201202268l 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種可實現高單體轉化率以及生產性 的曱基丙烯酸酯聚合物的製造方法。 【先前技術】 曱基丙烯酸酯樹脂的工業生產方法中有藉由懸浮聚合 的方法及藉由塊狀聚合的方法。塊狀聚合法中，已知可不 使用懸浮聚合法中所使用的分散劑等添加劑，而製造透明 性優異的樹脂。專利文獻1及專利文獻2揭示有如下丙烯 酸酯樹脂的製造方法：於丙烯酸酯樹脂的製造中，在完全 混合型反應器内進行聚合，接著在塞流型反應器等管型反 應器内進行聚合，藉此取得生產性與物性的平衡。 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開2000-26507號公報 [專利文獻2]日本專利特開2003-2912號公報 專利文獻1揭示有如下丙烯酸酯樹脂的製造方法：於 丙烯酸酯樹脂的製造中，藉由繼槽型反應器之後使用管型 反應器，而取得生產性與物性的平衡。該文獻中記載有以 極限聚合率72%為最高值的實例，但並無關於進一步提高 聚合率的方法的記載。 ° 專利文獻2中有關於利用平衡聚合率來停止聚合的記 載，由聚合物的最終溫度來決定極限聚合率。該文獻中雖 記載有以極限聚合率68%為最高值的實例，但認為無法達 4 201202268 成超過該最兩值的極限聚合率。另外，關於決定平衡聚合 率的因素完全未進行說明。 【發明内容】 本，明的目的在於触一種在甲基丙烯酸醋單體的塊 狀聚合等中可實現高單體轉化率（極限聚合率）以及生產 性的甲基丙烯酸酯聚合物的製造方法。 *右依據基於平衡聚合率的觀點，則認為即便使添加於 管型反應H巾的起始劑量增加’亦無法提高聚合物的極限 ，σ率:但是，本發明者等人進行積極研究，結果獲知， 藉由在管型反應H巾的聚合_添域定量的起始劑，可提 高單體轉化率。另外獲知，藉由使作為甲基丙烯酸醋聚合 物，共聚合成分來使用的丙烯酸甲S旨的添加量增加，則即 ，疋與先m同量的起始劑使用量，亦可提高單體轉化率。 :::::現’本發明者等人發現，藉由在完全混合型反 Γ二s後’將該完全混合型反應器的下游的第二聚合 声坰棼Π:起始劑濃度以及(曱基)丙烯酸烷基酯的濃 度調整為規疋_’可提高單體轉化率，從而完成本發明。 =本發明是如下的甲基丙烯酸醋聚合物的製造方法， 其依序進行以下步驟： 於甲將甲基_酸曱01單獨或者包含曱基丙烯 “I至二sl以外的（曱基)丙稀酸燒基醋的單 合起始劑進行聚合，獲得第-_自由“ 步驟（b)，向配置於完全混合型反應器（八）的下游 201202268 的反應器⑻中供給第-衆料及第二自由絲合起始劑， 進行聚合，獲得第二漿料；以及 步驟（C)，將第二漿料去揮發；並且 上，曱基丙烯酸酯聚合物的製造方法的特徵在於：當 將上述單體中的曱基丙烯酸甲酯以外的（曱基)丙烯酸烷基 醋的含量設為x[wt%]，且將上述反應器（B)中的每單位 時間的第二自由基聚合起始劑供給量相對於每單位時間的 第一漿料供給量的重量比設為外卯㈣時，\與7滿足以下 式子： 8.5x+l23gyg-2.6x+45。 [發明的效果] 依據本發明，可提供一種即便是曱基丙烯酸酯單體的 塊狀聚合等，亦可實現高單體轉化率以及生產性的甲基丙 烯酸酯聚合物的製造方法。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 【實施方式】 本發明中，將曱基丙烯酸酯單體進行聚合來製造曱基 丙烯酸酯聚合物。所謂「曱基丙烯酸酯聚合物」，是指甲基 丙烯酸甲酯的均聚物或者甲基丙烯酸曱酯與曱基丙烯酸曱 酯以外的（甲基)丙烯酸烷基酯等共聚合成分（單體）的共 6 201202268 聚物。另外，所謂「（曱基)丙烯酸酯」，是指丙烯酸酯或者 甲基丙婦酸醋。 聚合方法例如可列舉塊狀聚合法、懸浮聚合法、溶液 聚合法。尤其就單體轉化率以及生產性的方面而言，較佳 為塊狀聚合法。該聚合方法可為連續式，亦可為分批式。 作為共聚合成分的甲基丙烯酸曱醋以外的（曱基)丙稀 酸烷基酯的具體例可列舉：丙烯酸甲酯（methyl acrylate)、 (曱基)丙稀酸乙S旨（ethyl (meth)acrylate )、（曱基)丙烤酸正 丙酯（n-propyl (meth)aCrylate )、（曱基）丙烯酸正丁酯 (n-butyl (meth)acrylate )、（曱基）丙烯酸異丁酯（i_butyl (meth)aCrylate )、（曱基）丙烯酸第三丁酯（tert_butyl (meth)aCrylate )、（曱基）丙烯酸第二丁酯（secbutyl (meth)aCrylate )、（曱基）丙烯酸正戊酯（n pentyl (meth)acrylate )、（甲基）丙烯酸正辛酯（n_〇ctyl (meth)aCrylate )、（曱基）丙烯酸月桂酯（lauryl (meth)acrylate )、（甲基）丙烯酸硬脂酯（steafyl (meth)acrylate )、（曱基）丙烯酸十三烷基酯（tridecyl (meth)acrylate )、（甲基）丙烯酸 2-乙基己酯（2-ethylhexyl (meth)acrylate )、（曱基）丙烯酸環己醋（cyd〇hexyl (meth)acrylate)。其中，較佳為丙烯酸曱酯、丙烯酸乙醋、 丙烯酸丁酯。作為共聚合成分的（曱基)丙烯酸烷基酯可僅 使用1種，亦可併用2種以上。 進而，亦可併用（曱基)丙烯酸烷基酯以外的單體作為 共聚合成分。此種單體的具體例可列舉：曱基丙烯酸 201202268 JO JJJlf (methacrylic acid)、丙稀酸（acrylic acid)、丁稀酸（crotonic acid )、乙稀基苯甲酸（vinyl benzoic acid )、富馬酸（fumaric acid)、衣康酸（itaconic acid)、馬來酸（maleic acid)、擰 康酸（citraconicacid)等一元酸或二元酸乙稀基單體；馬 來酸酐（maleic anhydride)等二元酸酐乙烯基單體；（曱基) 丙浠酸 2-經基乙酿（2-hydroxyethyl (meth)acrylate )、（曱基) 丙烯酸2-羥基丙酯、（曱基)丙烯酸3_羥基丙酯、（曱基)丙 烯酸2-羥基丁酯、（曱基)丙烯酸4-羥基丁酯、（曱基）丙烯 酸6-羥基己酯等具有羥基烷基的（曱基)丙烯酸酯；對（曱基) 丙烯酸2-經基乙醋的β-丁内酯（β-butyrolactone)開環加 成物、對（甲基）丙烯酸2-羥基乙酯的ε-己内酯 (ε-caprolactone)開環加成物、對（曱基）丙烯酸的環氧乙 烷（ethylene oxide)的開環加成物、對（曱基)丙烯酸的環 氧丙烧（propylene oxide)的開環加成物、（曱基)丙烯酸2-羥基乙酯或者（曱基)丙烯酸2-羥基丙酯的二聚物或三聚物 等末端具有羥基的（曱基）丙烯酸酯；4-羥基丁基乙烯基醚 (4-hydroxybutyl vinyl ether)、對羥基苯乙烯（p-hydroxy styrene)等其他含羥基的乙烯基單體；（甲基)丙烯酸苯酯 (phenyl (meth)acrylate )、（曱基）丙烯酸苄酯（benzyl (meth)acrylate )、（曱基）丙稀酸異冰片醋（is〇b〇rnyl (meth)acrylate )、苯乙烯；鄰甲基苯乙烯（〇_methyi styrene )、間甲基苯乙烯（m-methyl styrene )、對曱基苯乙 稀（p-methyl styrene)、α-曱基苯乙烯（α-methyl styrene)、 對乙基苯乙烯（p-ethyl styrene )、2,4-二曱基苯乙稀 8 201202268 (2,4-dimethyl styrene )、對正丁基苯乙稀（p-n-butyl styrene)、對第三丁基苯乙烯（p-tert-butyl styrene)等苯乙 稀系單體；丙烯腈（acrylonitrile )、曱基丙烯腈 (methacrylonitrile)、乙酸乙烯酯（vinyl acetate)、（曱基） 丙烯酸縮水甘油醋（glycidyl (meth)acrylate )、（曱基)丙稀 酸曱基縮水甘油 S旨（methylglycidyl (meth)acrylate )、烯丙 基縮水甘油基醚（allylglycidyl ether)等含環氧基的乙烯基 早體，（曱基）丙稀酸二曱基胺基乙S旨（dimethylaminoethyl (meth)acrylate )、（甲基）丙烯酸二乙基胺基乙醋 (diethylaminoethyl (meth)acrylate )、N-甲氧基曱基丙烯醯 胺（N-meliioxymethyl acrylamide)、N_曱氧基曱基曱基丙 缔酿胺（N-methoxymethyl methacrylamide)、N-乙氧基甲 基丙稀醯胺（N-ethoxymethyl acrylamide )、N-丙氧基曱基 丙烯酿胺（N-propoxymethyl acrylamide)、N-丁氧基曱基丙 稀醯胺（N-butoxymethyl acrylamide);(甲基）丙埽酸 2_經 基乙酯、（甲基)丙烯酸2·羥基丙酯、（曱基)丙烯酸4_經基 丁酯等具有羥基烷基的（曱基)丙烯酸酯。 用於聚合的單體中，曱基丙烯酸甲酯以外的（曱基)丙 烯酸烷基酯的量較佳為0.5重量百分比（wt%)〜2〇 wt〇/o。 另外’於併用（曱基)丙烯酸烷基酯以外的單體作為共聚合 成为的情況’ 5玄（曱基）丙婦酸烧基醋以外的單體的量較佳 為20 wt%以下。進而’用於聚合的單體較佳為包含8〇 wt% 〜99_5 wt%的曱基丙烯酸甲酯、及0.5 wt〇/0〜2〇 wt%的甲 基丙嫜酸曱醋以外的（曱基)丙烯酸烧基酯。若（甲基)丙稀酸 201202268 烧基醋的含量為0.5 wt%以上’則所得的甲基兩婦酸 合物的熱穩定性變得良好，成形時樹脂的熱分解難以^進 行，成形品中的氣泡的產生等外觀不良消失。另外j若 基)丙烯酸烷基酯的含量為20 wt%以下，則所得甲^ 酸酯聚合物的耐熱性變得良好，該成形品並無由熱 變形，可良好地用於一般的用途。 [步驟（a)] 本發明中的步驟（a)是將上述單體供給至完全混合型 反應器（A)中，利用第一自由基聚合起始劑進行聚人而 獲得第一漿料的步驟。 σ 第一自由基聚合起始劑只要在步驟（a)中的反應系統 的溫度下分解產生自由基即可。 上述第一自由基聚合起始劑的具體例可列舉：過氧化 -3,5,5-二曱基己酸第三丁酯（tert-butyl peroxy-3,5,5-trimethylhexanate )、過氧化月桂酸第三丁酯 (tert-butyl peroxylaurate)、過氧化異丙基單碳酸第三丁西旨 (tert-butyl peroxyisopropyl monocarbonate)、過氧化異丙 基單碳酸第三己酯（tert-hexyl peroxyisopropyl monocarbonate )、過氧化乙酸第三丁 g 旨（tert-butyl peroxyacetate)、1，1-雙（第三丁基過氧化)3,3,5-三曱基環己 烧（l,l-bis(tert-butylperoxy)3,3,5-trimethylcyclohexane)、 U-雙（第三丁基過氧化）環己烷 (1，1 -bis(tert-butylperoxy)cyclohexane )、過氧化 2-乙基己 酸第三丁酯（tert-butyl peroxy 2-ethylhexanate )、過氧化異 201202268 丁酸第三丁 g旨（tert-butyl peroxyisobutyrate )、過氧化 2_ 乙 基己酸第三己基-己醋 （tert-hexyl-hexyl peroxy 2-ethylhexanate )、二第三丁基過氧化物（di-tert-butyl peroxide )、2,5-二曱基-2,5-雙（第三丁基過氧化）己烷 (2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane)等有機過 氧化物；2-(胺曱醯基偶敗）-異丁腈（2-(carbamoyl azo)-isobutyronitrile )、1，Γ-偶氮雙（1-環己烷甲腈） (1，1'42〇13丨3(1-〇3^1〇116\&116 0&1：1)011办丨16))、2,2’-偶氮雙異丁 腈（2,2'-azobisisobutyronitrile)、2,2’-偶氮雙(2-曱基丁腈） (2,2’-azobis(2-methylbutyronitrile))、2,2’-偶氮雙異 丁酸二 曱酯（dimethyl 2,2’-azobisisobutyrate)、2,2’-偶氮雙(2,4,4-三曱基戊烧）（2,2’-azobis(2,4,4-trimethylpentane))、2,2，-偶 氮雙(2-曱基丙烧）（2,2’-azobis(2-methylpropane))等偶氮化 合物；過硫酸鉀等過硫酸鹽；氧化還原（redox)系聚合起 始劑。第一自由基聚合起始劑可僅使用1種，亦可併用2 種以上。 自由基聚合起始劑較佳為相對於所使用的溫度的半衰 期為10秒以上3 0分鐘以下的起始劑。若半衰期適度較長， 則自由基聚合起始劑在聚合系統内均勻擴散後分解，容易 熱分解的养聚物的產生得到抑制。另外，若半衰期適度較 短，則於緊急情況運轉停止時’難以產生反應液的黏度變 高所造成的再啟動困難之類的問題。 第一自由基聚合起始劑的使用量只要根據步驟（a)中 的反應系統的聚合溫度、反應物的平均滯留時間、作為目 201202268 標的單體轉化率等諸多條件來適當決定即可。尤其就獲得 末端雙鍵量少的耐熱分解性優異的甲基丙烯酸酯聚合物的 方面而言’第一自由基聚合起始劑的使用量較佳為相對於 單體1莫耳為5.〇xl〇-5莫耳以下，另外，就工業生產性的 方面而言，較佳為5.〇xlCT6莫耳以上。 步驟（a)的聚合時亦可使用鏈轉移劑^特佳為使用硫 醇（mercaptan)化合物。硫醇化合物的具體例可列舉：正 丁基硫醇、異丁基硫醇、正辛基硫醇、正十二烧基硫醇、 第二丁基硫醇、第二-十二烷基硫醇、第三丁基硫醇等具有 炫基或者經取代的燒基的一級、二級或三級硫醇；苯基硫 醇、甲硫酚（thiocresol )、4-第三丁基甲硫紛 (4-tert-butyl-〇-thi〇Cres〇l)等芳香族硫醇；硫代乙醇酸 (thioglycolic acid )及其酯；乙二硫醇（ethylene thi〇giyc〇1) 等碳數3〜18的硫醇。其中，較佳為第三丁基硫醇、正丁 基硫醇、正辛基硫醇、正十二烷基硫醇。鏈轉移劑可僅使 用1種’亦可併用2種以上。 就保持製品強度且獲得可進行成形加工的適度聚合度 (通常作為成形材料秘卫業上使㈣範目是最終去除揮 發成分後的聚合物的重量平均分子量為7萬〜15萬），並 且製造雜分解性優異的？基_㈣聚合物的方面而 言，鍵轉移劑的使用量較佳為相對於單體100莫耳百分比 (mol/0)為〇.〇1则伙叫m〇1%，更佳為〇 〇5福％〜〇 5 mol% 〇 於以溶液聚合進行步驟（a)的情況，使用惰性溶劑。 12 201202268 °玄丨3性溶劑的具體例可列舉：曱醇、乙醇、甲笨、二曱笨、 丙酮曱基異丁基酮、乙笨、曱基乙基酮、乙酸丁酯。其 中’較佳為曱醇、曱苯、乙苯、乙酸丁醋。惰性溶劑可僅 使用1種，亦可併用2種以上。 