47075 A7 B7 五、發明説明（1 ) (請先閲讀背面之注意事項再樓寫本頁) 本發明係關於-種用以製造氯乙烯聚合物之方法。更 明讀地’本案係關於-種藉由在聚合作用期間變化擾拌條 ，件來製造-具有降低含量之凝聚物、良好之機械安定性及 降低含量之未反應單體的氯乙烯聚合物乳膠之方法。 為了製造一氯乙烯聚合物乳膠或糊漿樹脂，氯乙烯可 藉由一孔化聚合流程來聚合化，其中聚合作用係藉由在— 設有一冷卻夾層之加壓聚合反應器中，利用一陰離子或非 離子性表面活性劑作為一乳化劑、一水溶性過氧化物作為 —聚合作用起始劑以及水作為一分散介質，並較溫和地攪 拌该反應器中的内容物來生效。在該乳化聚合作用過程 中，一氯乙烯單體係藉由該表面活性劑之作用而被乳化成 微小液滴，且聚合作用係在覆有一層表面活化劑微膠粒的 各液滴内發生，以產生呈乳膠形式並具有一為約〇 至〇 5 V m之粒子直徑的聚合物粒子。 經濟部智慧財產局員工消費合作社印製 為了製造包含具有較由該乳化聚合流程所製成之粒子 聚合物粒子更大之粒子直徑的氯乙烯聚合物乳膠，可進行 一種種核乳化聚合作用，其中聚合作用係在由一預備聚合 作用所製借之聚合物種核的存在下發生，且該乳化劑之用 量被控制在一對應於20至60%用以覆蓋各液滴整個表面所 需之理論用量的量，俾避免新生微小粒子之產生，且僅有 種核粒子增長。 至於用以製造氯乙烯聚合物乳膠或糊漿樹脂的其他流 程’有一種微懸浮聚合化流程可被述及，其中一由單體、 一表面活性劑、一油溶性聚合作用起始劑及其他物種所組 本紙張尺度適用中國國家樣隼（CNS ) A4規格（210X297公釐） 470752 A7 B7 五、發明説明（2 ) 經濟部智慧財產局員工消費合作社印製 成之混合物係藉由利用諸如一均質機在一水性分散介質中 分散成微小㈣，並隨後進行聚合作用；以及_種種核微 懸淨聚合作用流程，其中聚合作用係在—由預備微懸浮聚 合作用所製備出之聚合物種的存在下發生，該聚合作用係 以-可避免新生粒子產生僅有種粒子增長的方式進行。 在該乳化聚合作用、種核乳化聚合作用、微懸浮聚合 作用及種核微懸浮聚合作用之流程中，攪拌係利用一攪拌 器來進行，以移除聚合反應所產生之聚合熱，並將單體饋 入反應器中之反應址。若該搜拌太弱，則反應熱不可能完 全被移除，且該聚合混合物之溫度被升高至一不適當的程 度，而造成在聚合物品質與操作安全性上的問題，以及單 體饋入反應址的阻礙與聚合反應之延遲。相反地，若該攪 拌過強，增長之聚合物粒子偶爾會凝聚而導致粗糙之粒子 或鋼垢，所製造出之乳膠具有丨良之機械安定性，有時會 造成易受熱之非所欲奶油狀產物，該奶油狀產物亦會造成 聚合物品質與操作安全性上的問題。 因此，攪拌係在一恆定強度下於聚合作用期間藉由利 用溫和擾拌條件下進行。之強度係經選定而至—使得 在最終聚合階段會展現較低機械安定性之聚合物乳膠仍具 有可接受程度之安定性。因Λ ’即使在聚合化速率係由聚 合作用起始階段中之單體擴散來決定的步驟中，溫和的反 應仍會發生。再者，當聚合反應完成後回收未反應單體時， 攪拌需停止’因為此時聚合物乳膠之機械安定性會較最终 聚合階段為差。此會導致由該聚合物乳膠回收單體的降低。47075 A7 B7 V. Description of the invention (1) (Please read the notes on the back before writing this page) The present invention relates to a method for manufacturing vinyl chloride polymers. More clearly, this case is about-a kind of vinyl chloride polymer with reduced content of agglomerates, good mechanical stability, and reduced content of unreacted monomers by changing the stirrer bar during the polymerization Latex method. In order to make vinyl chloride polymer latex or paste resin, vinyl chloride can be polymerized by a pore polymerization process, wherein the polymerization is performed by using an anion in a pressure polymerization reactor provided with a cooling interlayer. Or a non-ionic surfactant acts as an emulsifier, a water-soluble peroxide acts as a polymerization initiator and water acts as a dispersion medium, and the contents of the reactor are gently stirred to take effect. During the emulsification polymerization process, a single vinyl chloride system is emulsified into tiny droplets by the action of the surfactant, and the polymerization occurs in each droplet covered with a layer of surfactant micelles. To produce polymer particles in the form of a latex and having a particle diameter of about 0 to 0.05 V m. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs in order to produce vinyl chloride polymer latex containing a larger particle diameter than the particle polymer particles made by the emulsification polymerization process, a kind of nuclear emulsification polymerization can be performed, where Polymerization occurs in the presence of a polymer seed core made by a preliminary polymerization, and the amount of the emulsifier is controlled to correspond to 20 to 60% of the theoretical amount required to cover the entire surface of each droplet The amount of plutonium avoids the generation of new tiny particles, and only the nuclear particles grow. As for the other processes used to make vinyl chloride polymer latex or paste resin, there is a microsuspension polymerization process that can be mentioned, one of which consists of monomers, a surfactant, an oil-soluble polymerization initiator, and others. The paper size set by the species is applicable to the Chinese national sample (CNS) A4 (210X297 mm) 470752 A7 B7 V. Description of the invention (2) The mixture printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is used by using The homogenizer disperses into tiny mashes in an aqueous dispersion medium and then performs polymerization; and _ various nuclear micro-suspension polymerization processes, where the polymerization is in the presence of polymer species prepared by preliminary micro-suspension polymerization It happens that the polymerization is performed in such a way that new particles can be avoided and only particles can grow. In the processes of emulsification polymerization, seed-core emulsion polymerization, micro-suspension polymerization, and seed-core micro-suspension polymerization, stirring is performed by using a stirrer to remove the polymerization heat generated by the polymerization reaction, and separate the polymerization heat. The volume is fed into the reaction site in the reactor. If the search is too weak, the reaction heat cannot be completely removed, and the temperature of the polymerization mixture is raised to an inappropriate level, causing problems in polymer quality and operational safety, and monomers. Obstacles fed to the reaction site and polymerization delay. On the contrary, if the stirring is too strong, the growing polymer particles may occasionally agglomerate and cause rough particles or steel scale. The latex produced has good mechanical stability and sometimes causes undesired creaminess that is susceptible to heat. Product, the creamy product also causes problems in polymer quality and handling safety. Therefore, the stirring is performed at a constant intensity during the polymerization by using mild stirring conditions. The strength is selected so that polymer latexes that exhibit low mechanical stability during the final polymerization stage still have an acceptable level of stability. Since Λ ', even in the step where the polymerization rate is determined by the monomer diffusion in the initial stage of the polymerization, a mild reaction will still occur. Furthermore, when the unreacted monomer is recovered after the polymerization reaction is completed, the stirring needs to be stopped 'because the mechanical stability of the polymer latex at this time will be inferior to the final polymerization stage. This results in a reduction in monomer recovery from the polymer latex.
本紙張尺度適用中國國家榇準（CNS ) A4liir^~^i5T (請先閲讀背面之注意事項再填寫本頁) 裝· 訂 I •線 470752 A7 B7 經 濟 部 智 慧 財 產 局 8 工 消 合 作 社 印 製 本紙張又度適用中國國家標準（CMS ) A4規格（210x297公釐 五、發明説明（3 ) 發明簡述 依前所述’本發明之—主 ^ 要目的在於提供一種用以製 造一氣乙烯聚合物之方法，发由 其中该聚合反應物係在依特定 聚合作用階段而適當地變化的條 ^诛件下破攪拌，以產生罝有 降低含量之凝聚體、展現良好 开之機械安定性並含有降低含 罝之未反應早體的聚合物乳勝。 在本發明之一態樣中，1传描 ”如如供一種用以製造氣 聚合物之方法，其包含在一措挫取 '、歸 攪拌聚合反應器中，藉由一乳 化或種核乳化聚合流程來聚合化氧^ & 士 匕乳乙烯或一由氣乙烯盥此 聚單體所構成之混合物，同時， 〃 ^ 於一由〇%轉化至6〇%轉化（不含）之第-時期期間，每 單位體積液相之淨授掉出力被維持在〇^〇.3kw/m 圍内； 早巴 於一由_轉化至75%轉化（不含）之第二時期期間，每 單位體積液相之淨攪拌出力被維持在該第一時期所使用之 淨攪拌出力之50%至1〇〇%的範圍内； 於一由75%轉化至聚合作用終止之第三時期期間，每 單位體積液相之淨揽拌出力被維持在該第一時期所使用之 淨攪拌出力之20%至50%的範圍内；以及 於聚合作用終止後回收未反應單體時，每單位體積液 相之淨«出力被料在刻咖kw/m3的範圍内。 在本發明之另一態樣中，其係提供一種用以製造氯乙 烯聚合物之方法’其包含在_攪拌聚合反應器中，藉由一 微懸浮或種微懸浮聚合流程來聚合化氯乙烯或―由“烯 ^衣 j!訂. —. '線 ----- (請先閲讀背面之注意事項再填寫本頁} 470752 五、發明説明（4 與共聚單體所構成之混合物，同時， m於一㈣轉化至轉化（不含）之第一時期期間，每 早位體«相之淨„出力被维持在謂錢2 圍内，· 旳轨 於一由4〇%轉化至75%轉化（不含）之第二時期期間，每 早位體積液相之淨攪拌出力被維持在該第一時期所使用之 淨攪拌出力之50%至1〇0%的範圍内； 於-由75%轉化至聚合作用終止之第三時期期間，每 單位體積液相之淨授拌出力被維持在該第一時期所使用之 淨擾拌出力之丨5%至50%的範圍内；以及 於聚合作用終止後回收未反應單體時，每單位體積液 相之淨攪拌出力被維持在〇 〇〇〇1至〇 〇〇〇8 kw/m3的範圍内。 發明詳述 經濟部智慧財產局員工消費合作社印製 在依據本發明之用以製造氣乙烯聚合物的方法中，特 定之攪拌條件被使用在乳化聚合作用、種核乳化聚合作 用、微懸浮聚合作用或種核微懸浮聚合作用中。氣乙烯係 單獨地或作為一單體混合物進行聚合化，該單體混合物依 該單體混合物之總重量計係較佳為含有至少5〇重量％且更 佳為至少75重量％之氯乙烯’以及一或多種不超過5〇重量％ 且更佳為不超過25重量％可與氯乙烯共聚合之烯屬不飽和 單體。 至於可與氯乙烯共聚合之烯屬不飽和單體的特定例 子’則可提及諸如乙烯及丙烯之烯烴；諸如乙酸乙烯酯及 丙酸乙烯醋之乙稀醋；諸如丙稀酸及異丁烯酸之未儉和單 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 470752 A7 B7 五、發明説明（ 羧酸；諸如丙烯酸曱酯、丙烯酸乙酯、丙烯酸正丁酯、2_ 經乙基丙浠酸酯、異丁稀酸乙酯及n，n_二甲基胺乙基異丁 烯酸酯之未飽和單羧酸酯；諸如丙烯醯胺異丁烯醯胺之未 飽和醯胺；諸如丙烯腈及異丁烯胯之未飽和腈；諸如馬來 酸及s馬酸之未飽和二羧酸；此等未飽和二羧酸之酯類及 醯胺，N-取代馬來醯胺；諸如乙埽甲醚及乙烯乙醚之乙烯 醚；以及諸如亞氣乙烯之亞乙烯化合物。 本發明之方法中，攪拌聚合混合物之強度係依聚合作 用期間單體之粒子轉化而變化，且亦在聚合作用完成後回 收未反應單體時被適當地選定。 經濟部智慧財產局員工消費合作社印製 (請先聞讀背面之注意事項再填寫本育) 決定聚合作用期間單體轉化的方法並無特定限制，該 轉化可藉由下列方法來決定：諸如光線散射法來測量聚合 物粒子濃度與其粒子直徑，或藉由測量反應器夾層内冷卻 水之溫度與流速及聚合溫度，由反應器内之測量值總合出 放熱值，以及由該總合放熱值求出轉化狀況。特別是，後 法較佳，其中該轉化狀況係由測量來決定反應器夾層内冷 部水之流速及溫度以及聚合溫度。此乃因為該轉化可在無 實質延遲下被測定，因此，淨攪拌出力可藉由將該轉化測 疋值傳輪至攪拌器之馬達而被直接且適當地控制。 用於本發明之方法的聚合反應器並無特定限制，且可 具有任何構造及形狀。例如，該反應器可設有一外夾層或 —内夾層或一回流冷凝器。設有一内夾層之反應器係特別 有利，其優點在於因熱量轉移所造成之熱量喪失為最小， 因而可正確地測量反應器内之放熱及單體之轉化。聚合混 470752 A7 B7 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁} 合物在反應器内擾拌之流程及授掉裝置並無特別限制。至 於攪拌槳片，則可使用諸如富得勒(pfaudler)槳片、多重富 得勒槳片、鰭狀槳片、多重鰭狀槳片、布魯馬琴(b__ 槳片、錨式槳片、迴圈槳片、Max_Blend槳片及全區域槳片。 所使用之導流並無特別限制，對於授掉導流器之例子則 可提及管狀導流器、指狀導流器與D_型導流器。 當聚合作用係藉由本發明方法中之乳化聚合或種核乳 化聚合流程來進行時，（1)在一由0%轉化至轉化（不含） 之第-時期期間，每單位體積液相之淨授掉出力被维持在 0.1至0.3kW/m3的範圍内；⑵在„由6⑽轉化至75%轉化（不 含）之第二時期期間，每單位體積液相之淨攪拌出力被維持 在該第一時期所使用之淨搜掉出力之5 〇 %至i 〇 〇 %的範圍 内；⑶在-由75%轉化至聚合作用終止之第三時期期間， 每單位體積液相之淨攪拌出力被維持在該第一時期所使用 之淨攪拌出力.之20%至50%的範圍内；以及（4)在聚合作用 終止後回收未反應單體時，每單位體積液相之淨攪拌出力 被維持在0.0001至〇.〇〇〇8 kW/m3的範圍内。 經濟部智慧財產局員工消費合作社印製 至於用於本案發明書及所附申請專利範圍令的「—由 0%轉化至60%轉化（不含）之第一時期」此片語，我們係音 欲表示該第一時期是由〇%轉化延伸至6〇%轉化，但上限 60%被排除在該第一時期之特定範圍以外。換言之，⑽％轉 化被排除在該第一時期以外，但被包含在後續之第二時期 内。同理，在第二時期令「75%轉化（不含）」此名詞係指限 值75%轉化被排除在該第二時期以外，但被包含在後續之 本紙張尺度適用中國國家榇準（CNS ) A4規格（21〇χ29?公釐） 470752 經濟部智慧財產局員工消費合作社印製 A7 ._____ B7五、發明説明（7 ) 第三時期内。 