至加熱器(15)並 進入脫揮槽(17) ’脫揮槽(17)內氣壓低於1.3xl03Pa，再次去除剩餘的殘留單體及溶劑。 以達到光學級要求高純度。 在脫揮槽(Π)中，聚合物成熔融狀由高黏度齒輪泵(40)輸出。在管路中可安裝線上 攪拌器(11)，以利於紫外線防止劑、潤滑劑、離型劑等助劑的添加混合。 添加後聚合物經過濾裝置(12)以去除粒徑在80μπι以上的雜物，然後由模頭(13)以麵 條狀拉出切粒，乾燥，篩選，去粉，包裝，貯運。 本發明所公開的技術方案是連續式本體聚合法，整個工藝主要分爲反應聚合、閃蒸 脫揮和拉絲造粒等生產工序，和現有技術相比，有如下優點： 1·高度安全性 在ΜΜΑ本體的聚合中不論有沒有共聚單體’聚合物的高粘度都會降低正在增長中 聚合物分子的流動性，減緩鏈終止速率，該現象稱作爲凝膠現象。它會導致聚合反應速 率急劇增力D，同時反應熱的大量生成和超高分子聚合物的形成。凝膠現象會造成反應暴 走(run away) ’而且這種反應的控制十分困難。 本發明所公開的技術方案結合進料配方和工藝控制成功解決上述凝膠現象。通過減 小快速反應放熱，可以簡便控制反應速率和產品的分子量。確保生產線裝置高度的安全 性。在反應混合物中加入溶劑使得利用揮發氣冷凝器來冷卻帶走反應熱成爲可行。與其 他冷卻形式相比，這是一個轉移熱量的有效方法，降低了裝置成本。揮發氣冷凝器冷卻 也可以把、溶解在反應物中有害的氧氣除掉，所以改善生成產品的性能和顏色。 2.避免凝膠累積，提高產品物性與色澤 本發明所公開的技術方案，其配方和操作條件的選擇可以確保在容器壁和傳送管線 內不會發生聚合物的逐漸積累，這種累積會造成操作事故和終端產品的有害的凝膠。 3·低能耗環保潔淨 本發明所公開的技術方案，其反應系統中有效地使用了引發劑、共聚單體和鏈轉移 劑。在脫蟑過程中減小了低分子量的部分，高效益的脫揮過程是產品品質和均勻性的— 個重要因讀。原料到最後產品的使用率極高。與懸浮法相比’溶液法減少了原料的消耗， 同時無水參予反應，減少脫水、乾燥等能源耗用，並減免汙水處理，是一種更潔淨的環# 200918562 丁藥i 〇 4. 反應系統多功能性 本發明所公開的技術方案，其反應系統具有良好的靈活應變能力，可以調節產品的 多分散性（分子量分佈）和共聚單體比率，複使滿足生產物與其他工業產品的可加工性。 發展新的ΡΜΜΑ產品’可以製成多分散性小於2.2的產品。通過簡單變動生產原料工 藝操作條件可以獲得高分散性產品。. 5. 產品耐候性 與懸浮法生產ΡΜΜΑ相比’所公開的技術方案沒有弓丨入懸浮劑或乳化劑，因此生 產的產品不會受到添加齊!ί的影響。典型的產品分析表明沒有檢測到灰含量，而懸浮法會 包含15〜25ppm的灰含量’這樣減小了霧度，改善了產品加工的耐候性。 6. 無水聚合 所公開的技術方案由於沒有水的加入’所以廢水的處理量降到最低限度，唯一需要 處理的水是由進料MMA單體帶進來的。這些水可以在聚合過程中自動從單體中分離出 來。 7·系統全封閉 所公開的技術方案是全封閉系統，沒有廢氣排放，沒有危害員工的難聞氣體。 8·產品無黑斑 · 用本發明所公開的技術方案生產的ΡΜΜΑ產品不會有黑斑，而懸浮法廠出的產品 一般都有黑斑。 9·回收系統環保節能 本發明所公開的技術方案’其回收系統引入了精製塔，能利用脫揮過程的蒸氣過熱 能量從而節約能源，這也減小了冷凝器尺寸和水的用量。 【實施方式】 結合具體實施例對本發明作詳細說明，本實施例在以本發明技術方案爲前提下 進行實施，給出了詳細的實施方式和具體的操作過程，但本發明的保護範圍不限於下述 的實施例。 實施例1 如圖1所示’ 一種光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備，由精製 200918562 蒸餾裝置、聚合反應裝置、兩段脫揮裝置和拉絲造粒裝置串聯組合而成，包括：主原料 儲槽1、共聚單體儲槽2、溶劑儲槽3、回收單體儲槽4、預熱器5、進料精製塔6、再 沸器7、聚合反應槽8、回收精製塔9、添加劑配製槽1〇、線上攪拌器11、過濾裝置12、 模頭13、加熱器al4、加熱器M5、脫揮槽al6、脫揮槽bl7、冷凝器al8〜冷凝器e22 ' 貯罐a23、b24、泵a25〜泵j34、控制閥a35〜控制閥C37和高黏度齒輪泵a38〜高黏度 齒輪栗c40 ; 其中，主原料儲槽1、共聚單體儲槽2、溶劑儲槽3和回收單體儲槽4分別從位於 各自底部的出料口通過泵a25、泵b26、'泵c27和泵d28及輸送管道連接至預熱器5的 進料口，預熱器5的出料口通過輸送管道連接至進料精製塔ό底部的進料口，進料精製 «塔6進料口的下方安裝有再沸器7，進料精製塔6頂部的1號出料口通過輸送管道連接 至冷凝器al8的1號進料口 ’進料精製塔6底部的2號出料口通過泵e29及輸送管道連 接至塔內中部的2號排放口，貯罐a23的1號出料口通過泵β〇及輸送管道連接至在進 料精製塔6內部上方的1號排放□，在輸送管道進入1號排放口之前安裝有控制閥〇35， 聚合反應槽8的進料口通過輸送管道和泵f30與控制閥a35之間的輸送管道相連通，聚 合反應槽8爲單一聚合槽，內有攪拌器用以持續混合高粘度流體，貯罐a23的2號出料 口通過輸送管道連接至冷凝器al8的2號進料口，貯罐a23的3號出料口是一安全泄閥， 聚合反應槽8上部的1號出料口通過管道連接至冷凝器bl9的進料口，冷凝器M9內夾 套迴圈冷熱水、蒸氣或熱媒，冷凝器al8的出料口和冷凝器M9的出料口都通過輸送管 道和連接冷凝器c20與冷凝器d21之間的2條輸送管道中的1號輸送管道相連通，連接 f k 在冷凝器M9出料口的輸送管道上安裝有控制閥b36,氣體輸送管道上安裝有控制閥C37 並且和冷凝器M9與控制閥b36之間的輸送管道相連通，聚合反應槽8下部的2號出料 口通過高黏度齒輪泵a38及輸送管道連接至加熱器al4的進料口，脫揮槽al6安裝在加 熱器al4的下方並和加熱器al4的出料口直接連接，脫揮槽al6上方的一號出料口通過 輸送管道連接至回收精製塔9的進料口，脫揮槽al6下方的二號出料口通過高黏度齒輪 泵b39及輸送管道連接至加熱器M5的進料口，脫揮槽M7安裝在加熱器M5的下方並 和加熱器bl5的出料口直接連接，脫揮槽M7上方的一號出料口通過輸送管道連接至冷 凝器e的雄料口，脫揮槽bl7下方的二號出料口通過高黏度齒輪泵C40及輸送管道連接 至線上攪畔器11的進料口，添加劑配製槽10的出料口通過輸送管道和連接脫揮槽M7 出料口與賴上擾拌器11進料口之間的輸送管道相連通，線上攪拌器11的進料口通過輸 11 200918562 送管道連接至過濾裝置12的進料口，過濾裝置12的出料口通過輸送管道連接至模頭 13，冷凝器e22的1號出料口通過輸送管道連接至貯罐b24的進料口，冷凝器e22的2 號出料口連接有泵h32和排放管道’貯罐b24的1號出料口通過輸送管道和連接冷凝器 C20與冷凝器d21之間的2條輸送管道中的2號輸送管道相連通，貯罐b24的2號出料 口通過泵i33及輸送管道連接至回收精製塔9內部上方的1號排放口 ’回收精製塔9頂 部的1號出料口通過輸送管道連接至冷凝器c20的進料口，回收精製塔9底部的2號出 料口通過泵j34及輸送管道連接至塔內中部的2號排放口’冷凝器d21的出料口連接有 栗g31和有纟放管道，回收單體儲槽4的另—個出料口通過輸送管道和泵i33與回收精製 塔9內部上方的1號排放口之間的輸送管道相連通。 實施光學級聚甲基丙燦酸甲醋連續式溶液聚合工藝時，單體、共聚物、穩定劑、分 子量調節劑'引發劑、溶劑按①精製蒸餾'②聚合反應、③閃蒸脫揮和④拉絲造粒四步 驟操作完成，各組份的選用物質和用量如表2所示： 表2 組份 選用物質 用量（千克/小時） 主單體 甲基丙烯酸甲酯 4295 共聚物 丙烯酸甲酯 225 表2(續) 組份 選用物質 用量（千克/小時） 溶劑 甲苯 500 引發劑 二叔戊基過氧化物 0.85 分子調節劑 十二烷基硫醇 7.2 全部反應都在如上所述的光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備 內完成： ①精製蒸餾：從主原料儲槽卜共聚單體儲槽2、溶劑儲槽3、回收單體儲槽4中 輸送出的單體、共聚物、穩定劑、分子量調節劑和引發劑先經預熱器5加熱至90°C，然 後送入進科精製塔ό精製蒸餾，進料精製塔6內氣壓在8xl03Pa，除去內含的抑制劑和 殘留雜物； 12 200918562 ② 聚合反應：將經第①步精製蒸餾後的反應物輸送入聚合反應槽8發生沸騰式聚 合反應，聚合反應溫度控制在155。(：，氣壓爲〇.35MPa ; ③ 閃蒸脫揮：脫揮採用兩段脫揮，第一段脫揮裝置包括•加熱器al4、脫揮槽al6 及回收精製塔9，第二段脫揮裝置包括：加熱器M5及脫揮槽M7， 將第②步反應聚合的生成物用高黏度齒輪泵a38輸送至加熱器aM加熱至230°C， 再輸送至脫揮槽al6，脫揮槽a16內氣壓在8xl03Pa，未反應單體在脫揮槽al6的真空中 蒸發並輸送至回收精製塔9精製蒸餾，回收精製塔9塔頂溫度在48°C，塔內氣壓在8x l〇3Pa，回流比1/2，未反應單體在回收精製塔9內經真空蒸餾後輸送至冷凝器c20和冷 凝器d21冷凝，冷凝後輸送至貯罐b24貯存’ 經第一段脫揮精製的生成物用高黏度齒輪泵M9輸送至加熱器M5加熱至240°C， 再輸送至脫揮槽M7，脫揮槽M7內氣壓低於1.3xl〇3Pa，未反應單體在脫揮槽M7的真 空中蒸發並輸送至冷凝器e22冷凝，冷凝後輸送至貯罐b24貯存； ④ 拉絲造粒：將經第③步閃蒸脫揮精製的生成物用高黏度齒輪泵c4〇輸送至線上 攪拌器11，添加紫外線防止劑、潤滑劑 '離型劑並混合後輸送至過濾裝置12，去除粒 徑大於80μιη的雜物，再經模頭13擠出切粒，乾燥包裝。 本實施例成品每小時產出2485千克，回收單體及溶劑爲2450千克’少許雜物如抑 制劑及寡聚物等由蒸餾塔底排出。 成品呈水白澄清膨粒，其物性檢測如表3所示： 表3 試驗方法ASTM 條件 單位 物性 物理性質 比重 D792 1.19 全光透射率 D1003 3mm % 92.6 折射率 D542 1.49 熱性質 熱變形溫度 D648 °C 100 維卡軟化點 D1525 °c 114 熔融指數 D1238 230〇C/3.8kgs g/lOmin 4.5 機械!'生質 抗拉強度 D638 1A/5 Kg/cm2 720 抗撓強度 D790 Kg/cm2 1,100 13 200918562 彎曲彈性率 D790 Kg/cm2 34,000 洛式硬度 D785 M Scale 101 異物 目視 50g (mm2) ^0.05 實施例2 光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備同實施例1，實施光學級聚 甲基丙烯酸甲酯連續式溶液聚合工藝時，除如下所述條件外： 1. 第①步精製蒸餾時：溶劑占反應物總重量的5% ;預熱器5加熱至60°c ;進料精 製塔6內氣壓在4xl03Pa ; 2. 第②步聚合反應時：聚合反應溫度控制在130T：; 3. 第③步閃蒸脫揮時：加熱器加熱至220°C ;脫揮槽al6內氣壓在4xl03Pa ; 回收精製塔9塔頂溫度在30°C，塔內氣壓在4xl03Pa ;加熱器M5加熱至220°C ; 其他各項條件都同實施例1。 實施例3 ' 光學，級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備同實施例1，實施光學級聚 甲基丙烯酸甲酯連續式溶液聚合工藝時，除如下所述條件外： 1. 第①步精製蒸餾時•溶劑占反應物總重量的17% ;預熱器5加熱至95°C ;進料 精製塔6內氣壓在2.5xl04Pa ; 2. 第②步聚合反應時：聚合反應溫度控制在145°C ; 3. 第③步閃蒸脫揮時：加熱器al4加熱至270°C ;脫揮槽al6內氣壓在2.5xl04Pa ; 回收精製塔9塔頂溫度在55°C，塔內氣壓在2.5xl04Pa ;加熱器M5加熱至255°C ; 其他各項條件都同實施例1。 實施例4 光學,极聚甲基丙燒酸甲酯連續式溶液聚合工藝所用設備同實施例：[，實施光學級聚 甲基丙烯酸甲酯連續式溶液聚合工藝時，除如下所述條件外： 1·第①步精製蒸餾時：溶劑占反應物總重量的30% ;預熱器5加熱至80°C ;進料 精製塔6內氣壓在4.7xl04Pa; 2.翁②步聚合反應時：聚合反應溫度控制在160T：; 14 200918562 3_第③步閃蒸脫揮時：加熱器al4加熱至320°C ;脫揮槽al6內氣壓在4.7xl04Pa ; 回收精製塔(9)塔頂溫度在80°C，塔內氣壓在4.7xl04Pa ;加熱器M5加熱至260°C ; 其他各項條件都同實施例1〇 實施例5 ' 光學級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備同實施例1，實施光學級聚 甲基丙烯酸甲酯連續式溶液聚合工藝時，具體選用光學級聚甲基丙烯酸甲酯及苯乙烯共 聚物連續式溶液聚合工藝，除主單體選用甲基丙烯酸甲酯、共聚物選用苯乙烯外，其他 各項條件都同實施例1。 