〇惰性溶劑的使用量較佳為在反應液組成物中小於5201202268l VI. Description of the Invention: [Technical Field] The present invention relates to a method for producing a mercaptoacrylate polymer which can achieve high monomer conversion rate and productivity. [Prior Art] Among the industrial production methods of mercapto acrylate resins, there are a method of suspension polymerization and a method of bulk polymerization. In the bulk polymerization method, it is known that a resin having excellent transparency can be produced without using an additive such as a dispersant used in the suspension polymerization method. Patent Document 1 and Patent Document 2 disclose a method for producing an acrylate resin in which polymerization is carried out in a completely mixed reactor in the production of an acrylate resin, followed by polymerization in a tubular reactor such as a plug flow reactor. In order to achieve a balance between productivity and physical properties. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-26507 [Patent Document 2] Japanese Laid-Open Patent Publication No. 2003-2912 discloses a method for producing an acrylate resin as follows: In the production of the acrylate resin, a balance between productivity and physical properties is obtained by using a tubular reactor after the tank type reactor. In this document, an example in which the ultimate polymerization ratio of 72% is the highest value is described, but there is no description about a method for further increasing the polymerization rate. ° Patent Document 2 relates to a record in which polymerization is stopped by an equilibrium polymerization ratio, and the ultimate polymerization rate is determined from the final temperature of the polymer. Although an example in which the ultimate polymerization ratio of 68% is the highest value is described in this document, it is considered that it is impossible to reach the limit polymerization ratio exceeding the maximum value of 4 201202268. In addition, the factors determining the equilibrium polymerization rate are not explained at all. SUMMARY OF THE INVENTION The purpose of the present invention is to produce a methacrylate polymer capable of achieving high monomer conversion (limit polymerization ratio) and productivity in bulk polymerization of methacrylic acid acrylate monomer and the like. . * The right is based on the viewpoint of the equilibrium polymerization rate, and it is considered that even if the initial dose added to the tubular reaction H towel is increased, the limit of the polymer cannot be increased, and the sigma ratio: However, the inventors of the present invention conducted active research, and as a result, It is known that the monomer conversion can be increased by quantifying the amount of the initiator in the polymerization of the tubular type H towel. Further, it has been found that by adding the amount of the acrylic acid to be used as the methacrylic acid vine polymer and the copolymerization component, the amount of the initiator used in the same amount as the first m can also increase the monomer. Conversion rates. ::::: Now, the inventors have found that by using the second mixed sonar downstream of the fully mixed reactor after the fully mixed type ruthenium s: the initiator concentration and The concentration of the alkyl acrylate alkyl acrylate is adjusted to increase the monomer conversion rate, thereby completing the present invention. The present invention is a method for producing a methacrylic acid vine polymer, which is sequentially subjected to the following steps: in which methyl ketone 01 is used alone or contains mercapto propylene "I to two sl (methane) The mono-initiator of dilute acid-based vinegar is polymerized to obtain the first--free "step (b), and the first-party and the first-stage material are supplied to the reactor (8) disposed downstream of 201202268 of the fully-mixed reactor (VIII). a second free-knit starter, which is polymerized to obtain a second slurry; and a step (C) to de-evaporate the second slurry; and the method for producing a mercaptoacrylate polymer is characterized in that The content of (mercapto)acrylic acid alkyl vinegar other than methyl methacrylate in the monomer is set to x [wt%], and the second radical polymerization initiation per unit time in the above reactor (B) is started. When the weight ratio of the supply amount of the agent to the first slurry supply amount per unit time is set to be external (four), \ and 7 satisfy the following formula: 8.5x + l23gyg - 2.6x + 45. [Effects of the Invention] According to the present invention, it is possible to provide a method for producing a methacrylate polymer which can achieve high monomer conversion rate and productivity even in the case of bulk polymerization of a mercapto acrylate monomer. The above and other objects, features and advantages of the present invention will become more <RTIgt; [Embodiment] In the present invention, a mercaptoacrylate monomer is polymerized to produce a mercaptoacrylate polymer. The term "mercapto acrylate polymer" means a homopolymer of methyl methacrylate or a copolymerization component such as an alkyl (meth) acrylate other than decyl methacrylate and decyl methacrylate. ) A total of 6 201202268 polymer. Further, the term "(fluorenyl) acrylate" means acrylate or methyl acetoacetate. Examples of the polymerization method include a bulk polymerization method, a suspension polymerization method, and a solution polymerization method. Particularly, in terms of monomer conversion rate and productivity, a bulk polymerization method is preferred. The polymerization method can be continuous or batchwise. Specific examples of the (mercapto)acrylic acid alkyl ester other than the methacrylic acid vinegar as a copolymerization component include methyl acrylate and (meth)acrylic acid. Acrylate, n-propyl (meth) a Crylate, n-butyl (meth)acrylate, isobutyl (meth) acrylate (i_butyl (meth) a Crylate ), tert-butyl (meth) a Crylate, secbutyl (meth) a Crylate, n-pentyl acrylate (n pentyl (meth)acrylate ), n-octyl (meth) a Crylate, lauryl (meth)acrylate Stefyl (meth)acrylate, tridecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (曱) Base) cyd〇hexyl (meth)acrylate. Among them, preferred are decyl acrylate, ethyl acrylate, and butyl acrylate. The alkyl (meth) acrylate which is a copolymerization component may be used alone or in combination of two or more. Further, a monomer other than the alkyl (meth) acrylate may be used in combination as a copolymerization component. Specific examples of such a monomer include thioglycol 201202268 JO JJJlf (methacrylic acid), acrylic acid, crotonic acid, vinyl benzoic acid, and fuma. a monobasic acid or a dibasic acid monomer such as fumaric acid, itaconic acid, maleic acid, citraconic acid; maleic anhydride; Amino acid anhydride vinyl monomer; (mercapto) 2-propionic acid 2-hydroxyethyl (meth)acrylate, (mercapto) 2-hydroxypropyl