在乳化聚合作用中，一聚合反應器被饋入純水、—乳 化劑及一水溶性聚合作用起始劑；將該反應器中之内容物 予以脫氣或利用一諸如氮氣之惰性氣體加以清除；將氯乙 '歸單獨地或與其他可共聚單體共同納入該反應器内；以及 進行攪拌，同時，在一由〇%轉化至60%轉化之第—時期期 間’每單位體積液相之淨攪拌出力被維持在一為〇·丨至〇3 kW/m之範圍内，且該反應器内之溫度被提高，以起始聚 合作用。該聚合作用之溫度係較佳為位在3〇至80°C下。 至於使用於此處的「每單位體積液相之淨攪拌出力」 此名詞’我們係意欲表示總攪拌輸入量與一變速器的驅動 負載量或者是一減速器與一攪拌器之間的差異，該差異再 除以反應器内之液相體積。每單位體積液相之淨攪拌出力 係以下列等式來計算： Pv=P/V=(NP · ρ · η3 · d5)/gc · V 其中pv :每單位反應器體積之淨攪拌出力（kW/m3) P :攪拌所需之出力（kW) V :反應器中之液相體積（m3) NP .功率數，其為一經實驗測定之定值。例如，富得勒槳 片具有一為1.5之功率數’ Max-Blend槳片及全區域槳片具 有一為2.5之功率數，以及迴圈紫片及 猫式槳片具有一為1.0之功率數。 ρ .反應器中液態内容物之密度（kg/cm3) η :(每秒）迴轉數 .I— II -111 1- II 11 I I - I II 1 m ' m I 1^1 n ϋ 、T备， (請先聞讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210x297公釐） 470752 A7 B7 五、發明説明（8 經 智 慈 財 產 局 畐 X 消費 合 作 杜 印 製 d :攪拌槳片之直徨（m) gc :重力轉換因子[(kg · m：)/Ug • sec2)] 至於決定Μ拌出力的另一種方法，其可為一種利用 一設在一用以驅動反應器之攪拌裝置的馬達上之安培計的 方法。在此方法中，-用以驅動一變速器或—減速器與撲 掉裝置的負載量係由-安培計來測量。該測量係在反應器 載入一單體混合物之前以及聚合作用期間進行。淨攪拌出 力（ρν)係由下式來計算： Pv=(El-E2)x EV/V 其中E1 .聚合作用期間所測得的電流； E2 .反應器載入一單體混合物之前所測得的電流； EV :有效電壓；以及 V:反應器内之液體體積 至於供用於乳化聚合作用之乳化劑的例子，可述及者 為諸如十二烷基苯颯及十四烷基苯颯之烷基苯颯；諸如二 辛基硫代號珀酸納及二己基硫代琥珀酸鋼之硫代琥珀酸 鹽’諸如月桂酸鈉及半-固化牛脂脂肪酸鈉之脂肪酸鹽，·諸 如聚氧乙烯月桂基-醚-硫酸鈉鹽及聚氧乙烯壬基-苯基_醚 硫酸納鹽之乙氧硫酸鹽；烷磺酸鹽；烷基醚磷酸酯鈉鹽； 以及諸如聚氧乙烯壬基苯基醚及聚氧乙烯脫水山梨醇月桂 酉日之非離子性表面活性劑。乳化劑之使用如下：藉由聚合 作用開始之前添加，或藉由在聚合作用期間添加以增大粒 子直徑’並聚合作用開始之前添加。依重量份之單體為 準’乳化劑之用量係較佳為位在〇.丨至5重量份，且更佳為 本紙張尺國家標❼NS) A4規格( -ti- (請先閱讀背面之注意事項再填寫本頁) .麥' -1]--------------------- 470752 A7 B7 五、發明説明（ 0.1至3重量份之範圍内。 對於水洛性聚合作用起始劑之例子，可述及者為諸如 '過硫酸納、過硫酸錢及過硫酸之水溶性過氧化物；諸如一 由該等水/合!生過氧化物或一諸如氣過氧化枯缚或氮過氧化 特丁炫之氫過氧化物與一諸如酸性亞硫酸納、亞硫酸錢或 抗壞血I之還原劑所構成之組合的氧化還原起始劑；以及 諸如2,2 -氮雜雙(2-曱基丙醯胺)二價酸鹽之水溶性雜氮化 合物。 在種核乳化聚合作用中，聚合反應器被饋入純水、— 種核聚合物、-水溶性聚合作用起始劑及一乳化劑；將反 應器中之内容物予以股名 .._ 脫乳’或利用一諸如氮之惰性氣體加 h月除，進#將氯乙婦單獨地或與其他可共聚單體丘同 饋入該反應器中；以及進行溫和檀掉，並將反應器内:溫 度升高以起始聚合作用。聚合溫度係較佳為位在30至歡 之範圍内。將額外之a i a 一 -卩之礼化劑加入該水性聚合混合物内，該 乳化劑係呈一不超過+ ;覆盍隨者聚合作用開始而持續增 長之粒子的表面所愛少田曰 所南之用置。因此，粒子安定性在聚合作 用期間得以維持。至於人 、X洛性聚合反應起始劑及乳化劑的 例子，可述及者係如前述於乳化聚合作用者。 在本發月之方法中，攪拌被進行’同時在乳化聚合 Z始顏轉化)至60%轉化(不含)的第一時期中，每單位 體積液相之淨攪拌出力被 ,,„ A 溉、准符在為0.丨至0.3 kw/m3,且較 kw; ;15至〇.25 之範圍内。若該淨撥拌出力小於01 一^則聚合作用之速率係由單體之擴散來決定，聚合 木紙張 (請先閲讀背面之注意事項再填寫本頁) 、1' 經濟部智慧財產局員工消費合作社印製 470752 A7 B7 五、發明説明（10 作用因而延長，熱量轉移速率 X古八 '且聚0熱之移除變得 刀。右該淨攪拌出力大於〇·3 kW/m3,則增長中之 /會傾向凝聚成膠膠凝塊或鋼垢 /之粒子 安定性會降低。 1所仔來合物乳膠之機械 她轉化至75%轉化(不含)的第 進行，同時，每單位 -時期所㈣ ㈣拌出力被維持在該第 使用之淨攪拌出力之至刪且較佳為6〇至 Γ:: Γ力圍内。若該淨授拌出力小於該第-時期所使用之 #攪拌出力的50%，則聚厶祚玥 K乍用之逮率係由單體之擴散來 決疋1合作用因而延長，熱量轉移速率降低，且聚合熱 之移除變得不充分。若該淨授掉出力大於該第一時期所使 用之淨攪拌出力的100%，則增長中之粒子會傾向凝聚成勝 凝塊或鋼垢’且所得聚合物《之機射定性會降低。 在75%轉化至聚合作用終止的第三時期中，授掉持續 進打’同時，每單位體積液相之淨授拌出力被維持在該第 一時期所使用之㈣拌“之鳩至鄉域佳為加至鄕 經 濟 部 智 慧 財 產 局 員 X 消 費 人 h 社 印 製 的範圍内。若該淨授拌出力小於該第一時期所使用之淨授 拌出力的20% ’則聚合作用之速率係由單體之擴散來決 定’聚合作用因而延長’熱量轉移速率降低，且聚合熱之 移除變得不充分。相反地，若該淨搜拌出力大於該第一時 期所使用之淨授拌出力的5〇%，則增長中之粒子會傾向凝 聚成谬凝塊或鋼垢，且所得聚合物乳膠具有不良之機械安 定性。 當轉化超過約85重量％時，聚合作用之速率會降低。 本紙浪尺度適用中國國家鱗（CNS )八4規格（2l〇Xi97公羡） ~----- 470752 A7 B7 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 五、發明説明（11 ) 因此’就產量觀之，聚合作用通常在85至95重量％之轉化 下終止。聚合作用之終止係藉由添加一諸如氩醌之聚合作 -用停止劑而生效，並同時將反應器内之溫度控制在一介於 30 C至0°C下，以回收未反應單體。為了回收未反應單體， 一設在反應器上部並界定位在液態内容物上之氣相的閥被 打開’俾將未反應單體引導至一與壓縮機相連接的回收系 統。反應器内之聚合物乳膠具有不良之安定性，故將之溫 和攪拌，即在每單位體積液相之淨攪拌出力為〇.〇〇〇1至 0.0008 kW/m3，且較佳為o.oooi至0.0005 kw/m;。若該淨攪 拌出力小於0.0001 kW/m3 ’則由液態内容物中回收未反應 單體會變得困難。相反地，若該淨攪拌出力超過〇.〇〇〇8 kW/m3 ’則聚合物粒子會傾向於凝聚成膠凝塊或鍋垢。只 要達成本發明之目的，使該淨攪拌出力維持在〇.〇〇〇丨至 0.0005 kW/m3之出力下的時間並無特別限制且可為短暫 的。開動-停止之控制可使用於攪拌。 在微懸浮聚合作用中，氯乙埽或一由氯乙稀、可共聚 烯屬不飽和單體、-油溶性聚合作用起始劑、一乳化劑與 諸如高級脂肪酸及其他添加劑之任擇聚合佐劑所構成的混 合物係在—水性介質中進行預混合，並藉由一均質機均質 化該混合物，以控制油性液滴之粒子直經。至於均質機的 例子，可述及者為膠體研磨機、振蘆授掉機及兩階段高壓 泵。將该均質液饋入一聚合反應器内，於該處，該液體被 溫和地挽拌，並提高該反應器之溫度，以起始聚合作用。 進行聚合作用，直到達成預定之轉化。聚合溫度係較佳為 (請先聞讀背面之注意事項再填寫本育) I 11« - « -I . .裝 訂 i |線_ 本紙張尺度賴t酬緖 470752 Μ Β7 五、發明説明（I2 位在30至80。(：之範圍内。 (請先閱讀背面之注意事項再填寫本頁) 就油溶性聚合作用起始劑的例子而言，可述者為有機 過氧化物，其包括諸如乙醢過氧化物、3,5,5_三甲基己醯過 氧化物、月桂醯過氧化物與苯曱酿過氧化物之二醯基過氧 化物；諸如曱乙酮過氧化物之酮過氧化物；諸如笨曱醯基 氫過氧化物、氫過氧化枯烯、對位_氫過氧化枯烯、氫過氧 化二異丙基笨及對位-氫過氧化甲烷；諸如特丁基過氧新戊 之過氧g曰，諸如_異丙基過氧1重碳酸輯及二乙己基過 氧重碳酸酯之過氧重碳酸酯；諸如乙醢環己基磺醯基過氧 化物之磺醯基過氧化物；諸如一種由一擇自於上述有機過 氧化物之有機過氧化物與一諸如離白粉之還原劑所構成的 組合的氧化還原型聚合作用起始劑；以及諸如2,2，-氮雜雙 異丁腈、2,2'-氮雜雙（2-甲基丁腈）、2,2，_氮雜雙（2,4_二甲基 戊胯）及2,2，-氮雜雙（4-甲氧基-2,4-二甲基戊胯之雜氮化合 物。至於乳化劑之例子，可述及者為載述於乳化聚合作用 者0 經濟部智慧財產局員工消費合作社印製 在種核微懸浮聚合作用中，一聚合反應器被饋入純 水、一含有殘留聚合作用起始劑之種核聚合物，以及任擇 之組份，將反應器之内容物予以脫氣或利用諸如氮之惰性 氣體加以清除，並隨後添加一乳化劑以及氯乙烯或—由氣 乙烯與一或多種可共聚烯屬不飽和單體所構成之混合物。 溫和攪拌該内容物，並提高反應器内之溫度以起始聚合作 用。較佳地’聚合作用係位在30至80 C之範圍内。至於乳 化劑之例子，可提及者為載述於乳化聚合作用中者。在種 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） 470752 A7 B7 五、發明説明（I3 ) 核微懸浮聚合作用的情形下，並不需要將聚合作用起始劑 添加至含種核聚合物之水性介’因為所使用之種核聚 合物含有殘留之聚合作用起始劑。 在微懸浮聚合作用或種核《浮聚合作用中，攪拌係 經進行，以使得在該由0%轉化至4〇%轉化（不含）之第一時 期期間’每單位體積液相之淨授拌出力被維持在〇 〇8至[ kW/m3之範圍内，且較佳為〇.丨至〇a 8 Wm3。若該淨攪拌出 力小於_ 則熱轉移速率會降低，且聚合熱之移 除會變得不充分。反之，若該淨授掉出力大於〇 2kw/m3, 則增長中之粒子會傾向凝聚成膠凝塊或鍋垢，且所得聚合 物乳膠具有不良之機械強度。 經 濟 部 智 慧 財 產 局 消 費 合 作 社 印 製 (請先閲讀背面之注意事項再填寫本頁) 在40%轉化至75%轉化（不含）的第二時期期間，攪拌係 經進行’以使得每單位體積液相之淨擾拌出力被維持在該 第一時期所使用之淨授拌出力之5〇%至1〇〇%且較佳為跑 100%的範圍内。若該淨授拌出力小於該第一時期所使用之 淨擾拌出力的5G%，則熱量轉移速率會降低，|聚合熱之 移除會變得不充分。反之，若該料“力大於該第—時 期所使用之淨攪拌出力的i 〇 〇 % ’則增長中之粒子會傾向凝 聚成膠凝塊或鍋垢’且所得聚合物乳膠具有不良之機械強 在由75%轉化至聚合作用終止的第三時期期間，攪拌 持續進行，以使得每單位體積液相之淨攪拌出力被維持在 該第一時期所使用之淨攪拌出力之15%至5〇%且較佳為跗 至30%的範圍内。若該淨授拌出力小於該第一時期所使用 本·氏張尺度適用中國國家標準（Cns ) A4規格（2i〇X 297公嫠） 470752 A7 B7 五、發明説明（l4 之淨授拌出力的15% ’則熱量轉移速率會降低，且聚合熱 之移除會變得不充分。反之’若該淨攪拌出力大於該第— 日^期所使用之淨檀拌出力的鄉，則增長中之粒子會傾向 凝聚成膠凝塊或鋼垢，且所得聚合物乳膠具有不良之機 強度。 # 在種核乳化聚合作用、微懸浮聚合作用及種核微懸浮 聚合作用t ’聚合作用通常在85至95%轉化下終止。當聚 合作用完成後回收未反應單體時，反應器内之聚合物= 具有不良之機械強度，因此’其被溫和地攪拌，即在每單 位體積液相之淨授拌出力為〇.〇〇〇1至〇 〇〇〇8 mm3下，且較 佳為在〇·讀至〇__5 kw/m3T。若淨攪拌出力小於〇卿 kW/m3’ ％由液態内容物中回收未反應單體會變得困難。 反之，若淨攪拌出力大於〇._8 kw/m3，則聚合物粒子會 傾向於凝聚成膝凝塊_垢。只要可達成本發明之目的， 淨攪摔出力維持於0.0001至〇._8 kw/m^範圍内的時間 並無特別限制且可為短暫的。開動·停止之控制可使用於搜 拌。 依據本心明之方法，搜拌出力係依聚合作用期間單體 之特定轉化而被適當地控制’或於回收未反應單體時被控 制。因此，聚合作用係有效地進行，聚合物凝膠甚少產生， 且所得之聚合物乳膠展現出良好的機械安定性，並具有降 低量之未反應單體。 現在，本發明將藉由下列實例來專，述，惟該等 實例並不意欲被用來限制本發明的申請專利範圍。 f紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐 (請先閲讀背面之注意事項再填寫本頁) 言 經濟部智慧財產局員工消費合作社印製 470752 A7 -------B7 五、發明説明~ ~~ — — 在下列實例與比較例中，氣乙婦聚合物乳勝係藉由下 列方法來評估。 > (請先閲讀背面之注意事項再填寫本頁) (1) 凝膠含量（重量％) #由-具有60篩目大小的金屬線篩來過濾一氣乙烯聚 合物乳膠，俾以收集粗製粒子。到下反應器内壁上的沈積 $。將收集之粗製粒子及該沈積物予以合併，再乾燥並接 著稱重。由此而得之凝膠重量依饋入反應器内之單體重量 為準，而以％表示之。 (2) 中心粒子直徑（从瓜） 中心粒子直桎係藉由利用—雷射散射粒子直徑測量裝 置（由 Malvern Co.所供應之Master Sizer Ms-2)來測量。 (3) 機械安定性（kW/m3) 將5升氣乙烯聚合物乳膠饋入一具有丨58爪爪内徑並設 置具有85 mm長槳片之攪拌器的5升錐形瓶中。在275 rpm 與70 C之/里度.下授拌§亥内容物’並在攪拌間始至粒子開始 凝聚的期間進行測量。機械安定性係由攪拌出力總值來表 示。 經濟部智慧財產局員工消費合作社印製 (4) 殘留單體含量（ppm) 在回收未反應單體的步驟之後，製備一具有已知固態 内容物的氯乙烯聚合物乳膠樣品。將該樣品加熱至1〇(rc， 以蒸發殘留之氯乙烯單體，並藉由氣相層析法來測量其在 蒸發氣態混合物内之含量。殘留之單體含量係依聚合物重 量而以ppm來表示。This paper size applies to China National Standards (CNS) A4liir ^ ~ ^ i5T (Please read the notes on the back before filling out this page) Binding · Order I • Line 470752 A7 B7 Intellectual Property Bureau of the Ministry of Economic Affairs 8 Printed by Industrial Consumers Cooperative The paper is again applicable to the Chinese National Standard (CMS) A4 specification (210x297 mm. 5. Description of the invention (3) Brief description of the invention according to the above-mentioned "The invention-the main ^" The main purpose is to provide a kind of ethylene polymer A method in which the polymerization reaction system is broken and agitated under conditions appropriately changed according to a specific polymerization stage to produce aggregates having reduced content, exhibiting good mechanical stability and containing reduced content. The polymer milk of unreacted early body wins. In one aspect of the present invention, 1 is described as "for a method for producing an aeropolymer, which includes a one-step process", and agitation polymerization. In the reactor, oxygen is polymerized by an emulsification or seed emulsification polymerization process ^ & ethylene styrene milk or a mixture of gaseous vinyl monomers, and 〃 ^ During the first period of conversion to 60% conversion (not included), the net output force per unit volume of liquid phase is maintained within the range of 0.3kw / m; Zaoba Yuyi converted from _ to 75% conversion During the second period (excluding), the net stirring output per unit volume of the liquid phase is maintained within the range of 50% to 100% of the net stirring output used in the first period; During the third period when the polymerization is terminated, the net stirring power per unit volume of liquid phase is maintained within the range of 20% to 50% of the net stirring output used in the first period; and unreacted is recovered after the polymerization is terminated. In the case of monomers, the net output per unit volume of liquid phase is expected to be in the range of kw / m3. In another aspect of the present invention, it provides a method for manufacturing a vinyl chloride polymer. Contained in _ agitated polymerization reactor, through a micro-suspension or micro-suspension polymerization process to polymerize vinyl chloride or ―ordered by olefin coating j! —. 