實施例6 光學，級聚甲基丙烯酸甲酯連續式溶液聚合工藝所用設備同實施例1，實施光學級聚 甲基丙烯酸甲酯連續式溶液聚合工藝時，具體選用光學級苯乙烯及丙烯腈共聚物連續式 溶液聚合工藝，各組份的選用物質和用量如表4所示，其他各項條件都同實施例1。 表4 組份 選用物質 用量(千克/小時） 主單體 苯乙烯 3000 表4(續) 組份 選用物質 用量(千克/小時） 共聚物 丙烯腈 1000 溶劑 乙苯 1000 引發劑 二叔戊基過氧化物 0.15 分子調節劑 十一院基硫醇 3.65 【圖式簡單說明】 第1圖 15 200918562 【主要元件符號說明】 表1 代號 部件名稱 代號 部件名稱 1 主原料儲槽 20 冷凝器c 2 共聚單體儲槽 21 冷凝器d 3 溶劑儲槽 22 冷凝器e 4 回收單體儲槽 23 貯罐a 5 預熱器 24 貯罐b 6 進料精製塔 25 栗a 7 再沸器 26 泵b 8 聚合反應槽 27 泵c 9 回收精製塔 28 泵d 10 添加劑配製槽 29 泵e 11 線上攪拌器 32 泵h 12 過濾裝置 33 泵i 13 模頭 34 栗j 14 加熱器a 35 控制閥a 15 加熱器b 36 控制閥b 16 脫揮槽a 37 控制閥c 17 脫揮槽b 38 高黏度齒輪泵a 18 冷凝器a 30 泵f 19 冷凝器b 31 杲g 表1(續) 代號 部件名稱 代號 部件名稱 39 萵黏度齒輪泵b 40 局黏度齒輪栗c 16200918562 ' VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention. IX. Description of the invention: [Technical field of the invention] The present invention relates to a method for preparing a polymer compound and a device used thereof Polymethyl methacrylate continuous solution polymerization process and equipment used. [Prior Art] Polymethyl methacrylate (English name Polymethyl Methacrylate, abbreviated as pMMA) is a rigid and transparent thermoplastic material with a wide range of applications. Its polymerization preparation methods include suspension method, emulsification method, bulk method and solution method. Among them, the finished product of the emulsification method is poor in transparency and expensive, and is not suitable for commercial production. The suspension preparation process is: adding an initiator to the MMA and the copolymer, polymerizing to a certain conversion rate, further adding a large amount of water and a suspending agent to further polymerize, and the PMMA is formed into a bead suspended in water, subjected to dehydration washing, drying and then extruding. Machine $_ 〇In the production process, 7JC and energy consumption are great, and because of the batch reaction, each step requires a lot of manual processing. For mass production, the economic benefits are not high, and it is not applicable because it contains ash. Advanced optical product applications. Legally. The monomer concentration is high, the gel is easily generated, and the reaction rate is fast, and the exothermic reaction of large-scale production is difficult to control. In the 1980s, PTI Corporation of the United States proposed a solution polymerization method to improve the aforementioned problems. U.S. Patent No. 4,728,701, issued on Mar. 1, 1988, discloses a method for the polymerization of a propionate; U.S. Patent No. 4,933,400, issued on June 12, 1990. A continuous solution polymerization method of methyl acrylate vinegar is disclosed, but these polymerization methods use a solvent ratio of up to 60% of the feed, the reaction rate is too slow, and the reactor volume is significantly increased, resulting in a high investment amount, and the process is also There are the following disadvantages: 1. The polymerization temperature is lower than 100 ° C, the use of the initiator, and the molecular adjustment of the dose is relatively increased, affecting the purity and recovery and purification problems. 2. The two-stage polymerization tank is used because the copolymerization rate ratio of ruthenium and its copolymer such as ruthenium or osmium is different, so that the copolymerization ratio of the first-stage reaction and the second-stage reaction-forming polymer may have a difference in migration. 3. The devolatilization process is poor. When the solid content in the polymerization process reaches 40% or more, the polymerization solution is preheated by the gear pump to the shell-and-tube heater, and the flow is from bottom to top, and the polymerization solution passes through the heating tube of the heater, and At the end, the outlet pressure is controlled by the control valve to maintain the liquid state in the tube. In this way, the heat transfer coefficient is low, the heating effect is not good, and the heater is bulky. The polymerization solution has a long residence time and is prone to oligomers and oligomers. Seriously affect quality. 200918562 In addition, commercially available methyl methacrylate is generally added with an inhibitor of more than 10 ppm, 働 6-tert-butyl-34-dimethylphenol (trade name Topanol A), which is optically transparent to the product. Light, turbidity and color have an effect, so removal of this inhibitor and debris is a necessary consideration. SUMMARY OF THE INVENTION In order to overcome the deficiencies of the prior art, improve the production efficiency and product quality of PMMA, and reduce the production energy consumption, the present invention discloses an optical grade polymethyl methacrylate continuous solution polymerization process and equipment used therefor, and the present invention The object is achieved by the following technical solutions: An apparatus for optical grade polymethyl methacrylate continuous solution polymerization process, which comprises a refinery distillation device, a poly-reaction device, a two-stage devolatilizer device and a wire drawing granulation unit in series Formed into: main raw material storage tank (1), comonomer storage tank (2), solvent storage tank (3), recovery monomer storage tank (4) 'preheater (5), feed refining tower ( 6), reboiler (7), polymerization reactor (8), recovery refining tower (9), additive preparation tank (1 〇), on-line