acrylate, (mercapto) acrylic acid 3-hydroxypropyl Ester, (hydroxy) (hydroxy) (hydroxy) 2-hydroxybutyl, (hydroxy) (hydroxy) (hydroxy) (hydroxy) (hydroxy) (hydroxy) (hydroxy) hydroxyalkyl (meth) acrylate; Base 2) β-butyrolactone ring-opening adduct of 2-ethyl acetoacetate, ε-caprolactone (2-caprolactone) of 2-hydroxyethyl (meth)acrylate Adduct, ring-opening adduct of ethylene oxide of (meth)acrylic acid, p-(meth)acrylic acid a ring-opening adduct of propylene oxide, 2-hydroxyethyl (meth) acrylate or a dimer or trimer of 2-hydroxypropyl (meth) acrylate having a hydroxyl group ( Mercapto) acrylate; 4-hydroxybutyl vinyl ether, p-hydroxy styrene and other hydroxyl-containing vinyl monomers; phenyl (meth) acrylate ( Phenyl (meth)acrylate ), benzyl (meth)acrylate, is〇b〇rnyl (meth)acrylate, styrene; o-methyl Styrene (〇_methyi styrene), m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl P-ethyl styrene, 2,4-dimercaptostyrene 8 201202268 (2,4-dimethyl styrene ), p-butyl styrene, p-tert-butylbenzene Phenylene monomer such as ethylene (p-tert-butyl styrene); acrylonitrile, methacrylonitrile, vinyl acetate (vinyl acetate), glycidyl (meth)acrylate, (methylglycidyl (meth)acrylate), allyl glycidyl ether (methyl acetate) Allylglycidyl ether) and other epoxy group-containing vinyl precursors, (dimethylaminoethyl (meth)acrylate), diethylaminoethyl (meth)acrylate Nitrolylethyl (meth)acrylate, N-meliioxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxylated N-ethoxymethyl acrylamide, N-propoxymethyl acrylamide, N-butoxymethyl acrylamide; a (mercapto) acrylate having a hydroxyalkyl group such as 2-ethyl perfluoroacetic acid, 2-hydroxypropyl (meth)acrylate, or 4-butylidene (meth) acrylate. Among the monomers used for the polymerization, the amount of the alkyl (meth) acrylate other than methyl methacrylate is preferably 0.5% by weight (wt%) to 2 Å by weight. Further, the amount of the monomer other than the monomer other than the alkyl (meth) acrylate is preferably 20% by weight or less. Further, the monomer used for the polymerization preferably contains 8% by weight to 99% by weight of methyl methacrylate, and 0.5% 〇/0 to 2% by weight of methyl propyl phthalate (曱). Base) acrylic acid ester. When the content of (meth)acrylic acid 201202268 calcined vinegar is 0.5 wt% or more, the thermal stability of the obtained methylated women's acid compound is good, and thermal decomposition of the resin during molding is difficult to carry out, and the molded article is difficult to be formed. The appearance defect such as the generation of bubbles disappears. Further, when the content of the alkyl acrylate is 20% by weight or less, the heat resistance of the obtained methyl ester polymer becomes good, and the molded article is not thermally deformed, and can be suitably used for general use. [Step (a)] In the step (a) of the present invention, the above monomer is supplied to the completely mixed reactor (A), and the first radical polymerization initiator is used to carry out the polymerization to obtain the first slurry. step. The σ first radical polymerization initiator may be decomposed to generate a radical at the temperature of the reaction system in the step (a). Specific examples of the above first radical polymerization initiator include tert-butyl peroxy-3,5,5-trimethylhexanate, and peroxidation. Tert-butyl peroxylaurate, tert-butyl peroxyisopropyl monocarbonate, tert-hexyl peroxyisopropyl monocarbonate ), tert-butyl peroxyacetate, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexene (l,l-bis(tert) -butylperoxy)3,3,5-trimethylcyclohexane), U-bis(tert-butylperoxycyclohexane), third ethyl peroxyhexanoate Tert-butyl peroxy 2-ethylhexanate, peroxidation 201202268 tert-butyl peroxyisobutyrate, tert-hexyl-hexyl peroxy 2-ethylhexanate ), di-tert-butyl peroxide, 2,5-dimercapto-2,5-bis (t-butyl) Oxidized) organic peroxide such as hexane (2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexane); 2-(amine sulfhydryl)-isobutyronitrile (2-(carbamoyl azo) )-isobutyronitrile ), 1, Γ-azobis(1-cyclohexanecarbonitrile) (1,1'42〇13丨3(1-〇3^1〇116\&116 0&1:1) 011 丨16)), 2,2'-azobisisobutyronitrile (2,2'-azobisisobutyronitrile), 2,2'-azobis(2-mercaptobutyronitrile) (2,2'-azobis (2-methylbutyronitrile)), 2,2'-diazobisisobutyrate (dimethyl 2,2'-azobisisobutyrate), 2,2'-azobis(2,4,4-tridecylpentene (2,2'-azobis(2,4,4-trimethylpentane)), 2,2,-azobis(2-methylpropane), etc. An azo compound; a persulfate such as potassium persulfate; a redox-based polymerization initiator. The first radical polymerization initiator may be used alone or in combination of two or more. The radical polymerization initiator is preferably an initiator having a half-life of 10 seconds or more and 30 minutes or less with respect to the temperature used. If the half-life is moderately long, the radical polymerization initiator is uniformly dispersed in the polymerization system and decomposed, and the generation of the easily decomposed ferrite is suppressed. Further, if the half-life is moderately short, it is difficult to cause a problem of difficulty in restarting due to an increase in the viscosity of the reaction liquid when the emergency operation is stopped. The amount of the first radical polymerization initiator to be used may be appropriately determined depending on various conditions such as the polymerization temperature of the reaction system in the step (a), the average residence time of the reactants, and the monomer conversion ratio of the target 201202268. In particular, in terms of obtaining a methacrylate polymer excellent in thermal decomposition resistance with a small amount of terminal double bonds, the amount of the first radical polymerization initiator used is preferably 5. Å relative to the monomer 1 〇. The xl〇5 mole is below, and in terms of industrial productivity, it is preferably 5.〇xlCT6 mole or more. The chain transfer agent may also be used in the polymerization of the step (a), and it is particularly preferable to use a mercaptan compound. Specific examples of the thiol compound include n-butyl mercaptan, isobutyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, second butyl mercaptan, and second-dodecyl sulfur. a primary, secondary or tertiary thiol having a thiol or substituted alkyl group such as an alcohol or a tert-butyl thiol; phenyl thiol, thiocresol, 4-tert-butyl sulfonate (4) -tert-butyl-〇-thi〇Cres〇l) and other aromatic thiols; thioglycolic acid and its ester; ethylene dithiol (ethylene thi〇giyc〇1) and other carbon number 3~18 Mercaptan. Among them, preferred are tert-butyl mercaptan, n-butyl mercaptan, n-octyl mercaptan, and n-dodecyl mercaptan. The chain transfer agent may be used alone or in combination of two or more. Maintaining the strength of the product and obtaining a moderate degree of polymerization that can be subjected to the forming process (usually as a material for the forming of the material, the weight average molecular weight of the polymer after the final removal of the volatile component is 70,000 to 150,000), and is manufactured. Excellent in miscibility? In terms of the base polymer, the amount of the bond transfer agent is preferably 100% by mole relative to the monomer (mol/0). 