'Line ----- (Please read the back first Please pay attention to this page before filling in this page} 470752 V. Description of the invention (4 Mixture with comonomer At the same time, during the first period when m is transformed into transformation (not included), the output of each early body «phase of the net« is maintained within the range of 谓 2, and the 旳 track is transformed from 40% to During the second period of 75% conversion (excluding), the net agitation output of each early volume liquid phase is maintained within the range of 50% to 100% of the net agitation output used in the first period; During the third period when 75% of the polymerization is terminated, the net stir-out force per unit volume of liquid phase is maintained within the range of 5% to 50% of the net disturbance stir-out force used in the first period; and When the unreacted monomer is recovered after the end of the action, the net stirring output per unit volume of the liquid phase is maintained in the range of 0.001 to 8000 kw / m3. Detailed description of the invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs In the method for producing gaseous ethylene polymers according to the present invention, specific stirring conditions are used in emulsion polymerization, seed core emulsion polymerization, and microsuspension polymerization. Or seed nuclear microsuspension polymerization. Gas vinyl is polymerized individually or as a monomer mixture, which preferably contains at least 50% by weight and more preferably at least 75% by weight of vinyl chloride based on the total weight of the monomer mixture. And one or more ethylenically unsaturated monomers that are copolymerizable with vinyl chloride in an amount of not more than 50% by weight and more preferably not more than 25% by weight. As for specific examples of ethylenically unsaturated monomers which can be copolymerized with vinyl chloride, mention may be made of olefins such as ethylene and propylene; vinyl acetates such as vinyl acetate and vinyl propionate; such as acrylic acid and methacrylic acid The size of the paper and the single paper are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 470752 A7 B7 V. Description of the invention (Carboxylic acid; such as ethyl acrylate, ethyl acrylate, n-butyl acrylate, 2_ Unsaturated monocarboxylic acid esters of ethyl propionate, ethyl methacrylate and n, n-dimethylamine ethyl methacrylate; unsaturated amines such as acrylamide and methacrylamide; such as Unsaturated nitriles of acrylonitrile and isobutylene fluorene; unsaturated dicarboxylic acids such as maleic acid and s-maleic acid; esters and amines of these unsaturated dicarboxylic acids, N-substituted maleimidine; such as acetamidine Methyl ether and vinyl ether of vinyl ether; and vinylene compounds such as vinylene. In the method of the present invention, the strength of the stirred polymerization mixture is changed according to the particle transformation of the monomers during the polymerization, and also after the polymerization is completed Recovery of unreacted orders It is appropriately selected at the time of printing. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this education) There are no specific restrictions on the method of monomer conversion during polymerization. The conversion can be achieved by The following methods are used to determine: such as the light scattering method to measure the polymer particle concentration and its particle diameter, or by measuring the temperature and flow rate of the cooling water in the reactor interlayer and the polymerization temperature, and the measured values in the reactor are combined to give an exothermic value, And the conversion status is obtained from the total exothermic value. In particular, the post method is preferred, where the conversion status is determined by measurement to determine the flow rate and temperature of the cold water in the reactor interlayer and the polymerization temperature. This is because the conversion can It is measured without substantial delay, and therefore, the net agitation output can be directly and appropriately controlled by transmitting the conversion measurement value to the motor of the agitator. The polymerization reactor used in the method of the present invention is not specific Restricted, and can have any configuration and shape. For example, the reactor may be provided with an outer sandwich or-an inner sandwich or a reflux condenser. An inner sandwich is provided The reactor system is particularly advantageous. Its advantage is that the heat loss caused by heat transfer is minimal, so it can accurately measure the exotherm and monomer conversion in the reactor. Polymerization Mix 470752 A7 B7 V. Description of the invention ((please first Read the notes on the back and fill in this page} There are no special restrictions on the process of mixing and mixing of the compounds in the reactor. As for the stirring paddles, such as pfaudler paddles, multiple richer paddles, etc. Paddle paddles, fin paddles, multiple fin paddles, bruma (b__ paddles, anchor paddles, loop paddles, Max_Blend paddles, and full-area paddles. The flow guide used is not special Restriction. For examples of deflectors, tubular deflectors, finger deflectors, and D-type deflectors can be mentioned. When the polymerization is by the emulsification polymerization or seed emulsion polymerization process in the method of the present invention In the coming period, (1) during the first period of conversion from 0% to conversion (excluding), the net output force per unit volume of liquid phase is maintained in the range of 0.1 to 0.3 kW / m3; „The second period from 6⑽ to 75% conversion (excluding) In the meantime, the net stirring output per unit volume of the liquid phase is maintained within the range of 50% to 100% of the net search output used in the first period; (3) The conversion from -75% to the end of the polymerization During the three periods, the net stirring output per unit volume of the liquid phase was maintained within a range of 20% to 50% of the net stirring output used in the first period; and (4) the unreacted monomer was recovered after the polymerization was terminated. At that time, the net stirring output per unit volume of the liquid phase was maintained in the range of 0.0001 to 0.0008 kW / m3. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed the phrase "—the first period from 0% to 60% conversion (excluding)" used in the present invention and the attached patent application order. It means that the first period is extended from 0% to 60% conversion, but the upper limit of 60% is excluded from the specific range of the first period. In other words, the ⑽% conversion is excluded from the first period, but is included in the subsequent second period. Similarly, in the second period, the term "75% conversion (excluding)" means that the limit of 75% conversion is excluded from the second period, but is included in the subsequent paper standards that apply the Chinese National Standard ( CNS) A4 specification (21 × 29? Mm) 470752 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ._____ B7 V. Description of invention (7) Within the third period. In the emulsion polymerization, a polymerization reactor is fed with pure water, an emulsifier and a water-soluble polymerization initiator; the contents of the reactor are degassed or purged with an inert gas such as nitrogen. ; Into the reactor alone or together with other copolymerizable monomers; and stirring, while agitating, during a first period from 0% to 60% conversion, per unit volume of liquid phase The net agitation output was maintained within a range of 0.1 to 0.3 kW / m, and the temperature in the reactor was increased to initiate polymerization. The polymerization temperature is preferably at 30 to 80 ° C. As for the "net agitation output per unit volume of liquid phase" used herein, the term 'we are intended to indicate the difference between the total agitation input and the driving load of a transmission, or the difference between a reducer and an agitator. The difference is divided by the liquid phase volume in the reactor. The net agitation output per unit volume of liquid phase is calculated by the following equation: Pv = P / V = (NP · ρ · η3 · d5) / gc · V where pv: net agitation output per unit volume of reactor (kW / m3) P: output required for stirring (kW) V: volume of liquid phase in the reactor (m3) NP. power number, which is a fixed value determined by experiments. For example, Fullerer blades have a power number of 1.5 'Max-Blend blades and full-area blades have a power number of 2.5 and loop purple and cat blades have a power number of 1.0 . ρ. Density of liquid contents in the reactor (kg / cm3) η: (seconds) revolutions. I— II -111 1- II 11 II-I II 1 m 'm I 1 ^ 1 n ϋ, T (Please read the precautions on the back before filling this page) This paper size applies Chinese National Standard (CNS) A4 size (210x297 mm) 470752 A7 B7 V. Description of the invention (8 by the Intellectual Property Office 畐 X Consumer