stirrer (11), filtration device (12), die (13), heater ( 14), heat exchanger (15), devolatilization tank (16), devolatilization tank (17), condenser (18), (19), (20), (21), (22), storage tank ( 23), (24), pump (25), (26), (27), (28), (29), (30), (31), (32), (33), control valve (35), (36), (37) and high viscosity gear pumps (38), (39), (40). wherein 'the main raw material storage tank (1), the comonomer storage tank (2), the solvent storage tank (3) and the recovery monomer storage tank (4) are respectively pumped from the discharge ports at the respective bottoms ( 25), the pump (26), the pump (27) and the pump (28) and the delivery pipe are connected to the feed port of the preheater (5), and the discharge port of the preheater (5) is connected to the feed through the transfer pipe A feed port at the lower part of the refining tower (6), a reboiler installed below the feed port of the feed refining tower (6), and a discharge port No. 1 at the top of the feed refining tower (6) is connected by a delivery pipe to a condensation Feeder No. 1 of the feeder (18), the No. 2 discharge port at the bottom of the feed refining tower (6) is connected to the No. 2 discharge port in the middle of the tower through the pump (29) and the transfer pipe, and the storage tank (23) The No. 1 discharge port is connected to the No. 1 inlet above the inside of the feed refining tower (6) through a pump (30) and a transfer pipe, and a control valve (35) is installed before the transfer pipe enters the No. 1 inlet. The polymerization reaction tank ( 8) The feed port is connected through a conveying pipe and a conveying pipe between the pump (30) and the control valve (35), the polymerization reaction tank (8) is a single polymerization tank, and there is a stirring facility, and the storage tank (23) No. 2 outlet is connected to the cold through the pipeline The No. 2 discharge port of the vessel (18), the No. 3 discharge port of the storage tank (23) is a drain valve, and the No. 1 discharge port at the upper part of the polymerization reaction tank (8) is connected to the condenser (19) through a pipe. In the feed inlet, the condenser (19) is trapped in the loop of cold water, the discharge port of the condenser (19) and the discharge port of the condenser (18) are both passed through the transfer pipe and the condenser (20) and the condenser are connected. (21) The first one of the two conveying pipes is connected to the conveying pipe, and the connecting pipe connected to the outlet of the condenser (19) is equipped with a control valve (36). The gas conveying pipe is provided with a control valve (37). The No. 2 discharge port in the lower part of the polymerization reaction tank (8) is connected to the feed port of the heater (1.4) through a high-viscosity 200918562 degree gear pump (38) and a transfer pipe, and the devolatilizer tank (16) is installed in the heater (14). Underneath, and directly connected to the discharge port of the heater (14), the No. 1 discharge port above the devolatilization tank (16) is connected to the feed port of the recovery refining tower (9) through a transfer pipe, and the devolatilization tank (16) The second discharge port below is connected to the feed port of the heater (15) through a high-viscosity gear pump (39) and a transfer pipe, and the devolatilizer (17) is installed below the heater (15) and with the heater ( 15) Discharge Directly connected, the No. 1 discharge port above the devolatilization tank (Π) is connected to the inlet of the condenser (22) through the conveying pipe, and the No. 2 discharge port below the devolatilization tank (17) passes through the high viscosity gear pump ( 40) and the delivery pipe is connected to the feed port of the line agitator (11), the discharge port of the additive preparation tank (1〇) is passed through the conveying pipe and the connection devolatilization tank (Π) discharge port and the line agitator (11) The feed pipe between the feed ports is connected, and the feed port of the line agitator (11) is connected to the feed port of the filter device (12) through a transfer pipe, and the discharge port of the filter device (12) is connected to the feed pipe through the transfer pipe The No. 1 discharge port of the die (13), condenser (22) • is connected to the feed port of the storage tank (24) through a transfer pipe, and the outlet 2 of the condenser (22) is connected to the vacuum pump (32) and discharged. The No. 1 discharge port of the pipeline and the storage tank (24) is connected through the conveying pipe and the No. 2 conveying pipe in the two conveying pipes connecting the condenser (20) and the condenser (21), the storage tank (24) The No. 2 discharge port is connected to the No. 1 inlet above the inside of the recovery refining tower (9) through a pump (33) and a transfer pipe, and the No. 1 discharge port at the top of the recovery refining tower (9) is conveyed. The pipeline is connected to the inlet of the condenser (20), and the outlet No. 2 at the bottom of the recovery refining tower (9) is connected to the inlet No. 2 of the middle of the tower through the pump (34) and the conveying pipeline, and the condenser (21) The discharge port is connected with a vacuum pump (31) and a discharge pipe. The other inlet port of the recovery monomer storage tank (4) passes between the delivery pipe and the pump (33) and the discharge port No. 1 above the recovery