1298330 t 九、發明說明： 本發明係關於產生微粒聚合物之改良，尤指聚苯乙烯顆 粒。 本發明尤適於產生EPS珠粒，但該方法可以用以製備任 何可由懸浮聚合反應生產之微粒聚合物，尤指苯乙烯系均 聚物和共聚物，及乙烯基均聚物和共聚物。適當單體之實 例包括乙烯系脂肪族單體，如丙烯酸和甲基丙烯酸之醋 類’丙烯晴，#乙烯系芳香族單體，如苯乙烯和取代苯乙 稀。 每年生產數以百萬噸計之可膨脹聚苯乙烯（Eps)。Eps係 以珠粒形式產生並用以製備各種產物，例如從薄壁杯至包 農材料，至建築用之大型石塊。 不同最終用途需要不同尺寸之EpS珠粒，典型上如下： 200-600微米-杯盤 400-800微米-薄壁包裝材料 600-1 1 〇〇微米-正常包裝材料 900-2000微米-絕緣板塊材料。 在這些目標尺寸範圍外之EPS珠粒典型上被認定為"規格 外（〇ff-SpeCificati〇n)”材料，且通常實質上價格較低。 EPS通常由懸浮聚合法產生，其中將苯乙稀在自由基產 生斋存在下聚合。將以此方式產生之聚苯乙烯（ps)珠粒浸 潰發泡劑，典型上為Cw烴，如戊烷，以產生可膨脹聚苯 乙稀（EPS)珠粒。 然而，懸浮聚合產生廣泛尺寸分布之ps珠粒，且該？8或 63748-970214.doc 1298330 EPS珠粒必需經尺寸分級，即分離為具有適用於所需要最 終用途之顆粒尺寸範圍之部份。 雖然懸浮聚合反應環境之變化可以使EPS產生劑能夠將 具有特疋所需尺寸之聚合物珠粒部份最佳化，例如，作為 薄壁包裝材料，所有珠粒產量中大部份將依然為較不希望 之級數或將為規格外尺寸。 在德國專利第GB_A_14164〇5號中，瑟吉水（Sekisui)敘述 一種方法，其中苯乙烯之懸浮聚合反應係在尺寸小於最終 產物所需形式尺寸之聚苯乙烯晶種存在下進行。 典型上該瑟吉水法可以如二階段懸浮聚合反應般進行。 s形成例如具有形式尺寸約9〇〇微米之較小顆粒時，第一 階段便終止。其後將該小珠粒分級以便移除過小和過大部 份，留下ps晶種，例如尺寸400至1800微米，其後將該晶 種用於第二懸浮聚合階段，以產生關於所需顆粒尺寸分佈 較傳統懸浮聚合反應中達成者狹窄。然而，即使本方法產 生種具有廣泛顆粒尺寸分佈之產物，且分級步驟之複雜 性提高，因為其必需在第一聚合反應階段中產生之較小顆 粒上進行。 以傳統和瑟吉水法產生之Eps分級包含顆粒尺寸範圍， 例如差異數百微米之顆粒直徑。此對於將Eps珠粒處理為 %脹聚苯乙烯產物之加工具有不利影響。 在恥脹聚苯乙烯產物配方中，首先將Eps珠粒預膨脹以 產生自由流動之膨脹顆粒，典型上使用溫度低於1〇〇。〇之 流，其後在填封於模型中並以蒸氣處理前，典型上在丨1〇 63748-970214.doc 1298330 至120 C，在空氣通過之儲倉中燒至顆粒完全膨脹並燃 燒。 需要燒期間，以使預膨脹之顆粒發展模製法必需之彈 性。 EPS珠粒中顆粒尺寸分佈並未在預膨脹珠粒中簡單地複 製，而尺寸方佈放寬，且產生廣泛密度分佈，因為在相同 環境下EPS珠粒越小將越不膨脹，珠粒越大，越導致包含 混合物之燒儲倉，其包括小型高密度顆粒和較大型低密 度顆粒。在燒儲倉中發生自較小型較高密度顆粒沉降， 導致從儲倉供料至模型之預膨脹顆粒混合物不均勻，因此 導致权製產物之最終岔度和強度改變。於是分級Ep$珠粒 之廣泛顆粒尺寸分佈’因此預膨脹顆粒導致難以產生膨脹 聚苯乙烯產物，並使產物品質不均且難以控制。 頃發現能夠產生實質上單分散（即單一尺寸）聚合物晶種 顆粒，其能夠用於懸浮聚合反應中以產生較大型，單依然 實夤上單分散聚合物顆粒，例如尺寸適於一種Ep$代表性 最終用途之實質上單分散EPS顆粒。此聚合物顆粒生產方 法係於世界專利第W099/19375號中敘述。將世界專利第 W099/19375號之揭示併入本文供參考。 由於產物係實質上單分散，不需要機械分級，因此導致 生產設備和加工期間之合理節省。此外，未產生不希望之 級數’因而導致有效產量合理地提高且廢棄物減少。此 外，避免或降低在分級EPS產物内與廣泛顆粒尺寸範圍相 關之問題。 63748-970214.doc 1298330 在世界專利第W099/19375號中聚苯乙烯顆粒生產法之 顆粒尺寸膨脹循環較耗時，頃發現該方法可以加速倘若在 至少一個膨脹循環中，晶種於多少類似歐洲專利第ep-b-3905號（辛德福（Sintef))和美國專利第US-A-4530956號（烏 格斯達（Ugelstad))中所述之烏格斯達聚合法之方法中預膨 脹，將該揭示併入本文供參考。 聚合物珠粒可以藉由在水性分散液中將單體和聚合引發 劑（或觸媒）擴散於聚合物晶種中而產生。該晶種膨脹，繼 之引發聚合反應，例如加熱，以活化該引發劑，產生較大 之聚合物顆粒。由於膨脹和聚合而增加之最大體積通常為 約x5或更低。後來約翰烏格斯特教授（pr〇fess〇r以匕1298330 t IX. INSTRUCTIONS: The present invention relates to improvements in the production of particulate polymers, especially polystyrene particles. The invention is particularly suitable for the production of EPS beads, but the process can be used to prepare any particulate polymer which can be produced by suspension polymerization, especially styrenic homopolymers and