Cooperation Du printed d: Straight 徨 of agitating paddle (m) gc: Gravity conversion factor [(kg · m:) / Ug • sec2)] As another method for determining the stirring force of M, it can be a method using A method of driving an ammeter on a motor of a stirring device of a reactor. In this method, the amount of load used to drive a transmission or reducer and flutter is measured by an ammeter. The measurement is performed before the reactor is charged with a monomer mixture and during the polymerization. The net agitation output (ρν) is calculated by the following formula: Pv = (El-E2) x EV / V where E1. The current measured during the polymerization; E2. The current measured before the reactor is loaded with a monomer mixture EV: effective voltage; and V: liquid volume in the reactor. Examples of emulsifiers for emulsification polymerization can be mentioned such as dodecylbenzenehydrazone and tetradecylbenzenehydrazone. Benzyl hydrazone; thiosuccinates such as dioctyl thiosodium peroxoate and dihexyl thiosuccinate steel 'such as sodium laurate and semi-cured tallow fatty acid sodium fatty acid salts, such as polyoxyethylene lauryl -Ether-sodium sulfate and polyoxyethylene nonyl-phenyl ether ether sodium ethoxy sulfate; alkane sulfonate; alkyl ether phosphate sodium salt; and such as polyoxyethylene nonylphenyl ether and Polyoxyethylene sorbitan lauryl is a non-ionic surfactant. The emulsifier is used as follows: by adding before the polymerization starts, or by adding during the polymerization to increase the particle diameter 'and adding before the polymerization starts. Based on the weight of monomers, the amount of emulsifier is preferably in the range of 0.1 to 5 parts by weight, and more preferably this paper rule national standard (NS) A4 specification (-ti- (Please read the back Note for this page, please fill in this page). Mai '-1] --------------------- 470752 A7 B7 V. Description of the invention (in the range of 0.1 to 3 parts by weight) For examples of hydrous polymerization initiators, mention may be made of water-soluble peroxides such as' sodium persulfate, persulfate, and persulfuric acid; Or a redox initiator such as a combination of gas peroxidation or nitrogen peroxytebutine hydroperoxide and a reducing agent such as acidic sodium sulfite, sodium sulfite or ascorbic acid I; and such as A water-soluble heteronitrogen compound of 2,2-azabis (2-amidinopropylamidamine) divalent acid salt. In the seed-core emulsification polymerization, the polymerization reactor is fed with pure water, a core polymer, -Water-soluble polymerization initiator and an emulsifier; give the contents of the reactor a stock name .. _ demilk 'or use an inert gas such as nitrogen and remove it for a month, enter # Chloroethyl is fed into the reactor alone or together with other copolymerizable monomer mounds; and gentle sanding is carried out, and the inside of the reactor is raised: the temperature is increased to initiate the polymerization. The polymerization temperature is preferably located at Within the range of 30 to Huan. Add additional aia a-卩 the ceremonial agent to the aqueous polymerization mixture, the emulsifier is a not more than +; covering the surface of particles that continue to grow as the polymerization begins Ai Shaoda said that the stability of the particles is maintained during the polymerization. As for the examples of human, X-based polymerization initiators and emulsifiers, the aforementioned can be mentioned in the emulsion polymerization In the method of the present month, the stirring is performed 'while the first period of emulsification polymerization (Z) conversion to 60% conversion (excluding), the net stirring output per unit volume of liquid phase is, Irrigation and standard characters are in the range of 0.1 to 0.3 kw / m3, and more than kw ;; 15 to 0.25. If the net stirring power is less than 01 to ^, the polymerization rate is diffused by the monomer To decide, polymer wood paper (please read the notes on the back before filling Page), 1 'Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 470752 A7 B7 V. Description of the invention (10 The effect is prolonged, the heat transfer rate X ancient eight', and the removal of the heat of the heat becomes a knife. Right this net stir When the output is greater than 0.3 kW / m3, the stability of the particles that are growing / will tend to condense into gel gel or steel scale will be reduced. The mechanical properties of a latex compound latex will be converted to 75% (not Inclusive), at the same time, the mixing power per unit-period is maintained within the range of the net mixing power used and preferably within the range of 60 to Γ :: Γ. If the net mixing When the output is less than 50% of the #stirring output used in the first period, the catch rate of the polymer is determined by the diffusion of the monomer. 1 The cooperation is prolonged, the heat transfer rate is reduced, and the heat of polymerization is reduced. Its removal became insufficient. If the net delivery force is greater than 100% of the net stirring output force used in the first period, the growing particles will tend to agglomerate into clumps or steel scales, and the resulting polymer will have a reduced qualitative shot. In the third period when 75% of the polymerization is terminated, the continuous feed is given off. At the same time, the net mixing power per unit volume of liquid phase is maintained at the same level used in the first period. In order to be added to the scope printed by the Consumers of Intellectual Property Bureau of the Ministry of Economic Affairs, X Consumers. If the net blending force is less than 20% of the net blending force used in the first period, then the rate of polymerization is determined by the monomer. Diffusion determines the 'polymerization and therefore prolongation'. The heat transfer rate decreases and the removal of polymerization heat becomes insufficient. Conversely, if the net search force is greater than 50% of the net charge force used in the first period , The growing particles will tend to agglomerate into lumps or steel scales, and the resulting polymer latex has poor mechanical stability. When the conversion exceeds about 85% by weight, the rate of polymerization will decrease. The paper scale is applicable to China National Scale (CNS) 8-4 specification (2l0Xi97 public envy) ~ ----- 470752 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) In other words, the polymerization is usually terminated at a conversion of 85 to 95% by weight. The termination of the polymerization is effected by adding a polymerization-stopping agent such as argonquinone, and at the same time the temperature in the reactor is controlled between To recover unreacted monomers at 30 C to 0 ° C. In order to recover unreacted monomers, a gas-phase valve located in the upper part of the reactor and positioned on the liquid content was opened. It is guided to a recovery system connected to the compressor. The polymer latex in the reactor has poor stability, so it is gently stirred, that is, the net stirring output per unit volume of liquid phase is from 0.0000 to 1 0.0008 kW / m3, and preferably from o.oooi to 0.0005 kw / m ;. If the net stirring output is less than 0.0001 kW / m3 ', it will become difficult to recover unreacted monomers from the liquid content. Conversely, if If the net agitation output exceeds 0.0000 kW / m3 ', the polymer particles tend to agglomerate into a gel or scale. As long as the purpose of the invention is achieved, the net agitation output is maintained at 0.000.丨 The time under the output of 0.0005 kW / m3 is not special It can be short-lived. Start-stop control can be used for stirring. In micro-suspension polymerization, chloroacetam or one is initiated by chloroethylene, copolymerizable ethylenically unsaturated monomer,-oil-soluble polymerization A mixture of an agent, an emulsifier and an optional polymeric adjuvant such as a higher fatty acid and other additives is pre-mixed in an aqueous medium, and the mixture is homogenized by a homogenizer to control the particles of oily droplets Straight through. As an example of a homogenizer, a colloid mill, a vibrating shaker, and a two-stage high-pressure pump can be mentioned. The homogeneous liquid is fed into a polymerization reactor, where the liquid is gently Stir and raise the temperature of the reactor to initiate polymerization. Polymerization is carried out until a predetermined conversion is achieved. The polymerization temperature is better (please read the notes on the back before filling in this education) I 11 «-« -I.. Binding i | Thread _ This paper size is based on 470752 Μ B7 V. Description of the invention (I2 It is in the range of 30 to 80. (:: (Please read the precautions on the back before filling out this page) As an example of an oil-soluble polymerization initiator, the organic peroxide can be described, which includes such as Acetyl peroxide, 3,5,5_trimethylhexamethylene peroxide, lauryl peroxide and benzoyl peroxide-derived peroxoyl peroxide; ketones such as ethylacetone peroxide Peroxides; such as benzyl hydroperoxide, cumene hydroperoxide, para-cumene hydroperoxide, diisopropyl hydroperoxide, and para-hydroperoxide; such as tert-butyl Peroxy neopentyl peroxyg, such as _ isopropyl peroxy 1 bicarbonate and diethylhexyl peroxy bicarbonate peroxy bicarbonate; such as sulfonyl cyclohexylsulfonyl peroxide Fluorenyl peroxide; such as an organic peroxide selected from the above-mentioned organic peroxides and a reducing agent such as white powder A combined redox polymerization initiator; and such as 2,2, -azabisisobutyronitrile, 2,2'-azabis (2-methylbutyronitrile), 2,2, -nitrogen Heterobis (2,4_dimethylpentamidine) and 2,2, -azabis (4-methoxy-2,4-dimethylpentamidine). As examples of emulsifiers, Referred to as described in Emulsion Polymerization. 