refining tower (9). The conveying pipes are connected. An optical grade polymethyl methacrylate continuous solution polymerization process, which comprises a monomer, a copolymer, a stabilizer, a molecular weight adjustment, an initiator, a solvent, a refined distillation, a 2 polymerization reaction, a 3 flash devolatilization, and 4 Wire drawing granulation four-step operation is completed 'all reactions are completed in the apparatus for the optical grade polymethyl methacrylate continuous solution polymerization process according to claim 1 or 2, characterized in that: 1 refined distillation: from the main raw material Storage tank (1), comonomer storage tank (2), solvent storage tank (3), recovery monomer storage tank (the monomer, copolymer and solvent transported in the sentence are heated to 6〇 by preheater (3) °C~12〇. (:, then sent to the feed refining tower (6) refined distillation 'in the feed refining tower gas pressure in 4xl03Pa~4.7xl04Pa, remove the contained inhibitor and residual impurities; 2 polymerization: the first The reaction product after the first step of refining and distillation is sent to the polymerization reaction tank (8) for boiling polymerization, and the polymerization temperature is controlled at 130 ° C to 160 ° C; 3 flash devolatilization: devolatilization uses two stages of devolatilization, the first stage The devolatilizer includes: a heater (14), a detachment tank (16) and the recovery refining tower (9), the second stage devolatilizer includes: a heat exchanger (15) and a devolatilization tank (17) '200918562 'The second step reaction polymerization product is made of a high viscosity gear pump (38) The feed to the heater (14) is heated to 22〇t>c~ 260T: and then sent to the devolatilization tank (16), and the gas pressure in the devolatilization tank (16) is 4xl〇Jpa~4.7xl〇4pa 'not The reaction monomer is evaporated in a vacuum of the devolatilization tank (16) and sent to a recovery refining tower (9) to refine the distillation. The recovery tower (9) has a temperature of 30 at the top of the column. (: ~80t, the gas pressure in the column is 4x1. 4.7Xl〇4Pa, unreacted monomer is vacuum distilled in the @refinery tower (9) and sent to the condenser (20) and the condenser (21) for condensation, condensed and transported to the storage tank (24) for storage. The refined product is transported to the heater (15) with a high-viscosity gear pump (39) and heated to 220 ° C to 26 (TC, and then sent to the devolatilization tank (17). Ux10% 'unreacted monomer is evaporated in vacuum in devolatilization tank (17) and sent to condenser (22) for condensation, cold stomach storage; 4 wire granulation: the third step flash devolatilization purification The material is transported to the line with a high viscosity gear pump (40) The stirrer (11) is added with an ultraviolet preventive agent, a lubricant, and a release agent, and then mixed and sent to a filtering device (12) for filtration to remove impurities, and then extruded and diced by a die (13), and dried and packaged. The optical grade polymethyl methacrylate continuous solution polymerization process, the monomer used for the polymerization reaction is any one of methyl methacrylate and styrene, and the copolymer is methyl acrylate, ethyl acrylate, benzene. Any one of ethylene, acrylonitrile and malic anhydride; the solvent used for the polymerization is selected from toluene or ethylbenzene in an amount of 5% to 30% by weight of the total reactant; and in the third step, the granulation is removed by means of a device. The particle size of the debris is greater than 80 μm. According to the disclosed technical solution of the present invention, the comonomer and the recovered monomer are aggregated in a certain proportion and quantity from each storage tank and heated and fed into the feed refining tower for distillation and purification. The purpose of the distillation refining is to remove the monomer inhibitor. And residual impurities and moisture, while removing the oligomers and impurities of the recycled materials. ® is the first stomach # produced by optical grade. 'Distilled refined raw materials are mixed with a certain proportion of initiators, molecular regulators and other added by-products are stable at a certain rate " into the polymerization reaction tank. The polymerization tank has a pressure-bearing structure' jacket to control the exotherm of the polymerization reaction with a heat medium, vapor, or hot and cold water loop (REFLUX) to control the temperature of the polymerization reaction. In order to achieve optimum polymerization molecular structure and economic efficiency, the reaction temperature is preferably controlled at 130 to 160 °C. The polymerization tank has a good agitation mixing effect while utilizing agitation to avoid problems such as accumulation of polymer scale on the walls of the tank. In order to avoid the polymer from being generated in the top condenser and the tank wall, a proper proportion of solvent is added. The solvent is added in an amount of 5% to 3% by weight based on the total weight of the reactants, and the focus is on diluting the volatile organic vapor monomer concentration. The solvent condensate also has the function of brushing to avoid polymer formation. After the polymerization reaction, the proportion of solids in the total weight is more than 50%, and is pumped to the heater a to preheat to 22 (rc ~ 260.): The design and operating conditions of the heater are the requirements of the devolatilization process. The polymer solution of 50% solids has a ratio of solids to total weight of 98 to 99% after the first stage. The devolatilization tank (16) is vacuum controlled, and the pressure is about 200918562 at 4xl03Pa to 4.7xl04Pa, which is not involved. Reactive monomer and solvent shellfish devolatilization tank (16 vol. volatilization into a matching recovery tower (9). Use the necessary heating in the devolatilization process. This part of the recovered steam heat is converted to refined distillation, so The waste heat is greatly utilized to achieve the energy saving effect. The polymer in the devolatilization tank (16) is sent to the heater (15) and enters the devolatilization tank (17). The pressure in the devolatilization tank (17) is lower than 1.3x10 Pa, and the remaining is removed again. Residual monomer and solvent. High purity required to achieve optical grade. In the devolatilization tank, the polymer is melted and output by a high viscosity gear pump (40). An in-line stirrer can be installed in the pipeline (11) ) to facilitate the addition and mixing of additives such as UV inhibitors, lubricants, and release agents. After the addition, the polymer is filtered through the filtering device (12) to remove the impurities having a particle diameter of 80 μm or more, and then the pellets are pulled out by the die (13) in the form of noodles, dried, sieved, powdered, packaged, and stored. The disclosed technical solution is a continuous bulk polymerization method, and the whole process is mainly divided into production processes such as reaction polymerization, flash devolatilization and wire drawing granulation. Compared with the prior art, the following advantages are obtained: 1. High safety in ΜΜΑ The high viscosity of the polymer in the bulk polymerization, whether or not the comonomer 'polymer, reduces the fluidity of the growing polymer molecule and slows the chain termination rate. This phenomenon is called a gel phenomenon. It causes a sharp increase in the polymerization rate. D, at the same time, a large amount of heat of reaction and formation of ultra-high molecular polymer. The gel phenomenon causes a run away ' and the control of this reaction is very difficult. The disclosed technical solution combines the feed formulation and The process control successfully solves the above gel phenomenon. By reducing the rapid reaction exotherm, the reaction rate and the molecular weight of the product can be easily controlled. Safety. The addition of solvent to the reaction mixture makes it possible to use a volatile gas condenser to cool away the heat of reaction. This is an effective method for transferring heat compared to other forms of cooling, reducing the cost of the unit. Cooling can also remove harmful oxygen dissolved in the reactants, so the performance and color of the resulting product are improved. 2. Avoid gel accumulation, improve product physical properties and color. The technical solution disclosed in the present invention, its formulation and operating conditions The choice can ensure that there is no gradual accumulation of polymer in the container wall and the transfer line, which accumulation can cause operational accidents and harmful gelation of the end product. 3. Low energy consumption, environmental cleanliness, the technical solution disclosed in the present invention, Initiators, comonomers, and chain transfer agents are effectively used in the reaction system. The low molecular weight fraction is reduced during the dislocation process, and the high-efficiency devolatilization process is an important factor in product quality and uniformity. The use of raw materials to the final product is extremely high. Compared with the suspension method, the solution method reduces the consumption of raw materials, while participating in the reaction without water, reducing the energy consumption such as dehydration and drying, and reducing the sewage treatment, is a cleaner ring. #200918562 丁药i 〇4. Reaction system Multifunctionality The technical solution disclosed in the present invention has a reaction system with good flexibility and can adjust the polydispersity (molecular weight distribution) and comonomer ratio of the product, and can satisfy the processing of the product and other industrial products. Sex. The development of new niobium products can be made into products with a polydispersity of less than 2.2. Highly dispersible products can be obtained by simply changing the operating conditions of the raw material processing process. 5. Product weatherability Compared to the suspension process, the disclosed technical solution does not have a suspending agent or emulsifier, so the product produced is not affected by the addition. A typical product analysis indicates that no ash content is detected, and the suspension method will contain a ash content of 15 to 25 ppm' which reduces haze and improves weatherability of product processing. 6. Anhydrous Polymerization The disclosed technical solution minimizes the amount of wastewater treated because there is no water addition, and the only water that needs to be treated is brought in by the feed MMA monomer. This water can be automatically separated from the monomer during the polymerization process. 