〇1 is called m〇1%, more preferably 〇〇. 5%%~〇5 mol% In the case of carrying out the step (a) by solution polymerization, an inert solvent is used. 12 201202268 ° Specific examples of the xanthene tribasic solvent include decyl alcohol, ethanol, methyl phenanthrene, diterpene, acetone acetonyl isobutyl ketone, ethyl bromide, decyl ethyl ketone, and butyl acetate. Among them, preferred are decyl alcohol, terpene benzene, ethylbenzene, and acetic acid butyl vinegar. The inert solvent may be used alone or in combination of two or more. The amount of the inert solvent used is preferably less than 5 in the composition of the reaction liquid.
Wt/ο。更佳為進行不使用惰性溶劑的塊狀聚合，但若惰性 /谷劑的使用量在反應液組成物中小於5 wt%，則基本上不 損及耐熱分解性，另外與塊狀聚合同樣地利用凝膠效果， 由此可藉由使用少量的自由基聚合起始劑來有效地提高單 體轉化率。 所明兀全混合型反應器（A)，是指使所供給的原料在 利用授拌裝置等來均勻混合的㈣下反應較置^完全混 合型反應H (A)可為分㈣卿反應$，亦可為連續式 管型反應器。槽型反應器可使用具備供給口、取出口及攪 拌裝置的槽型反縣置。猜裝置難為具有敍反應區 域整體的混合性能。管型反應器較佳為塞流型反應器，更 佳為内裝有靜態混合器的附夾套的管型反應器。若内裝有 靜態混合H，前利用獅效果來使反應的均勻化及^應 液的流動變得穩^。靜祕的難為Noritake CompanJ (股）公司製造的靜態混合器、或住友重機械（股）公司 製造的Through The Mixer。完全混合型反應器（A)可僅 使用1種’亦可併用2種以上。另外’亦可將旧反應器 串聯連接。 & 步驟（a)中，於完全混合型反應器（A)内將包含單 13 201202268 5及合起始劑的原料組成物在適度條件下加 …，使甲基丙烯W單體的—部分聚合 聚合溫度只要在獲得具有所靈置㈣儿方更付矛策科。 圍内適當設定即可?;==的第-漿料的範 庙吳L 射反絲作為完全混合型反 應器⑷來貫施步驟⑷的情況，例如可自】贼〜⑽ 的範圍内選擇。於繼槽型反應器 # d反應器中實施步驟（a)的情況 自〇入口溫度11(rc〜1贼（較佳為n(rc〜14(rc)、出^ 溫度120C〜18(TC (較佳為靴〜〗。 35 tv驟7(:)中獲件的第一漿料中的單體轉化率較佳為 35^/。〜7〇 wt% ’更佳為& wt%〜6Q讓。該些範圍的 限值於在槽型反應器中保持槽内的均勻性，充分達成槽 内的混合、傳熱而進行穩定運轉的方面有意^ =於達到充分的單體轉化率而提高生產性的方面有意 步驟（a)巾獲得的第—漿料的溫度較佳為ii〇<>c〜 C ’更佳為12〇°C〜16(rc。該些範圍的下限值於抑制 二聚物的生成，且維持揮發成分錢後的聚合物的透明 ^果^強度的方面有意義。另外，上限值於抑制由凝膠 =起的聚合速度的加速現象，以高單體轉 運轉的方岭絲。 ^ 6型反應器内，例如可以如下方式進行聚合。藉由 ° 單體中導入I氣等惰性氣體或者將原料單體在減壓 201202268 yj y 々if :保持—定時間’而使溶氧濃度為2重量ppm以下，更佳 量ppm以下。若以上述方式降低溶氧濃度’則聚合 j穩定進行，另外即便在聚合步驟中長時間保持高溫， 亦土本上不產生著色成分而獲得高品質的聚合物。 接著，自完全混合型反應器（A)中取出第一漿料， 供給至與龄纽合型反絲⑷連接配置的反應器（b) 中。第一漿料亦可在輸送至反應器（B)中之前進行冷卻。 [步驟（b)；] 本發明中的步驟（b)是將上述步驟（a)中獲得的第 一漿料以及第二自由基聚合起始劑供給至配置於完全混合 型反應器（A)的下游的反應器（B)中而進行聚合，獲得 第一黎料的步驟。 該步驟（b)中，當將單體中的曱基丙烯酸曱酯以外的 (曱基)丙烯酸烧基酯的含量設為x[wt%]，且將反應器（B) 中的每單位時間的第二自由基聚合起始劑供給量相對於第 一漿料供給量的重量比設為y[ppm]時，X與y滿足以下的 式子。 8.5x+123 ^y^-2.6x+45 上述式子中，藉由滿足y2-2.6x+45的關係，可於短 時間内提高單體轉化率。另外，藉由滿足8,5x+123gy的 關係’可製造熱穩定性優異的曱基丙烯酸g旨聚合物。若熱 穩定性優異，則成形時樹脂的熱分解難以進行，成形品中 15 201202268 的氣泡的產生等外觀不良消失。 第二自由基聚合起始劑例如可使用與第一自由基聚合 Ϊ始劑相同的起始劑。關於第二自由絲合起始劑的使用 置’只要滿足上述式子，則可與第一自由基聚合起始劑相 同。 步驟（b)巾，為了在短時間内提高單體轉化率，較佳 為於較步驟（a)更高的溫度下進行聚合。因此，第二自由 基聚合起始趣概為使陳第-自由絲合起始劑更高 溫分解型的自由基聚合起始劑。具體而言，第二自由基聚 合起始劑較佳為使用具有較步驟（b)中的平均溫度下的第 一自由基聚合起始劑的半衰期更長的半衰期的自由基聚合 起始劑。進而，第二自由基聚合起始劑亦可將具有較步驟 (b)t的平均溫度下的第一自由基聚合起始劑的半衰期更 長的半衰期的自由基聚合起始劑、及與第一自由基聚合起 始劑相同的自由基聚合起始劑併用。藉由併用2種自由基 聚合起始劑，可減少為了獲得相同的單體轉化率而必需2 聚合起始劑的量》 第一自由基聚合起始劑可分為多次添加。於此情況 下，將每次的第二自由基聚合起始劑相對於每單位時間所 供給的漿料的重量比[ppm]的合計設為y[ppm]。 反應器（B)的具體例可列舉與先前所說明的完全屍 合型反應器（A)的具體例相同的反應器，特佳為管型反 應器。反應器（B)可僅使用1種，亦可併用2種以上。 另外，亦可將1種反應器串聯連接。 201202268 步驟（b)中，於反應器（B)内將包含第一漿料及第 二自由基聚合起始劑的組成物在適度條件下加熱，使第一 毁料中存在的單_ —部分聚合，獲得第二㈣。聚合溫 度只要以第二㈣成為所需單體轉辦的方式適當設定即 可。 步驟（b)巾獲得的第二祕巾的單雜化率較佳為 0 wt/〇 9〇 wt/0 ’更佳為7〇 wt%〜wt%。該些範圍的 於適度抑制漿料的黏度，減少使製程内流動時的壓 有意義。另外，下限值於減少殘存單體而降 低其後的去揮發步驟的負擔的方面有意義。 應器（Β)的内壁的溫度較佳為125<>C〜21(TC，更 物麟有義。另外，上限值於製程内的聚合 物維持&動性而進行穩定運轉的方 [步驟（c)] 我 二榮t==r(e)是將上述步驟⑴中獲得的第 步驟\c〇, 基丙烯咖聚合物的步驟。藉由該 熱^高。甲基叫酸賭聚合物中的殘存單體量減少，财 中而實二漿料投人至去揮發擠出機 可進-步加所得嶋^ 為不超過250。(：的溫产丰播…7料的情況，較佳為設 咖〜0 ! MPa的；f去揮發擠出機中，較佳為於咖1 的祕下㈣第二轉，將以甲基丙婦酸醋 17 201202268 OO lilA "一. 一.Wt/ο. More preferably, the bulk polymerization is carried out without using an inert solvent. However, if the amount of the inert/trol agent used is less than 5 wt% in the reaction liquid composition, the thermal decomposition resistance is not substantially impaired, and the bulk polymerization is the same as in the bulk polymerization. By utilizing the gel effect, it is possible to effectively increase the monomer conversion rate by using a small amount of a radical polymerization initiator. The all-mixing type reactor (A) means that the supplied raw materials are uniformly mixed by means of a mixing device or the like (4), and the reaction is more complete than the fully mixed type reaction H (A). It can also be a continuous tubular reactor. The trough type reactor can be used in a trough type with a supply port, an outlet, and an agitation device. It is difficult to guess that the device has the mixed performance of the overall reaction area. The tubular reactor is preferably a plug flow reactor, more preferably a jacketed tubular reactor having a static mixer therein. If static mixing H is installed inside, the lion effect is used to make the reaction uniform and the flow of the liquid becomes stable. It is difficult to make a static mixer made by Noritake CompanJ Co., Ltd. or a Through The Mixer made by Sumitomo Heavy Industries Co., Ltd. The fully mixed reactor (A) may be used alone or in combination of two or more. Alternatively, the old reactors can be connected in series. & In step (a), in the fully mixed reactor (A), the raw material composition containing the single 13 201202268 5 and the starter is added under moderate conditions to make a part of the methyl propylene W monomer. The polymerization polymerization temperature is as long as it is obtained by having a genus (4). The appropriate setting in the circumference can be made; the case of the first-slurry of the first-slurry is the case of the complete mixed-type reactor (4), and the step (4) can be carried out, for example, from the range of the thief ~ (10). The step (a) is carried out in the tank type reactor #d reactor from the inlet temperature 11 (rc~1 thief (preferably n (rc~14(rc), outlet temperature 120C~18 (TC ( Preferably, the shoe is -> 35 tv. The conversion rate of the monomer in the first slurry obtained in the step 7 (:) is preferably 35^/.