0 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the nuclear microsuspension polymerization, a polymerization reactor is fed with pure water and a residual polymerization initiator. Nuclear polymer, and optional components, degassing the reactor contents or removing it with an inert gas such as nitrogen, and then adding an emulsifier and vinyl chloride or—by gas ethylene and one or more A mixture of olefinically unsaturated monomers is copolymerized. The content is stirred gently and the temperature in the reactor is increased to initiate the polymerization. Preferably the 'polymerization is in the range of 30 to 80 C. As for emulsification Examples of agents can be mentioned in the emulsion polymerization. Applicable to the size of the paper National Standard (CNS) A4 specification (210 × 297 mm) 470752 A7 B7 V. Description of the invention (I3) In the case of nuclear microsuspension polymerization, it is not necessary to add a polymerization initiator to the water content of the nuclear polymer containing the seed The reason is that the core polymer used contains residual polymerization initiator. In microsuspension polymerization or seed core "floating polymerization, stirring is performed so that the conversion from 0% to 40% During the first period of conversion (not including), the net stirring-out force per unit volume of liquid phase is maintained in the range of 008 to [kW / m3, and preferably 0.1 to 〇a 8 Wm3. If this If the net agitation output is less than _, the heat transfer rate will decrease, and the removal of polymerization heat will become insufficient. Conversely, if the net dropout force is greater than 0 2 kw / m3, the growing particles will tend to agglomerate into gel lumps or scale, and the resulting polymer latex has poor mechanical strength. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page). During the second period of 40% to 75% conversion (excluding), the stirring process is performed to make per unit volume The net disturbing stirring out power of the liquid phase is maintained in the range of 50% to 100% and preferably 100% of the net stirring out stirring force used in the first period. If the net stir-out force is less than 5G% of the net disturbance stir-out force used in the first period, the heat transfer rate will decrease, and the removal of the polymerization heat will become insufficient. Conversely, if the material "force is greater than i 00% of the net stirring output used in the first period", the growing particles will tend to agglomerate into gels or scales "and the resulting polymer latex has poor mechanical strength During the third period from the conversion of 75% to the termination of the polymerization, the stirring is continued so that the net stirring output per unit volume of the liquid phase is maintained at 15% to 50% of the net stirring output used in the first period and It is preferably in the range of 跗 to 30%. If the net blending force is smaller than the Bianzhang scale used in the first period, the Chinese National Standard (Cns) A4 specification (2i0X 297 cm) is applicable. 470752 A7 B7 V. Description of the invention (15% of the net agitation output force of 15% ', then the heat transfer rate will be reduced, and the removal of the polymerization heat will become insufficient. Otherwise, if the net agitation output force is greater than the net used in the first-day ^ period In the township of sandalwood, the growing particles tend to agglomerate into gel clumps or steel scale, and the resulting polymer latex has poor mechanical strength. # Emulsion polymerization in seed nuclei, microsuspension polymerization, and microsuspension in seed nuclei Polymerization t 'The polymerization usually ends at 85 to 95% conversion. When the unreacted monomer is recovered after the polymerization is completed, the polymer in the reactor = has poor mechanical strength, so' it is gently stirred, i.e. per unit The net stir-out force of the volume liquid phase is from 0.0001 to 0.008 mm3, and preferably from 0.00 to 5 kw / m3T. If the net stir-out force is less than 0 kW / m3 It is difficult to recover unreacted monomers from the liquid content. Conversely, if the net stirring output is greater than 0. 8 kw / m3, the polymer particles tend to agglomerate into knee clots. As long as the cost can be reached For the purpose of the invention, the time for which the net agitation force is maintained in the range of 0.0001 to 0._8 kw / m ^ is not particularly limited and may be short-lived. The control of starting and stopping can be used for searching. According to the method of the heart, The extraction power is appropriately controlled depending on the specific conversion of the monomers during the polymerization, or it is controlled when the unreacted monomers are recovered. Therefore, the polymerization is effectively performed, polymer gels are rarely generated, and the obtained Polymer latex shows good mechanical stability And has a reduced amount of unreacted monomer. Now, the present invention will be specifically described by the following examples, but these examples are not intended to be used to limit the scope of patent application of the present invention. F The paper scale is applicable to the country of China Standard (CNS) A4 specification (210 X 297 mm (please read the precautions on the back before filling this page), printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy, printed 470752 A7 ------- B7 V. Description of the invention ~ ~~ — — In the following examples and comparative examples, Qi-E-Fu polymer milk is evaluated by the following methods. ≫ (Please read the precautions on the back before filling this page) (1) Gel content ( % By weight) # A wire ethylene polymer latex was filtered by a wire sieve having a mesh size of 60 mesh, and scooped to collect crude particles. Deposit $ onto the inner wall of the lower reactor. The collected coarse particles and the sediment are combined, dried and then weighed. The gel weight thus obtained is based on the weight of the monomer fed into the reactor, and is expressed in%. (2) Central particle diameter (from melon) The central particle diameter is measured by using a laser scattering particle diameter measuring device (Master Sizer Ms-2 supplied by Malvern Co.). (3) Mechanical stability (kW / m3) Feed 5 liters of gaseous ethylene polymer latex into a 5 liter conical flask with an inner diameter of 58 claws and a stirrer with an 85 mm long paddle. § HAI contents' were stirred at 275 rpm and 70 C / rev. And measured from the beginning of the stirring room until the particles started to agglomerate. Mechanical stability is expressed by the total value of the stirring output. (4) Residual monomer content (ppm) After the step of recovering unreacted monomers, a sample of vinyl chloride polymer latex with a known solid content is prepared. The sample was heated to 10 ° C to evaporate the residual vinyl chloride monomer, and its content in the evaporated gaseous mixture was measured by gas chromatography. The residual monomer content was determined by Expressed in ppm.