7. The system is completely enclosed The disclosed technical solution is a fully enclosed system with no exhaust emissions and no unpleasant gas that harms employees. 8. The product has no black spots. The enamel products produced by the technical solution disclosed by the present invention do not have dark spots, and the products produced by the suspension method generally have dark spots. 9. Recycling system environmental protection and energy saving The technical solution disclosed in the present invention has introduced a refining system which can utilize the steam superheat energy of the devolatilization process to save energy, which also reduces the size of the condenser and the amount of water. The embodiments of the present invention are described in detail with reference to the specific embodiments. The embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation procedures are given, but the scope of protection of the present invention is not limited thereto. The following examples. Embodiment 1 As shown in FIG. 1 , an apparatus for an optical grade polymethyl methacrylate continuous solution polymerization process is a combination of a refining 200918562 distillation apparatus, a polymerization reaction apparatus, a two-stage devolatilization apparatus, and a wire drawing granulator. , including: main raw material storage tank 1, comonomer storage tank 2, solvent storage tank 3, recovery monomer storage tank 4, preheater 5, feed refining tower 6, reboiler 7, polymerization reaction tank 8, recovery Refinement column 9, additive preparation tank 1 线上, on-line stirrer 11, filter unit 12, die 13, heater a14, heater M5, devolatilization tank a6, devolatilization tank bl7, condenser aal8 to condenser e22' Tanks a23, b24, pump a25 to pump j34, control valve a35 to control valve C37, and high viscosity gear pump a38 to high viscosity gear pump c40; wherein main material storage tank 1, comon monomer storage tank 2, solvent storage tank 3 And the recovery monomer storage tank 4 is connected to the feed port of the preheater 5 through the pump a25, the pump b26, the 'pump c27 and the pump d28 and the transfer pipe from the discharge ports at the respective bottoms, and the discharge of the preheater 5 The mouth is connected to the feed port at the bottom of the feed refining tower through a conveying pipe, and the feed is refined «Tower 6 A reboiler 7 is installed below the feed port, and the No. 1 discharge port at the top of the feed refining tower 6 is connected to the No. 1 feed port of the condenser a8 through the transfer pipe to the No. 2 discharge port at the bottom of the feed refining tower 6. Connected to the No. 2 discharge port in the middle of the tower by the pump e29 and the transfer pipe, the No. 1 discharge port of the tank a23 is connected to the No. 1 discharge □ above the inside of the feed refining tower 6 through the pump β〇 and the transfer pipe. A control valve 〇 35 is installed before the delivery pipe enters the No. 1 discharge port, and the feed port of the polymerization reaction tank 8 communicates with the transfer pipe between the transfer pipe and the pump f30 and the control valve a35, and the polymerization reaction tank 8 is a single polymerization tank. There is a stirrer for continuously mixing the high-viscosity fluid, and the No. 2 discharge port of the storage tank a23 is connected to the No. 2 feed port of the condenser a8 through the conveying pipe, and the No. 3 discharge port of the storage tank a23 is a safety release valve. The No. 1 discharge port in the upper part of the polymerization reaction tank 8 is connected to the feed port of the condenser bl9 through a pipe, and the condenser M9 is jacketed with hot water, steam or heat medium, the discharge port of the condenser a8 and the condenser M9. The discharge port passes through the conveying pipe and connects the condenser c20 and the condenser d21 The No. 1 conveying pipe of the two conveying pipes is connected, and the connecting fk is connected with a control valve b36 on the conveying pipe of the discharge port of the condenser M9, and the control pipe C37 is installed on the gas conveying pipe and the condenser M9 and the control valve are installed. The conveying pipe between b36 is connected, and the outlet No. 2 of the lower part of the polymerization reaction tank 8 is connected to the feeding port of the heater aal4 through the high-viscosity gear pump a38 and the conveying pipe, and the detaching groove a6 is installed under the heater aal4 And directly connected to the discharge port of the heater al4, the No. 1 discharge port above the devolatilization tank al6 is connected to the feed port of the recovery refining tower 9 through the conveying pipe, and the No. 2 discharge port below the detachment groove al6 passes through the high The viscosity gear pump b39 and the delivery pipe are connected to the feed port of the heater M5, and the devolatilization tank M7 is installed below the heater M5 and directly connected to the discharge port of the heater bl5, and the first discharge above the vortex groove M7 The port is connected to the male port of the condenser e through a conveying pipe, and the second discharging port below the devolatilizing groove bl7 is connected to the feeding port of the line chander 11 through the high-viscosity gear pump C40 and the conveying pipe, and the additive preparing tank 10 Outlet through the pipeline The discharge port connecting the