~7〇wt% 'better is & wt%~6Q The limit of the range is such that the uniformity in the tank is maintained in the tank type reactor, and the mixing and heat transfer in the tank are sufficiently achieved to perform stable operation, which is intentional to achieve sufficient monomer conversion rate. In terms of productivity, the temperature of the first slurry obtained by the step (a) towel is preferably ii 〇 <> c 〜 C ' more preferably 12 〇 ° C ~ 16 (rc. The lower limit of the range It is effective in suppressing the formation of a dimer and maintaining the transparency of the polymer after the volatile component is added. In addition, the upper limit is an acceleration phenomenon in which the polymerization rate from the gel is suppressed, and the monomer is high. In the type 6 reactor, for example, the polymerization can be carried out as follows: by introducing an inert gas such as I gas into the monomer or by using the raw material monomer under reduced pressure 201202268 Yj y 々 if : keeps the time constant and makes the dissolved oxygen concentration 2 ppm by weight or less, more preferably ppm or less. If the dissolved oxygen concentration is lowered in the above manner, the polymerization j is stably performed, and even if it is long in the polymerization step High temperature is maintained, and a high-quality polymer is obtained without coloring the composition. Next, the first slurry is taken out from the completely mixed reactor (A) and supplied to the connection with the aged-type reverse yarn (4). In the reactor (b), the first slurry may also be cooled before being sent to the reactor (B) [Step (b);] The step (b) in the present invention is obtained in the above step (a) The first slurry and the second radical polymerization initiator are supplied to a reactor (B) disposed downstream of the complete mixing reactor (A) to carry out polymerization, and a step of obtaining a first material is obtained. In b), when the content of (mercapto)acrylic acid alkyl ester other than decyl decyl acrylate in the monomer is set to x [wt%], and the second per unit time in the reactor (B) The weight ratio of the radical polymerization initiator supply amount to the first slurry supply amount is set to y [ppm] X and y satisfy the following formula: 8.5x+123 ^y^-2.6x+45 In the above formula, by satisfying the relationship of y2-2.6x+45, the monomer conversion rate can be improved in a short time. In addition, by satisfying the relationship of 8,5x+123gy, it is possible to produce a thioglycolic acid g-polymer which is excellent in thermal stability. When the thermal stability is excellent, thermal decomposition of the resin during molding is difficult, and in the molded article, 15 201202268 The appearance defect such as generation of bubbles disappears. The second radical polymerization initiator may be, for example, the same initiator as the first radical polymerization initiator. The use of the second free-stranding initiator can be the same as that of the first radical polymerization initiator as long as the above formula is satisfied. In the step (b), in order to increase the monomer conversion rate in a short time, it is preferred to carry out the polymerization at a higher temperature than the step (a). Therefore, the second free radical polymerization is initially a radical polymerization initiator which makes the Chen-free silky starter higher temperature-decomposable. Specifically, the second radical polymerization initiator is preferably a radical polymerization initiator having a half life longer than the half life of the first radical polymerization initiator at the average temperature in the step (b). Further, the second radical polymerization initiator may also have a half-life radical polymerization initiator having a longer half-life than the first radical polymerization initiator at an average temperature of the step (b) t, and A radical polymerization initiator is used in combination with the same radical polymerization initiator. By using two kinds of radical polymerization initiators in combination, it is possible to reduce the amount of 2 polymerization initiator required to obtain the same monomer conversion. The first radical polymerization initiator can be divided into a plurality of additions. In this case, the total weight ratio [ppm] of the second radical polymerization initiator to the slurry supplied per unit time is set to y [ppm]. Specific examples of the reactor (B) include the same reactors as the specific examples of the fully cloagulated reactor (A) described above, and particularly preferably a tubular reactor. The reactor (B) may be used alone or in combination of two or more. Alternatively, one type of reactor may be connected in series. 201202268 In step (b), the composition comprising the first slurry and the second radical polymerization initiator is heated in a reactor (B) under moderate conditions to cause a single portion in the first reject. Aggregate to obtain the second (four). The polymerization temperature may be appropriately set as long as the second (four) is a desired monomer transfer. The single hybridization rate of the second secret towel obtained in the step (b) towel is preferably 0 wt / 〇 9 〇 wt / 0 ' more preferably 7 〇 wt% ~ wt%. These ranges are used to moderately inhibit the viscosity of the slurry and to reduce the pressure during flow in the process. Further, the lower limit value is significant in terms of reducing the residual monomer and reducing the burden of the subsequent devolution step. The temperature of the inner wall of the reactor (Β) is preferably 125 <> C to 21 (TC, which is more advantageous. In addition, the upper limit is used for the stable operation of the polymer in the process to maintain & [Step (c)] I Er Rong t==r(e) is the step of the first step obtained in the above step (1), the step of the base propylene polymer. By the heat is high. The amount of residual monomer in the polymer is reduced, and the second and second slurry can be injected into the de-evaporation extruder to increase the amount of 嶋^ to not exceed 250. (: The temperature of the product is high. Preferably, it is set to 0~ MPa; f to the volatilization extruder, preferably in the secret of the coffee 1 (four) second turn, will be methyl acetoin 17 201202268 OO lilA " One.
就、左濟f生方面而5，未反應的曱基丙稀酸酿單體 發物較佳為於冷凝n巾凝縮而雜後，作為步驟⑷的原 料，再利用。此時’更佳為將揮發物中所含的甲基丙稀酸 s曰單體的二聚物等高軸成分藉由_而分離去除後，作 為步驟（a )的原料而再利用。 以上述方式製造的曱基丙烯酸酯聚合物例如可作為成 形材料來使用。此時，視需要可添加高級醇類、高級脂肪 酸酯類等潤滑劑、紫外線吸收劑、熱穩定劑、著色劑、抗 靜電劑等。 ~ [實例] 以下，利用實例來對本發明進行更詳細的說明，但該 些實例並不限定本發明。此外，聚合物的分子量的測定是 利用以下方法進行。 〈藉由凝膠渗透層析法（gel permeation chromatography，GPC)的分子量測定〉 使用Tosoh公司製造HLC-8020作為GPC裝置，且使 用2根Tosoh公司製造的GMHXL作為管柱。溶劑是使用 四氫呋喃（tetrahydrofuran，THF) ’使用Tosoh公司製造 的TSK標準聚苯乙烯來製作校正曲線，試料是使用靜置溶 18 201202268 解的浪度0.1 g/dl的溶液。重量平均分子量Mw是利用gpc 資料處理裝置（Tosoh公司製造的資料裝置Sc_8〇.1〇 求出。 〈成形性的評價〉 使用PS-60E (曰精樹脂工業公司製造）作為成形機， 成形溫度是設為300。(：，製作渦狀的成塑體，並觀察其外 U ° … 〈實例1 > 使用圖1所示的裝置，以如下所述的方式來實施本發 明。 [步驟（a)] 向包含經純化的甲基丙稀酸甲酯98 wt〇/〇及丙浠酸甲 酯2 wt%的單體混合物中導入氮氣，使溶氧為〇 5 ppm。相 對於該單體混合物，將混合有作為鏈轉移劑的正辛基硫醇 0.157 mol%(0.23 wt%)、以及作為第一自由基起始劑的u_ 雙(第二丁基過氧化)3,3,5-三甲基環己烷2.67x1〇·5莫耳/單 體1莫耳（80 ppm)的原料組成物，一邊攪拌混合一邊連 續供給至經控制為聚合溫度135C»c的第一反應器n即完全 混合型反應器中’將原料組成物的反應區域的平均滯留時 間設為2.5卞時來實施聚合，獲得第一聚料。此外，該聚 合溫度（π5 c)下的1}1•雙(第三丁基過氧化)；3,3,5_三曱基 環己烷）的半衰期為23〇秒。 [步驟（b)] 接著，利用齒輪泵31自第一反應器11中連續取出第 201202268 二2二起始劑投入器21(内裝有住友重機械工孝⑷ =SMXThroughTheMixer的配管)’來添加作為第二 么基起始劑的i，1·雙(第三丁基過氧化)3,3,5_三甲::氧 烷’以使相對於每輕時間的漿料供給 ^ 厂，然後將其供給至第二反應器12即内裝;^ (股）製造的靜祕合糾料反絲（塞流型 接二著丁2氧化)3,3,5-三曱基魏燒的半衰期為54秒。 接者，將第二反應器12中聚合的漿料導入至與上 投入器22中’添加作為進-步的第二自由 “二第二丁基過氧化物’以使相對於每單位時間 的漿枓供給里的重量比成為40ppm，將其供給至與第二反 應器12相同的第三反應器13即内裝有驗咖 J股丄製造的㈣混合㈣f型反絲（塞流型反應器）] 中。又内壁溫度為170〇C，内壓為25 kg/Cm2G ’平均滯留 日^為20分鐘來實施聚合’獲得第二聚料。此外，該溫度 [步驟第三丁基過氧化物的半衰期為250秒。 接著’於！95。(：下將第二聚料自第二反應器21的出口 連續供給至去揮發擠出機14 (排氣擠出機型擠出機）中， 於270°C下將以未反應單體作為主成分的揮發物分離去 除，獲得甲基丙烯酸酯聚合物。 測定自去揮發擠出機14中取出的甲基丙稀酸酉旨聚合 201202268 物的量及所投入的原料單體的累計量，結果為相對於所投 二的原料的單體轉化率為78 wt%。另外，於小時的連 、，運轉中亦於聚合的控制方面無問題， ;器：，察中亦未確認到對裝置的附著物或異:物的生成 等。另外’對所得的甲基丙烯酸酯聚合物進行上述成形性 =認到氣泡的存在，成形品的外觀良好。 將結果不於表1。 〈實例2〉 除了將追加於第二反應器12[第—個反應器（Β)]中 量變更為6。ppm ’且將追加於第三反應器13[第 二個反應器（B)]中的賴劑量變更為⑼鹏以外，進 行，實例1同樣的操作。測定自铸發擠出機14中取出的 :基丙稀酸㈣合物的量及所投人的補單體的累計量， …果為相對於所投人的原料的單體轉化率為8G wt%。另 f ’於360小時的連續運轉十亦於聚合的控制方面無間 通’於運轉結錢的反應H_觀料絲相到對 物的生成等。另外’對所得的甲基丙稀酸醋 。，進仃上述成雜的評價，結果為未確認到氣泡的存 在’成形品的外觀良好。將結果示於表1。 〈實例3〉 除了將單體混合物中的曱基丙烯酸甲酯的量變更為 85 wt，’將丙婦酸甲g|的量變更為15加％，將追加於第^ 反應器12[第—個反應器⑻]中的起始劑量變更為^ ’，且將追加於第三反應器13[第二個反應器⑻]中的 201202268 起始劑量變更為15 ppm以外，進行與實例丨同樣的操作。 ，定自去揮發擠出機14令取出的甲基丙婦酸醋聚合物的 K及所投人的·單_累計量，結 原料的單體轉化率為73.另外，於3叫時的連續^ 合的控制方面無問題’於運轉結束後的反應器 内的觀察中亦未確認到對裝置_著物或異物的生成等。 另外’對所得的甲基丙烯酸S旨聚合物進行上述成形性的評 價’結果絲確糊聽畴在，成似的外觀良好。將 結果示於表1。將結果示於表1。 〈實例4〉 除了將追加於第二反應器12[第一個反應器（Β)]中 的起始劑量變更為60 ppm，且將追加於第三反應器u[第 二個反應器（B)]中的起始劑量變更為6()酵以外，進 行與實例3同樣的操作。測定自去揮發擠出機14中取出的 曱基丙烯_聚合物的量及所投人的原料單體的累計量， 結果為相對於所投人的原料的單體轉化率為77加％。另 外’於360小時的連續運轉中亦於聚合的控制方面益問 題，於運賴束㈣反應H⑽觀料絲輕到對裝置 的附著物或異物的生成等。另外，對所得的曱基丙稀酸醋 聚合物進行上述成形性的評價’結果為未確認到氣泡的存 在，成形品的外觀良好。將結果示於表i。 〈實例5〉 除了將追加於第二反應器12[第—個反應器⑻]中 的起始劑量變更為1〇〇 ppm，且將追加於第三反應器[第 22In the case of the left side, the unreacted mercaptoacrylic acid monomer is preferably used as a raw material of the step (4) after being condensed and condensed. In this case, it is more preferable to separate and remove the high-axis component such as the dimer of the methyl methacrylate s oxime monomer contained in the volatile matter, and then reuse it as a raw material of the step (a). The mercaptoacrylate polymer produced in the above manner can be used, for example, as a molding material. In this case, a lubricant such as a higher alcohol or a higher fatty acid ester, a UV absorber, a heat stabilizer, a colorant, an antistatic agent, or the like may be added as needed. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but these examples are not intended to limit the invention. Further, the molecular weight of the polymer was measured by the following method. <Molecular weight measurement by gel permeation chromatography (GPC)> HLC-8020 manufactured by Tosoh Corporation was used as a GPC apparatus, and two GMHXLs manufactured by Tosoh Corporation were used as a column. The solvent was prepared by using TSK standard polystyrene manufactured by Tosoh Corporation using tetrahydrofuran (THF). The sample was a solution having a wave length of 0.1 g/dl which was dissolved in a solution of 18 201202268. The weight average molecular weight Mw is obtained by using a gpc data processing device (a data device Sc_8〇.1〇 manufactured by Tosoh Corporation). <Evaluation of Formability> Using PS-60E (manufactured by Seiko Seika Co., Ltd.) as a molding machine, the molding temperature is It is set to 300. (:, a spiral shaped plastic body is produced, and the outer U ° is observed. <Example 1 > Using the apparatus shown in Fig. 1, the present invention is carried out in the following manner. [Step (a ]] Introducing nitrogen into a monomer mixture containing purified methyl methacrylate 98 wt 〇 / 〇 and 2 wt % methyl propyl acrylate to make the dissolved oxygen 〇 5 ppm. Relative to the monomer mixture , 0.157 mol% (0.23 wt%) of n-octyl mercaptan as a chain transfer agent, and u_bis (second butyl peroxy) 3,3,5-three as a first radical initiator A raw material composition of methylcyclohexane 2.67 x 1 〇·5 mol/monomer 1 mol (80 ppm) was continuously supplied to the first reactor n controlled to a polymerization temperature of 135 C»c while stirring and mixing. In the hybrid reactor, the polymerization was carried out when the average residence time of the reaction zone of the raw material composition was 2.5 卞. The first polymer is obtained. In addition, the half-life of 1}1•bis (t-butylperoxy); 3,3,5-tridecylcyclohexane at the polymerization temperature (π5 c) is 23〇 [Step (b)] Next, the gear pump 31 is used to continuously take out the 201202268 222 starter dispenser 21 (with Sumitomo Heavy Industries (4) = SMXThroughThe Mixer piping) from the first reactor 11' To add i,1·bis (t-butylperoxy) 3,3,5-trimethyl::oxane as a second base initiator to supply the slurry to the lighter per light time, Then, it is supplied to the second reactor 12, that is, the interior is installed; ^ (s) is made of a static and correcting anti-filament (the plug-flow type is coupled with the diced 2 oxidation) 3,3,5-trimethyl-based Wei-burning The half-life is 54 seconds. In addition, the slurry polymerized in the second reactor 12 is introduced into the upper input unit 22 to 'add the second free "second second butyl peroxide" as the further step to make the relative The weight ratio in the pulp supply per unit time is 40 ppm, and is supplied to the third reactor 13 which is the same as the second reactor 12, that is, the (four) mixed f-type anti-filament (manufactured by the tester). Plug Type reactor)]. The inner wall temperature is 170 〇C, the internal pressure is 25 kg/Cm2G 'the average retention time ^ is 20 minutes to carry out the polymerization' to obtain the second granule. In addition, the temperature [step third butyl The half life of the peroxide is 250 seconds. Then 'at! 95. (: the second polymer is continuously supplied from the outlet of the second reactor 21 to the devolverizing extruder 14 (exhaust extruder type extruder) Among them, volatiles containing unreacted monomers as a main component were separated and removed at 270 ° C to obtain a methacrylate polymer. The amount of the methyl methacrylate-derived polymer 201202268 taken out from the devolatization extruder 14 and the cumulative amount of the raw material monomers charged were measured, and as a result, the monomer conversion rate with respect to the raw materials to be fed was 78. Wt%. In addition, there was no problem in the control of polymerization during the operation of the hour, and the device was not confirmed to be attached to the device or the generation of the object. Further, the above-mentioned moldability of the obtained methacrylate polymer was confirmed. The presence of bubbles was recognized, and the appearance of the molded article was good. The results will not be as shown in Table 1. <Example 2> The amount of addition to the second reactor 12 [the first reactor (Β)] was changed to 6. The