裝置：GC-17A，設有FID 本紙張尺度適用中國國家標準（CNS)A4規格（210x297公釐） 470752 經濟部智慧財產局員工消費合作社印製 A7 —____B7_ 五、發明説明（16 ) 管柱：DB-WAX，0.53 mmx 30 mm，薄膜厚度 1 # m 溫度：管柱60°C，檢測150°C 載氣：氮，30 ml/分鐘。 實例1 將31.5克之去離子水、36克之過硫酸鉀與8.9克含有35 重量％由乳化聚合作用所製備出之中心直徑為0.55从m的 種核聚合物粒子的水性懸浮液饋入一具有内體積1〇〇升、 500 mm直徑與470 mm長並設有一具有260 mm槳直控與 75mm槳寬之富得勒振盪槳片的搪瓷玻璃聚合反應器中。將 反應器内容物予以脫氣，並將36克氯乙烯單體再饋入反應 器中’將該混合物之溫度提高至55°C並攪拌之，以起始聚 合反應。 為使聚合物粒子穩定地增長’一乳化劑係被持續地加 入該聚合混合物如下。在聚合作用起始之後，令聚合反應 進行而不添加.乳化劑。在15%轉化至50%轉化期間，將月桂 基硫酸酯鈉之水性15重量％溶液以11 .〇 mi/i%轉化增加之 用量加入該聚合混合物中。在5〇%轉化至75%轉化之期間， 將該月桂基硫酸酯鈉之水性15重量％溶液以46.0 mi/i%轉 化增加之用量加入該聚合混合物中。其後，將該月桂基硫 酸酯鈉之水性15重量％溶液以72.0 ml/1%轉化增加之用量 加入該聚合混合物中。 聚合作用起始時在11 〇 rpm下進行攪拌，且當反應器内 壓降至0.5 kg/cm2時於75%轉化下，將攪拌速率降至65 rpm。當反應器内壓降至1.5 kg/cm2時於88%轉化下，在15 本紙張尺度適用中國國家標準（CMS ) Μ規格（210X297公策） !. -I- I I 1 !-1--1 - ----- J 士^—1 - - 1 - - —- II :- 丁 I. -I I ______ I 0¾ 、-口 髮 (請先閲讀背面之注意事項再填寫本頁) 470752 經濟部智慧財產局員工消費合作社印製 A7 ------_B7_ 五、發明説明（17 ) —〜" rpm之攪拌速率與65至75 t之溫度下開始回收未反應單 體。其後，收集聚合物並評估其性質。結果示於表工。 1實例 藉由與實例1所述之相同流程而製備出一氯乙烯聚合 物乳膠，其中利用一具有26〇 mm紫月直徑之^ 來取代該具有260 mm槳片直徑及75 mm槳寬之富得勒攪拌 紫片，並變化授拌條件如下。所有之其他條件仍維持大致 相同。 聚合作用起始時在95 rpm下進行攪拌，且當反靡器内 壓降至0.5 kg/cm2時於75%轉化下，將攪拌速率降至57 rpm。當反應器内壓降至丨.5 kg/cm2時於88%轉化下，在 ι·ρπι之攪拌速率下開始回收未反應單體。其評估結果示於 表1。 實例,Ί 藉由與實例1所述之相同流程而製備出—氣乙稀聚人 物乳膠’其中利用一具有260 mm槳片直徑之通用迴圈樂片 來取代該具有260 mm槳片直徑及75 mm槳寬之富得勒授摔 槳片，並變化攪拌條件如下。所有之其他條件仍維持大致 相同。 聚合作用起始時在130 rpm下進行攪拌，且當反應II内 壓降至0·5 kg/cm2時於75%轉化下，將攪拌速率降至8〇 i"pm。當反應器内壓降至1.5 kg/cm2時於88%轉化下，在η rpm之攪拌速率下開始回收未反應單體。其評估結果示於 表1 〇 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0'乂297公釐） ------ ----------^------、11-----<鱗 f請先閲讀背面之注意事項再填寫本頁} 470752 A7 B7 五、發明説明（is ) 生較例1 (請先閲讀背面之注意事項再填寫本頁} 藉由與實例1所述之相同流程而製備出—氯乙烯聚合 ,物乳膠，其中當轉化達到75%時未降低攪拌速率，且在S 收未反應單體之步驟中未進行授拌，而所有之其他條件仍 維持大致相同。其評估結果示於表1。 藉由與實例1所述之相同流程而製備出一氯乙烯聚人 物乳膠，其中當轉化達到75%時，每單位體積液相之= 拌出力降低至聚合作用起始時所使用之63%，且在回收未 反應單體之步驟中未進行攪拌，而所有之其他條件仍維持 大致相同。其評估結果示於表1。 藉由與實例1所述之相同流程而製備出—氯乙烯聚人 物乳膠，其中當轉化達到75%時，每單位體積液相之淨^ 拌出力降低至.聚合作用起始時所使用之2 1 %，且在回收未 反應單體之步驟中未進行攪拌，而所有之其他條件仍維持 大致相同。其評估結果示於表1。 經濟部智慧財產局員工消費合作社印製 比較例4· 藉由與實例1所述之相同流程而製備出一氣乙稀聚入 物乳膠，其中當轉化達到75%時，每單位體積液相之淨攪 拌出力降低至聚合作用起始時所使用之丨3%，且在回收未 反應單體之步驟中未進行攪拌，而所有之其他條件仍維持 大致相同。其評估結果示於表1。 、 比較例Fi -2t- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 470752 經濟部智慧財產局員工消費合作社印製 A7 —一 ___ — B7 發明説明（19 ) 藉由與實例1所述之相同流程而製備出一氯乙烯聚合 物乳膝，其中當轉化達到75%時，每單位體積液相之淨攪 拌出力降低至聚合作用起始時所使用之21 %，且在回收未 反應單體之步驟中，每單位體積液相之淨攪拌出力降低至 〇·〇33 kW/cm2。所有之其他條件仍維持大致相同。其評估 結果不於表1。 實例 9 3 〇 比較ί歹丨j 第一時期（0%-40%鏟化） 丄 Ζ 3 4 5 .欖件迷準(rom) no 95 130 110 110 Ϊ10 110 1 in …出力(kWAn、 0.16 0.17 0.18 0.16 0.16 0.16 0 16 〇 1 6 乐一呀期（4〇%-75%鰱化） _撹#速率(rrnn) no 95 130 110 110 110 110 110 麵半出力(kWih^ 0.16 0.17 0.18 0.16 0.16 0.16 0.16 〇1 罘二日f期（75%韓化 撹袢速率imm) 65 57 80] 110 95 65 55 65 _半出力WtA 「6.032 0.04, Γ〇·04 0.16 0.1 0.033 0.09. 0 033 弟izg時期（回收夬；5 應單f 1) _ 搜拌速率(ipm) 15 10 15 - - • 65 -纖半出力，如3) 0.00041 0.0002 0.0003 - 〇 033 聚合時間(小時) 10 10 10 10 10 10 12 *1 10 乳膠之性晳 ~!一· 殘留单體含量 (DDm) 1500 1500 1500 3500 3500 3500 3500 1500 凝膠物含量 0.2 0.2 0.2 2 105 0.2 0.2 10 機械安定性 (kW/m3) 10 10 10 1 3 10 10 7 中心粒子直徑 ("m) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1聚合作用_間加長 如表1所示，當一乳化聚合作用係在滿足於本發明所 請條件下進行時（實例1至3 )，所得之聚合物乳膠具有降 低含量之凝聚物、良好之機械安定性及降低含量之殘留單 體。 本紙張尺度適用中國國家標隼（CNS ) Α4規格（210Χ297公釐） I^衣 „1T------線 (請先聞讀背面之注意事項再填寫本頁) 五、 發明説明（ 20 A7 B7 反之，當由聚合作用起始維持相同之淨攪拌出 — 成該聚合作用，且在回收反應單體之步驟中未進行 (比較例1)，所得之聚合物乳膠具有不良之機械安二生: 亚含有顯著含量之未反應單體。 當淨攪拌出力在75%轉化時僅少量降低， 虛™ -且在回收反 愿早體之步騾中未進行攪拌時（比較例2 )， ^ 孔膠亦含有大量凝聚物、具有不良之機械安定性，二人 顯著含量之未反應單體。 ”3 即使聚合作用的整個過程係在滿足於本發明所請條科 下進行Μ ’但S ’若未在时單體之步财進行授掉（比 較例3)’則所得之聚合物乳膠含有低量凝聚物並具有良対 之機械安定性，但含有顯著含量之未反應單體。 當淨授摔出力在75%轉化時降至遠低於本發明的程 度，且在回收反應單體之步驟十未進行攪拌時（比較^ 4)’所得之聚合物乳膠含有低量凝聚物並具有良好之機輔 安定性，I聚合作㈣間會延長且聚合物乳膠所殘存顯著 的單體含量。 即使聚合作用的整個過程係在滿足於本發明所請條件 下進行攪拌，但若在回收單體之步驟中，攪拌係在較本發 明所使用者更強的條件下進行（比較例5 )，則所得之聚入 物乳膠含有大量凝聚物’並具有不良之機械安定性。 實例4 藉由一於48°C下所進行之微懸浮聚合作用，由1〇〇重量 份之氣乙婦、0.5重量伤之十二烧基笨續酸鈉、θα重量 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、-° 經濟部智慧財產局員工消費合作社印製 五、發明説明（21 ) A7 B7 經 濟 部 智 慧 財 i. 局 消 費 人 η 社 印 製 之更月θ醇與〇·5重置份之月桂酿過氧化物製備出—含有π 重量％中心直徑為〇.55㈣之聚合物粒子的氯乙埽聚合物 乳膠。 將10公斤之則述氯乙烯聚合物乳膠、30公斤去離子水 及2〇0克之十二烧基苯場酸鈉饋入-具有内體積100升、500 mmj徑與470職長並設有一具有賴樂直徑與乃咖 槳寬之富得勒振盪紫片的塘£玻璃聚合反應器中。隨後， 在真空下將内容物予以脫氣，並接著再饋入36克氯乙烤。 將該混合物之溫度提高至62。〇，並在1〇〇rpm之速率下進行 攪拌’以起始聚合反應。當反應器之内壓降至〇 5 %於75%轉化下，將攪拌速率降至55卬旧並繼續攪拌。當反 應器内壓降至M kg/cm2時於88%轉化下，終止聚合作用。 隨後，將攪拌速率降低至丨5 ，並將該内容物之溫度升 高至65至75 °C之溫度下，俾回收未反應單體。其後，收集 該聚合物並評估其性質。結果示於表1。 實例5 藉由與實例4所述之相同流程而製備出一氯乙稀聚合 物乳膠，其中利用一具有260 mm槳片直徑之Max_Blend槳片 來取代該具有260 mm槳片直徑及75 mm槳寬之富得勒攪拌 樂片’並變化攪拌條件如下。所有之其他條件仍維持大致 相同。 聚合作用起始時在80 rpm下進行攪拌，並持續攪拌。 §轉化達到75%時，將授拌·速率降至45 rpm。當轉化達到 88%時，終止聚合作用，並將攪拌速率降低至1〇 rpm，以回 --^---- 本紙張尺度適用中國國家襟準（CNS ) A4規格（210X297公釐 (請先閲讀背面之注意事項再填寫本頁) 、-=β 470752 A7 B7 五、發明説明（22 ) ~ 收未反應單體。其評估結果示於表2。 實例6 (請先閱讀背面之注意事項再填寫本頁} 藉由與實例4所述之相同流程而製備出—氯乙稀聚人 物乳膠’其中利用一具有260 mm槳片直徑之通用迴圈紫片 來取代該具有260 mm槳片直徑及75 mm槳寬之富得勒授样 槳片’並變化攪拌條件如下。所有之其他條件仍維持大致 相同。 聚合作用起始時在Π〇 rpm下進行攪拌，並持續搜样。 s轉化達到75%時，將授拌速率降至60 rpm。當轉化達到 88%時，終止聚合作用，並將攪拌速率降低至15 rpm，以回 收未反應單體。其評估結果示於表2。 比較例 藉由與實例4所述之相同流程而製備出一氯乙烯聚合 物乳膠’其中當轉化達到75%時未降低攪拌.速率，且在回 收未反應單體.尤步驟中未進行擾拌，而所有之其他條件仍 維持大致相同。其評估結果示於表2。 比較仞I 7 經濟部智慧財產局員工消費合作社印製 藉由與實例4所述之相同流程而製備出一氯乙烯聚合 物乳膠’其中當轉化達到75%時，每單位體積液相之淨授 拌出力降低至聚合作用起始時所使用之55%，且在回收未 反應單體之步驟中未進行攪拌，而所有之其他條件仍維持 大致相同。其評估結果示於表2。 比較例只 藉由與實例4所述之相同流程而製備出一氯乙烯聚合 本紙張尺度朝巾關家標準（CNS ) ( 21GX297公釐)—~ ' 25 ' ~ ~ 470752 A7 ._________ B7 五、發明説明（23 ) 〜-— 物乳膠，其中當轉化達到75%時，每單位體積液相之㈣ 拌出力降低至聚合作用起始時所使用之1 7 %， 且在回收未 反應單體之步驟中未進行㈣，而所有之其他條件仍維持 大致相同。其評估結果示於表2。 比較咖丨9 藉由與實例4所述之相同流程而製備出—氣乙烯聚人 物乳膠，其中當轉化達到75%時，每單位體積液相之淨攪 拌出力降低至聚合作用起始時所使用之9%，且在回收未反 應單體之步驟中未進行攪拌，而所有之其他條件仍維持大 致相同。其評估結果示於表2。 比較例1 0 藉由與實例4所述之相同流程而製備出—氯乙稀聚合 物乳膠，其中當轉化達到75%時，每單位體積液相之淨攪 拌出力降低至聚合作用起始時所使用之1 7%，且在回收未 反應單體之步驟中’每單位體積液相之淨攪拌出力降低至 0.02 kW/cm2。所有之其他條件仍維持大致相同。其評估結 果不於表2 〇 (請先閱讀背面之注意事項再填寫本頁) -8 經濟部智慧財產局員工消費合作社印製 A2 實例 _比較例 一 4 5 6 6 7 + 丄 8 9 1 Π 第一時期（0%-40%奉 【化） 1 U 攪拌速率(rom) 100 80 110 100 100 — ----- 100 100 1 nn 麵働(kWAn3) 0.12 0.1 0.11 0.12 '0.12 0.12 0.12 0.ί4 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） 470752 A7 B7Device: GC-17A, equipped with FID This paper size is applicable to Chinese National Standard (CNS) A4 specification (210x297 mm) 470752 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 —____ B7_ V. Description of the invention (16) DB-WAX, 0.53 mmx 30 mm, film thickness 1 # m Temperature: column 60 ° C, detection 150 ° C Carrier gas: nitrogen, 30 ml / min. Example 1 An aqueous suspension of 31.5 g of deionized water, 36 g of potassium persulfate, and 8.9 g of a core polymer particle having a center diameter of 0.55 from m prepared by emulsification polymerization was fed into a container containing It has a volume of 100 liters, a diameter of 500 mm and a length of 470 mm, and is equipped with a Fullerer oscillating glass polymerization reactor with direct control of a 260 mm paddle and a 75 mm paddle width. The reactor contents were degassed, and 36 grams of vinyl chloride monomer was re-fed into the reactor 'to raise the temperature of the mixture to 55 ° C and stir to initiate the polymerization reaction. To stably grow polymer particles, an emulsifier system is continuously added to the polymerization mixture as follows. After the start of the polymerization, the polymerization was allowed to proceed without the addition of an emulsifier. During the 15% to 50% conversion, an aqueous 15% by weight solution of sodium lauryl sulfate was added to the polymerization mixture in an amount of 11.0 mi / i% conversion increase. During the period of 50% to 75% conversion, an aqueous 15% by weight solution of the sodium lauryl sulfate was added to the polymerization mixture in an amount of 46.0 mi / i% conversion increase. Thereafter, an aqueous 15% by weight solution of the sodium lauryl sulfate was added to the polymerization mixture in an amount of 72.0 ml / 1% conversion increase. The polymerization was stirred at 110 rpm at the beginning of the polymerization, and the stirring rate was reduced to 65 rpm when the internal pressure of the reactor dropped to 0.5 kg / cm2 at 75% conversion. When the internal pressure of the reactor dropped to 1.5 kg / cm2 at 88% conversion, the Chinese National Standard (CMS) M specification (210X297 public policy) was applied at 15 paper sizes !. -I- II 1! -1--1 ------ J 士 ^ —1--1--—- II:-Ding I. -II ______ I 0¾,-Oral (please read the precautions on the back before filling this page) 470752 Ministry of Economic Affairs Wisdom A7 printed by the Consumer Cooperative of the Property Bureau ------_ B7_ V. Description of the invention (17)-~ " Starts recovery of unreacted monomers at a stirring rate of rpm and a temperature of 65 to 75 t. Thereafter, the polymer was collected and evaluated for its properties. The results are shown in the table. Example 1 A vinyl chloride polymer latex was prepared by the same procedure as described in Example 1. A ^ with a diameter of 26 mm was used to replace the rich with a blade diameter of 260 mm and a blade width of 75 mm. Dehler stirs the purple flakes and changes the mixing conditions as follows. All other conditions remain approximately the same. Stirring was started at 95 rpm at the beginning of the polymerization, and at 75% conversion when the internal pressure of the reactor was reduced to 0.5 kg / cm2, the stirring rate was reduced to 57 rpm. When the internal pressure of the reactor dropped to 1.5 kg / cm2 at 88% conversion, unreacted monomers were recovered at a stirring rate of ι · ρπι. The evaluation results are shown in Table 1. Example, Ί Prepared by the same process as described in Example 1-Gas-Ethylene Diluted Polyester Latex 'where a universal loop music piece with a 260 mm paddle diameter is used instead of the 260 mm paddle diameter and 75 Fullerer propeller blades with mm paddle width are taught and the stirring conditions are changed as follows. All other conditions remain approximately the same. The polymerization was stirred at 130 rpm at the beginning of the polymerization, and at 75% conversion when the internal pressure of Reaction II dropped to 0.5 kg / cm2, the stirring rate was reduced to 80 pm. When the internal pressure of the reactor dropped to 1.5 kg / cm2 at 88% conversion, the unreacted monomer began to be recovered at a stirring rate of η rpm. The evaluation results are shown in Table 10. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0 '乂 297mm) ------ ---------- ^ --- ---, 11 ----- < Please read the notes on the back before filling in this page} 470752 A7 B7 V. Description of the invention (is) Comparison example 1 (Please read the notes on the back before filling This page} was prepared by the same procedure as described in Example 1-vinyl chloride polymerization, latex, in which the stirring rate was not reduced when the conversion reached 75%, and no step was performed in the step of collecting unreacted monomers. And all other conditions remained approximately the same. The evaluation results are shown in Table 1. A vinyl chloride polyemulsion was prepared by the same procedure as described in Example 1, where when the conversion reached 75%, per unit The volume of liquid phase = reduction of the stirring power to 63% used at the beginning of the polymerization, and no stirring was performed in the step of recovering unreacted monomers, while all other conditions remained substantially the same. The evaluation results are shown in the table 1. A vinyl chloride polymer latex was prepared by the same procedure as described in Example 1, where when the conversion reached At 75%, the net ^ stirring power per unit volume of liquid phase is reduced to 2 1% used at the beginning of the polymerization, and stirring is not performed in the step of recovering unreacted monomers, while all other conditions are maintained It is almost the same. The evaluation results are shown in Table 1. Comparative Example 4 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs · A gaseous ethylene polymer latex was prepared by the same process as described in Example 1. At 75%, the net stirring output per unit volume of the liquid phase is reduced to 3% used at the beginning of the polymerization, and no stirring is performed in the step of recovering unreacted monomers, while all other conditions remain substantially the same The evaluation results are shown in Table 1. Comparative Example Fi -2t- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 470752 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 — 一 ___ — B7 Description of the invention (19) A vinyl chloride polymer breast knee was prepared by the same procedure as described in Example 1. When the conversion reached 75%, the net stirring output per unit volume of liquid phase was reduced to polymerization. With 21% used at the beginning, and in the step of recovering unreacted monomers, the net stirring output per unit volume of the liquid phase is reduced to 0.033 kW / cm2. All other conditions remain substantially the same. The evaluation results are not in Table 1. Example 9 3 〇 Comparison of the first period (0% -40% shovel) 丄 Z 3 4 5 .Rom no 95 130 110 110 Ϊ10 110 1 in… Power output (kWAn, 0.16 0.17 0.18 0.16 0.16 0.16 0 16 〇1 6 Le Yi Ya period (40% -75% 鲢) _ 撹 #Speed (rrnn) no 95 130 110 110 110 110 110 surface half output (kWih ^ 0.16 0.17 0.18 0.16 0.16 0.16 0.16 〇1 The second day f period (75% Korean chemical conversion rate imm) 65 57 80] 110 95 65 55 65 _ half output WtA 「6.032 0.04, Γ〇 · 04 0.16 0.1 0.033 0.09. 0 033 Izg period (recovery 夬; 5 should be f 1) _ search rate (ipm) 15 10 15--• 65-fiber half output, such as 3) 0.00041 0.0002 0.0003-〇033 polymerization time (hours) 10 10 10 10 10 10 12 * 1 10 The properties of latex are clear ~! Residual monomer content (DDm) 1500 1500 1500 3500 3500 3500 3500 1500 Gel content 0.2 0.2 0.2 2 105 0.2 0.2 10 Mechanical stability (kW / m3) 10 10 10 1 3 10 10 7 Central particle diameter (" m) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1 Polymerization_interval lengthening is shown in Table 1. It shows that when an emulsification polymerization is performed under the conditions required by the present invention (Examples 1 to 3), the obtained polymer latex has reduced content of agglomerates, good mechanical stability, and reduced content of residual monomers. . This paper size is applicable to China National Standard (CNS) A4 specification (210 × 297 mm) I ^ yi „1T ------ line (please read the precautions on the back before filling out this page) 5. Description of the invention (20 A7 B7 Conversely, when the same net agitation is maintained from the beginning of the polymerization—the polymerization is completed and not performed in the step of recovering the reaction monomer (Comparative Example 1), the resulting polymer latex has poor mechanical safety. Health: It contains a significant amount of unreacted monomer. When the net agitation output is reduced at 75% conversion, only a small amount is used, and when agitation is not performed in the step of recovering anti-desirable early bodies (Comparative Example 2), ^ Cell gel also contains a large amount of aggregates, has poor mechanical stability, and a significant amount of unreacted monomers. "3 Even if the entire process of polymerization is performed under the satisfaction of the subject matter of the present invention, M 'but S' If the monomers are not granted in time (Comparative Example 3), the polymer latex obtained contains a low amount of aggregates and has good mechanical stability, but contains a significant amount of unreacted monomers. When the net Granted throw power drops to very low at 75% conversion The degree of the present invention, and when the stirring of the reaction monomer is not performed in step 10 (comparative ^ 4), the polymer latex obtained contains low amount of agglomerates and has good mechanical stability. And the polymer monomer has a significant residual monomer content. Even if the entire process of polymerization is performed under the conditions required by the present invention, if the monomer is recovered, the agitation is performed more than the user of the present invention. Under stronger conditions (Comparative Example 5), the obtained polymer latex contains a large amount of agglomerates and has poor mechanical stability. Example 4 Using a microsuspension polymerization at 48 ° C, 100 parts by weight of Qiyifu, 0.5 weight of dodecayl sodium monobutyrate, θα weight This paper size applies Chinese National Standard (CNS) A4 specification (210 X297 mm) (Please read the back Note: Please fill in this page again),-° Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (21) A7 B7 Intellectual Property of the Ministry of Economic Affairs i. 5 Preparation of laurel-peroxide-containing chloroethene polymer latex containing π wt% polymer particles with a center diameter of 0.55 ㈣. 10 kg of vinyl chloride polymer latex and 30 kg of deionized water And 200 grams of dodecyl benzoate sodium feed-with an internal volume of 100 liters, a diameter of 500 mm and a length of 470, and a pond with Laidle diameter and Naka paddle width of a Fuller's Oscillating Purple Tablet. In a glass polymerization reactor. The contents were then degassed under vacuum and then fed with another 36 grams of ethyl chloride. The temperature of the mixture was raised to 62.0 and performed at a speed of 100 rpm. Stir 'to initiate polymerization. When the internal pressure of the reactor was reduced to 0.5% at 75% conversion, the stirring rate was reduced to 55 ° C and stirring was continued. When the internal pressure of the reactor dropped to M kg / cm2 at 88% conversion, the polymerization was terminated. Subsequently, the stirring rate was reduced to 5 and the temperature of the content was raised to a temperature of 65 to 75 ° C, and the unreacted monomer was recovered. Thereafter, the polymer was collected and evaluated for its properties. The results are shown in Table 1. Example 5 A vinyl chloride polymer latex was prepared by the same procedure as described in Example 4, wherein a Max_Blend blade having a 260 mm blade diameter was used instead of the 260 mm blade diameter and 75 mm blade width. The Fullerer Stirrer Tablets' and varying the stirring conditions are as follows. All other conditions remain approximately the same. The polymerization was started at 80 rpm with continuous stirring. § When the conversion reaches 75%, reduce the mixing rate to 45 rpm. When the conversion reaches 88%, the polymerization is terminated and the stirring rate is reduced to 10 rpm to return-^ ---- This paper size applies to China National Standard (CNS) A4 specification (210X297 mm (please first Read the notes