devolatilization tank M7 is connected to the conveying pipe between the inlets of the scrambler 11 , and the inlet of the line agitator 11 is connected to the inlet of the filtering device 12 through the delivery line 11 200918562. The discharge port of the filtering device 12 is connected to the die 13 through a conveying pipe. The No. 1 discharge port of the condenser e22 is connected to the inlet of the storage tank b24 through a conveying pipe, and the pump No. 2 of the condenser e22 is connected with a pump. H32 and the discharge pipe 'the discharge port No. 1 of the storage tank b24 is connected through the conveying pipe and the No. 2 conveying pipe in the two conveying pipes connecting the condenser C20 and the condenser d21, and the discharging No. 2 of the storage tank b24 The port is connected to the No. 1 discharge port above the inside of the recovery refining tower 9 through the pump i33 and the delivery pipe. The No. 1 discharge port at the top of the recovery refining tower 9 is connected to the feed port of the condenser c20 through a transfer pipe, and the bottom of the refining tower 9 is recovered. The No. 2 discharge port is connected to the discharge port of the condenser No. 2 of the middle of the tower through the pump j34 and the transfer pipe. The discharge port of the condenser d21 is connected with the chestnut g31 and the discharge pipe, and the other one of the monomer storage tanks 4 is recovered. The discharge port passes through the conveying pipe and the pump i33 and the interior of the recovery refining tower 9 The conveying pipe between the No. 1 discharge ports of the square is connected. When the optical grade polymethyl methacrylate methyl vinegar continuous solution polymerization process is carried out, the monomer, the copolymer, the stabilizer, the molecular weight regulator 'initiator, the solvent are refined by distillation, the polymerization reaction, the 3 flash devolatilization and the 4 Wire drawing granulation is completed in four steps. The selected materials and dosage of each component are shown in Table 2: Table 2 Component selection substance dosage (kg/hr) Main monomer methyl methacrylate 4295 copolymer Methyl acrylate 225 Table 2 (continued) Component Selection Substance (kg/hr) Solvent Toluene 500 Initiator Di-tert-amyl peroxide 0.85 Molecular Modulator Dodecyl Mercaptan 7.2 All reactions are in optical grade poly The equipment used in the continuous solution polymerization process of methyl acrylate completes: 1 Refined distillation: monomer transported from the main raw material storage tank comonomer storage tank 2, solvent storage tank 3, recovery monomer storage tank 4, copolymerization The substance, the stabilizer, the molecular weight regulator and the initiator are first heated to 90 ° C by the preheater 5, and then sent to the refined refining tower for purification distillation, and the pressure in the feed refining tower 6 is 8×10 3 Pa, and the contained inhibitor is removed. The residue debris; 12 200918562 ② Polymerization: After the first step ① was purified by distillation boiling reactant delivery to the polymerization reaction vessel type polymerization reactor 8 occurs, the polymerization temperature was controlled at 155. (:, the pressure is 〇.35MPa; 3 flash devolatilization: devolatilization uses two stages of devolatilization, the first stage devolatilizer includes • heater al4, devolatilization tank al6 and recovery refining tower 9, the second stage devolatilization The apparatus comprises: a heater M5 and a devolatilization tank M7, and the product of the second step reaction polymerization is sent to the heater aM by a high viscosity gear pump a38 to be heated to 230 ° C, and then sent to the devolatilization tank a6, and the devolatilization tank a16 The internal pressure is 8xl03Pa, the unreacted monomer is evaporated in the vacuum of the devolatilization tank a6 and sent to the recovery refining tower 9 for refining distillation. The temperature of the top of the refining tower 9 is recovered at 48 ° C, and the gas pressure in the column is 8 x l 〇 3 Pa. 1/2, the unreacted monomer is vacuum distilled in the recovery refining column 9, and then sent to the condenser c20 and the condenser d21 for condensation, and then condensed and sent to the storage tank b24 for storage. The viscosity gear pump M9 is sent to the heater M5 to be heated to 240 ° C, and then sent to the devolatilization tank M7, the pressure in the devolatilization tank M7 is lower than 1.3xl 〇 3Pa, and the unreacted monomer is evaporated in the vacuum of the devolatilization tank M7. Conveyed to condenser e22 for condensation, condensed and transported to storage tank b24 for storage; 4 wire granulation: will be the third The product obtained by the flash devolatilization is transported to the in-line agitator 11 by a high-viscosity gear pump c4, and the ultraviolet ray preventing agent and the lubricant 'release agent are added and mixed, and then sent to the filtering device 12 to remove the foreign matter having a particle diameter larger than 80 μm. Then, the pellets are extruded through the die 13 and dried and packaged. The finished product of the present embodiment produces 2485 kg per hour, and the recovered monomer and solvent are 2450 kg. 