same operation as in Example 1 was carried out except that the dose added to the third reactor 13 [second reactor (B)] was changed to (9). The amount of the acrylic acid (tetra) compound and the cumulative amount of the monomer to be added taken out from the casting extruder 14 were measured, and the monomer conversion rate was 8 G with respect to the raw material to be injected. Wt%. In addition, the continuous operation of f' in 360 hours is also inconsistent in the control of polymerization, and the reaction of running the money H_the silk phase to the formation of the object. In addition, the resulting methyl acrylate vinegar. When the above-mentioned hybrid evaluation was carried out, the presence of bubbles was not confirmed. The appearance of the molded article was good. The results are shown in Table 1. <Example 3> In addition to changing the amount of methyl methacrylate in the monomer mixture to 85 wt, 'the amount of gamma-glycolate g|| was changed to 15% by weight, and it was added to the reactor 12 [the first] The initial dose in the reactor (8)] was changed to ^ ', and the starting dose of 201202268 added to the third reactor 13 [second reactor (8)] was changed to 15 ppm, and the same procedure as in Example 进行 was performed. operating. , the self-de-evaporation extruder 14 is used to take out the methyl acetoacetate polymer K and the amount of the person to be _ accumulated, the monomer conversion rate of the raw material is 73. In addition, at the time of 3 calls There is no problem in the control of the continuous control. In the observation of the reactor after the completion of the operation, the generation of the device, the foreign matter, and the like were not confirmed. Further, the results of the evaluation of the above-mentioned moldability of the obtained methacrylic acid S polymer were confirmed to be good, and the appearance was good. The results are shown in Table 1. The results are shown in Table 1. <Example 4> The initial dose added to the second reactor 12 [first reactor (Β)] was changed to 60 ppm, and was added to the third reactor u [second reactor (B The same operation as in Example 3 was carried out except that the starting dose in the case was changed to 6 (). The amount of the mercapto propylene-polymer taken out from the devolatization extruder 14 and the cumulative amount of the raw material monomers to be injected were measured, and as a result, the monomer conversion ratio with respect to the raw material to be injected was 77% by weight. In addition, in the continuous operation of 360 hours, it is also a problem in the control of polymerization. In the case of the transportation (4), the reaction H(10) is light to the attachment of the device or the formation of foreign matter. Further, the obtained mercaptopropionic acid vinegar polymer was evaluated for the above-mentioned moldability. As a result, the presence of bubbles was not confirmed, and the appearance of the molded article was good. The results are shown in Table i. <Example 5> The initial dose added to the second reactor 12 [the first reactor (8)] was changed to 1 〇〇 ppm, and was added to the third reactor [22th]
201202268 L 二個反應器（B)]中的起始劑量變更為1〇〇ppm以外，進 行與實例3同樣的操作。測定自去揮發擠出機14中取出的 甲基丙婦酸酉旨聚合物的量及所投入的原料單體的累計量， 結果為相對於所投入的原料的單體轉化率為83 wt%e另 外，於360小時的連續運轉中亦於聚合的控制方面無問 «I於運轉結束後的反應器内的觀察中亦未確認到對裝置 的附著物或異物的生成等。另外，對所得的曱基丙烯酸酯 聚合物進行上述成形性的評價，結果為未確認到氣泡的存 在’成形品的外觀良好。將結果示於表1。 〈比較例1〉 除了將追加於第二反應器12[第一個反應器（B)]中 的起始劑I變更為20 PPm，且將追加於第三反應器13[第 二個f應器（B)]中的起始劑量變更為15 ppm以外，進 行〃貫例1同樣的操作。測定自去揮發擠出機14中取出的 :基丙烯酸酯聚合物的量及所投入的原料單體的累計量， 二果為相對於所投入的原料的單體轉化率低至68，每 單位時間所獲得的樹脂量變少。將結果示於表卜 〈比較例2> 除了將，加於第二反應器12[第一個反應器（B)]以 反應。。13[弟一個反應器（B)]中的起始劑量變更 加以外’進行與實例3同樣的操作。駭自去揮發 H中取出的曱基丙烯酸酯聚合物的量及所投入的 3早體的累計量’結果為相對於所投人的原料的單體轉 罕低至50 wt%，每單位時間所獲得的樹脂量變少。將結 23 201202268 w —上 果示於表1。 〈比較例3〉 除了將追加於第二反應器12[第一個反應器（Β)]中 的起始劑罝變更為8〇 ppm，且將追加於第三反應器第 :個士應器（B)]中的起始劑量變更為8〇卯：以外，進 仃與實例1同樣的操作測定自去揮發擠出機14中取出的 甲基丙烯_旨聚合物的量及所投人的原料單體的累計量， 結果為相對於所投人的原料的單體轉化率為83加％。另 外，於360小時的連續運轉中亦於聚合的控制方面益問 題，於運轉結束後岐應H _觀察巾亦未確朗對裝置 的附著物或異物的生成等。但是，對所得的甲基丙稀酸醋 聚合物進行上述成雜的評價，結果為確㈣氣泡的存 在，成形品的外觀產生被稱為銀紋（silver)的白色帶，成 形不良。將結果示於表1。 〈比較例4〉 除了將追加於第二反應器21[第一個反應器（B)]中 的起始劑量變更為150 ppm’且將追加於第三反應器13[第 二個反應器（B)]中的起始劑量變更為i5〇ppm以外，進 行與實例3同樣的操作。測定自去揮發擠出機14中取出的 曱基丙烯酸酯聚合物的量及所投入的原料單體的累計量， 結果為相對於所投入的原料的單體轉化率為9〇 wt%。另 外’於360小時的連續運轉中亦於聚合的控制方面1無問 題，於運轉結束後的反應器内的觀察中亦未確認到對&置 的附著物或異物的生成等。但是，對所得的甲^丙烯^酯 24 201202268 聚合物進行上述成形性的評價’結果為確認到氣泡的存 在，成形品的外觀產生被稱為銀紋的白色帶，成形不良。 將結果示於表1。 將各實例及各比較例的條件以及所獲得的聚合物的特 性示於表1。 25 201202268 【I <】Jussrn 成形材料的特性 嗜剧BS «诤瘦椰遲 1 碡 m 重量 平均 分子 量 Mw 1 88000 87000 82000 77000 76000 90000 88000 87000 76000 殘存 二聚 物量 m cs ο CN CN Ο o 2 ο cn d v-> CN d ON d <s (S d CO o 墘你蛛铟φ| % ο S Ο o ο u-> (N o m ΙΤΪ d VO (N d S ό irj (N 〇 <N 4* od ο Ο 250.5 250.5 250.5 140.0 250.5 o r"H 250.5 ·2·6χ+45 οο σ； CO οο OS CO VO ν〇 VO 00 〇\ m 00 Os cn v〇 步驟（b) 聚合 起始 劑合 計(y) a & g w-> m s o s »n tn o S o CO 塞流型反應器（Νο·2) 聚合條件 許饀餘与资 这 οο § ΓΟ r- cn 00 00 v〇 沄 CO 00 § β鹚Μ Ή D朗妨 P 〇\ 〇\ On a\ on v> ON *«H t Os to 〇\ r*H 陡SB宙Ε Φ墩 S 宕 S 1 宕 S β躪as晓甸 〇〇 ο o r-^ o o o t> o 1 o o 沄 (S o ΓΊ <N «Ν o CN cs 1 o W-) <N cs 聚合起 始劑 1 〇, ο % U-) s o 1 g 日 日 |—| HH 门 HH 日 j—j 塞流型反應器（No.l〕 S v〇 <S v〇 3 VO VO σ\ 1 S o 俊 5®贫S * 1 β鹚as朗妨 〇〇 1 鉍伞破4?茶"《M料踩 ?: ?： 1 ?; 聚合起 始劑 曰 ο s s o 宕 1 g 续！ g ΗΗ HH HH NH Ji HH l-H 步驟（a) 完全混合 槽型反應 器 I聚合條件I _靼:®： ¥蛛 9, $, 9, * 9, 牛ίΓ使®岔E CN Vi <si <N CN CN \T) CN CS κη CN P CO m m tn W-) m r-M «Ο m V) m m 原料組成物 鏈轉移劑 χ〇 S ^ 0.157 0.157 0.157 0.157 0.157 0.157 0.157 0.157 0.157 I ο (N CD m (N d m <N 〇 m cs o m CN o cn <S o cn <s d o Uh P-l tLi tU 為 沄 (Ν 〇 ίΛ cs o CO <N o ΓΛ (N O C〇 CN o ΓΛ <N o cn <s o cs <N 聚合起 始劑 S a g g § g § g § g 续! S ΗΗ HH HH h-H ►—· ►-H HH 共聚單體 V〇 /^N Ο csi o CN o o iri 〇 wS o cs o wS o <N 〇 紫!驟 1 1 1 義 1< ο 〇6 Ον o 〇6 〇\ o 00 o oo o US 00 o 00 On o 00 o 00 On o iri oo 1實例1 1 |實例2 1 |實例3 1 |實例4 1 I實例5 I |比較例11 丨比較例2j |比較例3| 比較例4 201202268 一 ViFxr 〆 无/A 丈 表中的簡稱為如下所述。 •「MMA」：曱基丙烯酸甲酯 •「MA」：丙烯酸曱酯 •「I」：1，1-雙（第三丁基過氧化)3,3,5-三曱基環己烷 •「III」：二-第三丁基過氧化物 •「F」··正辛基硫醇 如表中所明示，各實例中單體轉化率充分。但各比較 例中單體轉化率並不充分。 雖然本發明已以較佳實施例揭露如上，然其並非用以 限^本發明，任何熟習此技藝者，在不脫離本發明之精神 =範圍内，當可作些許之更動與潤飾，因此本發明之保護 色圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1是實例中使用的裴置的概略構成圖。 