on the back and fill in this page again),-= β 470752 A7 B7 5. Description of the invention (22) ~ Unreacted monomers are collected. The evaluation results are shown in Table 2. Example 6 (Please read the notes on the back before Fill out this page} Prepared by the same procedure as described in Example 4-Chlorinated Ethylene Polyethylene Latex 'where a universal loop purple sheet with a 260 mm paddle diameter is used instead of the 260 mm paddle diameter and A 75mm paddle-wide Fullerer sample paddle 'and varying the stirring conditions are as follows. All other conditions remain approximately the same. At the beginning of the polymerization, stirring was performed at Π rpm, and the sample was continuously searched. S conversion reached 75 %, The mixing rate was reduced to 60 rpm. When the conversion reached 88%, the polymerization was terminated, and the stirring rate was reduced to 15 rpm to recover unreacted monomers. The evaluation results are shown in Table 2. Comparative Example A procedure was prepared from the same procedure as described in Example 4. Vinyl chloride polymer latex 'where the agitation rate is not reduced when the conversion reaches 75%, and unreacted monomers are recovered, especially in the step where no agitation is performed, while all other conditions remain approximately the same. The evaluation results are shown in Table 2. Comparative 仞 I 7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. A vinyl chloride polymer latex was prepared by the same process as described in Example 4. Where the conversion reaches 75%, the liquid phase per unit volume The net stirring-out force was reduced to 55% used at the beginning of the polymerization, and stirring was not performed in the step of recovering unreacted monomers, while all other conditions remained substantially the same. The evaluation results are shown in Table 2. Comparative Example: Only the same procedure as described in Example 4 was used to prepare a vinyl chloride polymer paper. The paper size standard (CNS) (21GX297 mm) — ~ '25' ~~ 470752 A7. _________ B7 V. Description of the invention (23) ~ -— latex, in which when the conversion reaches 75%, the stirring power per unit volume of the liquid phase is reduced to 17% used at the beginning of the polymerization, and the unreacted monomer is recovered Steps The process was carried out while all other conditions remained approximately the same. The evaluation results are shown in Table 2. Comparative coffee 丨 9 was prepared by the same procedure as described in Example 4-gas ethylene poly character latex, when the conversion reached 75 At%, the net agitation output per unit volume of liquid phase is reduced to 9% used at the beginning of the polymerization, and no agitation is performed in the step of recovering unreacted monomers, while all other conditions remain substantially the same. The evaluation results are shown in Table 2. Comparative Example 10 A chloroethylene polymer latex prepared by the same procedure as described in Example 4, wherein when the conversion reached 75%, the net stirring output per unit volume of the liquid phase was reduced. Up to 17% used at the beginning of the polymerization, and in the step of recovering unreacted monomers, the net stirring output per unit volume of the liquid phase was reduced to 0.02 kW / cm2. All other conditions remain the same. The evaluation results are not in Table 2 〇 (Please read the precautions on the back before filling this page) -8 Printed A2 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Example_Comparative Example 1 4 5 6 6 7 + 丄 8 9 1 Π The first period (0% -40% Bong) 1 U stirring rate (rom) 100 80 110 100 100 — ----- 100 100 1 nn noodles (kWAn3) 0.12 0.1 0.11 0.12 '0.12 0.12 0.12 0.ί4 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 470752 A7 B7
V 發明説明（24) 差_+時期ί40%-75%轉化） 速率(r〇m) 100 80 110 100 100 100 100 100 半出力《if) 0.12 0.1 0.11 0.12 0.12 0.12 0.12 0.14 弟二時期（75%轉化-) _^:拌速率(r〇m) 55 45 60 100 80 55 45 55 '萄半出力(kWAn3) 0.02 0..018 0.017 0.12 0.066 0.02 0.011 0.02 第四時期（回收未反應單體） jl：拌速率(mm) 15 10 15 - - 55 補半出力(kW/hi5) 0.0004 0.0002 0.0003 - - 0.02 立合時間(小時) 11 11 11 Ϊ1 L 11 11 10 Ί 11 _孔膠之性晳 殘留單體含量 —(ppm) 1700 1700 1700 3500 3500 3500 3500 1700 凝膠物含詈 0.15 0.15 0.15 1.5 1 0.15 0.15 1 機械安定性 .(kW/m3、 10 10 10 2 5 10 10 7 中心粒子直徑 (wm) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (請先閎讀背面之注意事項再填寫本頁) •裝' 如表2所示，當一種核微懸浮聚合作用係在滿足於本 發明所請條件下進行時（實例4至6 )，所得之聚合物乳膠 具有降低含量之凝聚物、良好之機械安定性及降低含量之 殘留單體。 反之，當由聚合作用起始維持相同之淨攪拌出力至完 成該聚合作用，且在回收反應單體之步驟中未進行攪拌時 (比較例6)’或者當淨攪拌出力在75%轉化時僅略為降低， 且在回收反應單體之步驟中未進行攪拌時（比較例了），所 得之聚合物乳膠含有大量凝聚物、具有不良之機械安定 性’並含有顯著含量之未反應單體。 即使聚合作用的整個過程係在滿足於本發明所請條件 下進行授拌’但是，若未在时單體之步驟中進行授掉（比 較例8)，則所得之聚合物乳膠含有低量凝聚物並具有良好 度適用中國國家標準（CNS ) A4規格（210X297公釐） 訂 線 經濟部智慧財產局員工消費合作社印製 470752 A7 ________ B7 五、發明説明（25 ) — ~" ~^ 一 ^ 之機械安定性，但含有顯著含量之未反應單體。 當淨攪拌出力在75%轉化時降至遠低於本發明的程 度，且在回收反應單體之步驟中未進行攪拌時（比較例 9 )，所得之聚合物乳膠含有低量凝聚物並具有良好之機械 安定性，但在聚合作用之最後階段，聚合混合物會非所欲 地升高’且聚合物乳膠所殘存顯著的單體含量。 即使聚合作用的整個過程係在滿足於本發明所請條件 下進灯授伴’但若在回收單體之步驟中，攪拌係在較本發 明所使用者更強的條件下進行（比較例1〇)，則所得之聚合 物乳膠含有大量凝聚物，並具有不良之機械安定性。 當-乳化聚合作用、種核乳化聚合作用、微懸浮聚合 作用或種核微懸浮聚合作用係在滿足於本發明所需之攪拌 條件下進行時，所得之聚合物乳膠具有降低含量之凝聚 物、良好之機械安定性及降低含量之殘留單體。 (請先間讀背面之注意事項再填寫本頁) -、言 經濟部智慧財產局員工消費合作社印製 尺 張，紙 本 一隼 ί標 ί家 國 國 中 用 適V Description of the invention (24) Poor period + 40% -75% conversion) Rate (r0m) 100 80 110 100 100 100 100 100 Half output "if" 0.12 0.1 0.11 0.12 0.12 0.12 0.12 0.12 0.14 Brother II period (75% Conversion-) _ ^: Mixing rate (r0m) 55 45 60 100 80 55 45 55 'Half output (kWAn3) 0.02 0..018 0.017 0.12 0.066 0.02 0.011 0.02 Fourth period (recover unreacted monomer) jl ： Mixing rate (mm) 15 10 15--55 Filling half output (kW / hi5) 0.0004 0.0002 0.0003--0.02 Standing time (hour) 11 11 11 Ϊ1 L 11 11 10 Ί 11 Content- (ppm) 1700 1700 1700 3500 3500 3500 3500 1700 Gel contains 0.15 0.15 0.15 1.5 1 0.15 0.15 1 Mechanical stability. (KW / m3, 10 10 10 2 5 10 10 7 Central particle diameter (wm) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 (Please read the precautions on the reverse side before filling out this page) • Installation 'As shown in Table 2, when a nuclear microsuspension polymerization is performed under the conditions required by the present invention ( Examples 4 to 6), the obtained polymer latex has reduced content of agglomerates, good mechanical stability and reduced content Conversely, when the same net agitation output is maintained from the beginning of the polymerization to the completion of the polymerization, and no agitation is performed in the step of recovering the reaction monomer (Comparative Example 6) 'or when the net agitation output is The 75% conversion was only slightly reduced, and when the stirring was not performed in the step of recovering the reaction monomer (comparative example), the obtained polymer latex contained a large amount of aggregates, had poor mechanical stability, and contained a significant amount of Reactive monomer. Even if the whole process of polymerization is carried out under conditions satisfying the requirements of the present invention, but if it is not carried out in the monomer step (Comparative Example 8), the resulting polymer latex Contains low amount of agglomerates and has good degree. Applicable to China National Standard (CNS) A4 specification (210X297mm). Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 470752 A7 ________ B7 V. Invention Description (25) — ~ " ~ ^ A ^ mechanical stability, but contains a significant amount of unreacted monomer. When the net stirring output was reduced to a level far lower than the present invention at 75% conversion, and when stirring was not performed in the step of recovering the reaction monomer (Comparative Example 9), the obtained polymer latex contained a low amount of agglomerates and had Good mechanical stability, but in the final stage of polymerization, the polymerization mixture will increase undesirably 'and the significant monomer content remaining in the polymer latex. Even if the entire process of polymerization is performed under the conditions required by the present invention, but in the step of recovering monomers, the stirring is performed under stronger conditions than the users of the present invention (Comparative Example 1) 〇), the polymer latex obtained contains a large amount of agglomerates and has poor mechanical stability. When -emulsion polymerization, seed core emulsion polymerization, microsuspension polymerization or seed core microsuspension polymerization is performed under the stirring conditions required by the present invention, the resulting polymer latex has a reduced content of agglomerates, Good mechanical stability and reduced residual monomer content. (Please read the notes on the back before filling out this page)-、 Yes. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed on paper.
I格 4¾ A4 S N i釐 公 7 9 2I grid 4¾ A4 S N i cm 7 9 2