'A few impurities such as inhibitors and oligomers are discharged from the bottom of the distillation column. The finished product is water white clarified expanded grain, and its physical property is tested as shown in Table 3: Table 3 Test method ASTM Condition unit physical property Physical property specific gravity D792 1.19 Total light transmittance D1003 3mm % 92.6 Refractive index D542 1.49 Thermal property heat distortion temperature D648 ° C 100 Vicat softening point D1525 °c 114 Melt index D1238 230〇C/3.8kgs g/lOmin 4.5 Machinery! 'Biomass tensile strength D638 1A/5 Kg/cm2 720 Flexural strength D790 Kg/cm2 1,100 13 200918562 Bending Elasticity D790 Kg/cm2 34,000 Rockwell hardness D785 M Scale 101 Foreign matter visual 50g (mm2) ^0.05 Example 2 Optical grade polymethyl methacrylate continuous solution polymerization process equipment used Example 1, when the optical grade polymethyl methacrylate continuous solution polymerization process is carried out, except for the following conditions: 1. In the first step of refining distillation: the solvent accounts for 5% of the total weight of the reactant; the preheater 5 Heating to 60 ° C; the pressure in the feed refining column 6 is 4xl03Pa; 2. In the second step of polymerization: the polymerization temperature is controlled at 130T:; 3. The third step is flashing devolatilization: the heater is heated to 220° C; the gas pressure in the devolatilization tank al6 is 4xl03Pa; the temperature of the top of the recovery refining tower 9 is 30 ° C, the gas pressure in the column is 4x1032Pa; the heater M5 is heated to 220 ° C; other conditions are the same as in the first embodiment. Example 3 'Optical, grade polymethyl methacrylate continuous solution polymerization process equipment used in the same manner as in Example 1, the optical grade polymethyl methacrylate continuous solution polymerization process, except for the following conditions: 1. In the first step of refining distillation, the solvent accounts for 17% of the total weight of the reactants; the preheater 5 is heated to 95 ° C; the pressure in the feed refining column 6 is 2.5 x 10 4 Pa; 2. The second step of polymerization: the polymerization temperature Controlled at 145 ° C; 3. The third step of flash devolatilization: heater al4 heated to 270 ° C; degassing tank al6 gas pressure at 2.5xl04Pa; recovery refining tower 9 tower top temperature at 55 ° C, inside the tower The gas pressure was 2.5 x 10 4 Pa; the heater M5 was heated to 255 ° C; the other conditions were the same as in Example 1. Example 4 Optical, very polymethyl methacrylate methyl ester continuous solution polymerization process equipment used in the same example: [, when the optical grade polymethyl methacrylate continuous solution polymerization process is carried out, except for the following conditions: 1. In the first step of refining distillation: solvent accounts for 30% of the total weight of the reactants; preheater 5 is heated to 80 ° C; the pressure in the feed refining column 6 is 4.7 x 10 4 Pa; 2. Weng 2 step polymerization: polymerization The reaction temperature is controlled at 160T:; 14 200918562 3_Step 3 flash devolatilization: heater al4 is heated to 320 ° C; degassing tank al6 gas pressure is 4.7xl04Pa; recovery refining tower (9) tower top temperature is 80 °C, the gas pressure in the column is 4.7xl04Pa; the heater M5 is heated to 260 °C; other conditions are the same as those used in the embodiment 1" optical grade polymethyl methacrylate continuous solution polymerization process Example 1, when the optical grade polymethyl methacrylate continuous solution polymerization process is implemented, the optical grade polymethyl methacrylate and styrene copolymer continuous solution polymerization process is selected, and the main monomer is selected from methyl methacrylate. The copolymer is made of styrene and other strips. The parts are the same as in the first embodiment. Example 6 Optical, grade polymethyl methacrylate continuous solution polymerization process equipment used in the same manner as in Example 1, the optical grade polymethyl methacrylate continuous solution polymerization process, specifically selected optical grade styrene and acrylonitrile copolymerization The continuous solution polymerization process, the selected materials and amounts of each component are shown in Table 4, and other conditions are the same as in the first embodiment. Table 4 Component Selection Substance (kg/hr) Main Monomer Styrene 3000 Table 4 (Continued) Component Selection Substance (kg/hr) Copolymer Acrylonitrile 1000 Solvent Ethylbenzene 1000 Initiator Di-tert-amyl Peroxidation Substance 0.15 Molecular Modulator 11-City Thiol 3.65 [Simple Description] Figure 1 200918562 [Main Component Symbol Description] Table 1 Code Part Name Code Part Name 1 Main Material Storage Tank 20 Condenser c 2 Comonomer Storage tank 21 condenser d 3 solvent storage tank 22 condenser e 4 recovery monomer storage tank 23 storage tank a 5 preheater 24 storage tank b 6 feed refining tower 25 chestnut a 7 reboiler 26 pump b 8 polymerization Tank 27 pump c 9 recovery refining tower 28 pump d 10 additive preparation tank 29 pump e 11 line agitator 32 pump h 12 filter unit 33 pump i 13 die 34 chestnut j 14 heater a 35 control valve a 15 heater b 36 Control valve b 16 devolatilization tank a 37 control valve c 17 devolatilization tank b 38 high viscosity gear pump a 18 condenser a 30 pump f 19 condenser b 31 杲g Table 1 (continued) Code part name code part name 39 Viscous tooth Board viscosity pump gear Li b 40 c 16