【主要元件符號說明】 U:第一反應器 12 :第二反應器 13 :第三反應器 14 :去揮發擠出機 21 :起始劑投入器 22 :起始劑投入器 31 :齒輪泵 27The same operation as in Example 3 was carried out except that the initial dose in the two reactors (B) was changed to 1 〇〇 ppm. The amount of the methyl acetoacetate-derived polymer taken out from the devolatization extruder 14 and the cumulative amount of the raw material monomers charged were measured, and as a result, the monomer conversion rate with respect to the input raw material was 83 wt%. In addition, in the continuous operation of 360 hours, there was no question about the control of the polymerization. In the observation of the reactor after the completion of the operation, the formation of deposits or foreign matter to the apparatus was not confirmed. Further, the obtained methacrylate polymer was evaluated for the above-mentioned moldability, and as a result, the presence of bubbles was not confirmed. The appearance of the molded article was good. The results are shown in Table 1. <Comparative Example 1> The starting agent I added to the second reactor 12 [first reactor (B)] was changed to 20 ppm, and was added to the third reactor 13 [the second f should be The same operation as in Example 1 was carried out except that the initial dose in the device (B) was changed to 15 ppm. The amount of the base acrylate polymer taken out from the devolatization extruder 14 and the cumulative amount of the raw material monomer charged were measured, and the monomer conversion rate was as low as 68 with respect to the input raw material, per unit. The amount of resin obtained at the time is reduced. The results are shown in the table. <Comparative Example 2> In addition, it was added to the second reactor 12 [first reactor (B)] for reaction. . The same operation as in Example 3 was carried out by changing the initial dose in 13 (the other reactor (B)). The amount of the thiol acrylate polymer taken out from the devolatilization of H and the cumulative amount of the 3 precursors charged was 'reduced to 50 wt% per unit time relative to the monomer of the raw material to be injected. The amount of resin obtained is reduced. The result is shown in Table 1. <Comparative Example 3> The initial agent 追加 added to the second reactor 12 [first reactor (罝)] was changed to 8 〇 ppm, and added to the third reactor: The starting dose in (B)] was changed to 8 〇卯: In addition, the same operation as in Example 1 was carried out, and the amount of methacrylic acid taken out from the devolatilizing extruder 14 and the amount of the polymer were measured. The cumulative amount of the raw material monomers was found to be 83% by weight with respect to the monomer conversion of the raw materials to be injected. In addition, in the continuous operation of 360 hours, the control of the polymerization is also problematic. After the operation, the H _ observation towel is not sure about the attachment of the device or the formation of foreign matter. However, the above-mentioned hybrid evaluation was carried out on the obtained methyl acetonate polymer, and as a result, it was confirmed that (4) bubbles were present, and the appearance of the molded article was caused by a white band called silver, which was defective in formation. The results are shown in Table 1. <Comparative Example 4> The initial dose added to the second reactor 21 [first reactor (B)] was changed to 150 ppm' and was added to the third reactor 13 [second reactor ( The same operation as in Example 3 was carried out except that the starting dose in B)] was changed to i5 〇 ppm. The amount of the mercaptoacrylate polymer taken out from the devolatization extruder 14 and the cumulative amount of the raw material monomers charged were measured, and as a result, the monomer conversion rate with respect to the input raw material was 9 wt%. In addition, in the continuous operation of 360 hours, there was no problem in the control of polymerization, and the formation of deposits or foreign matter to & was not observed in the observation in the reactor after the completion of the operation. However, the obtained moldability of the obtained polymer was observed. As a result, the presence of air bubbles was confirmed, and the appearance of the molded article was a white band called a silver streak, and the molding was poor. The results are shown in Table 1. The conditions of the respective examples and the respective comparative examples and the characteristics of the obtained polymer are shown in Table 1. 25 201202268 [I <] Jussrn The characteristics of the forming material Dr. BS «诤瘦椰迟1 碡m Weight average molecular weight Mw 1 88000 87000 82000 77000 76000 90000 88000 87000 76000 Residual dimer amount m cs ο CN CN Ο o 2 ο Cn d v-> CN d ON d <s (S d CO o 墘 your spider indium φ| % ο S Ο o ο u-> (N om ΙΤΪ d VO (N d S ό irj (N 〇< ;N 4* od ο Ο 250.5 250.5 250.5 140.0 250.5 o r"H 250.5 ·2·6χ+45 οο σ; CO οο OS CO VO ν〇VO 00 〇\ m 00 Os cn v〇Step (b) Start of polymerization Total (y) a & g w-> msos »n tn o S o CO plug flow reactor (Νο·2) Polymerization conditions Xu Yuyu and capital οο § ΓΟ r- cn 00 00 v〇沄CO 00 § β鹚Μ Ή D 朗 P P 〇 〇 On On On On On On On On On On On On On On ON r r r r r r r r r r r r r r r 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ο o r-^ ooo t> o 1 oo 沄(S o ΓΊ <N «Ν o CN cs 1 o W-) <N cs polymerization initiator 1 〇, ο % U-) so 1 g day |—| HH Door HH Day j—j Plug Flow Reactor (No.l) S v〇<S v〇3 VO VO σ\ 1 S o Jun 5® lean S * 1 β鹚as 朗 〇〇 1 铋 Umbrella break 4? Tea " "M material stepping?: ?: 1 ?; Polymerization initiator 曰ο sso 宕1 g continued! g ΗΗ HH HH NH Ji HH lH Step (a) Completely mixed tank reactor I polymerization conditions I _靼:®: ¥ spider 9, $, 9, * 9,牛ΓΓ®岔E CN Vi <si <N CN CN \T) CN CS κη CN P CO mm tn W-) m rM «Ο m V) mm Raw material composition chain transfer agent χ〇S ^ 0.157 0.157 0.157 0.157 0.157 0.157 0.157 0.157 0.157 I ο (N CD m (N dm <N 〇m cs om CN o cn <S o cn <sdo Uh Pl tLi tU is 沄(Ν 〇ίΛ cs o CO <N o ΓΛ (NOC〇CN o ΓΛ <N o cn <so cs <N polymerization initiator Sagg § g § g § g continued! S ΗΗ HH HH hH ►—· ►-H HH comonomer V 〇/^N Ο csi o CN oo iri 〇wS o cs o wS o <N 〇紫! 11 1 1 义1< ο 〇6 Ον o 〇6 〇\ o 00 o oo o US 00 o 00 On o 00 o 00 On o iri oo 1 instance 1 1 | example 2 1 | example 3 1 | example 4 1 I Example 5 I | Comparative Example 11 丨 Comparative Example 2j | Comparative Example 3 | Comparative Example 4 201202268 A ViFxr 〆 No / A The abbreviations in the table are as follows. • “MMA”: methyl methacrylate • “MA”: decyl acrylate • “I”: 1,1-bis (t-butyl peroxy) 3,3,5-trimethylcyclohexane • III": Di-tert-butyl peroxide • "F" · n-octyl mercaptan As shown in the table, the monomer conversion rate in each example is sufficient. However, the monomer conversion rate in each of the comparative examples was not sufficient. Although the present invention has been disclosed in the above preferred embodiments, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit of the invention. The protective color of the invention is subject to the definition of the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic configuration diagram of a device used in an example. [Explanation of main component symbols] U: First reactor 12: Second reactor 13: Third reactor 14: Devolatization extruder 21: Starter injector 22: Starter injector 31: Gear pump 27