copolymers, and vinyl homopolymers and copolymers. Examples of suitable monomers include vinyl aliphatic monomers such as acrylonitrile and methacrylic acid acrylonitrile, #vinyl aromatic monomers such as styrene and substituted styrene. Millions of tons of expandable polystyrene (Eps) are produced annually. Eps are produced in the form of beads and used to make a variety of products, such as from thin-walled cups to agricultural materials to large stones for construction. Different sizes of EpS beads are required for different end uses, typically as follows: 200-600 microns - cup tray 400-800 microns - thin wall packaging material 600-1 1 〇〇 micron - normal packaging material 900-2000 microns - insulating sheet material . EPS beads outside these target size ranges are typically identified as "outside (〇ff-SpeCificati〇n)" materials and are generally substantially lower in price. EPS is typically produced by suspension polymerization, in which styrene is present. Dilute polymerization in the presence of free radicals. The polystyrene (ps) beads impregnated in this way are foaming agents, typically Cw hydrocarbons, such as pentane, to produce expandable polystyrene (EPS). Beads. However, suspension polymerization produces ps beads of broad size distribution, and the ?8 or 63748-970214.doc 1298330 EPS beads must be size fractionated, ie separated into particle size ranges suitable for the desired end use. Part of the suspension polymerization environment allows the EPS generator to optimize the portion of the polymer bead that has the desired size, for example, as a thin-walled packaging material, most of the total bead yield. The fraction will remain the less desirable grade or will be the outer dimensions of the specification. In German Patent No. GB_A_14164〇5, Sekisui describes a method in which the suspension polymerization of styrene is small in size. The final product is carried out in the presence of a polystyrene seed of the desired size. Typically, the Sergi water process can be carried out as a two-stage suspension polymerization. When s forms, for example, smaller particles having a form size of about 9 microns, The stage is terminated. The beads are then fractionated to remove too small and too large portions, leaving ps seeds, for example 400 to 1800 microns in size, after which the seed is used in the second suspension polymerization stage. Produces that the desired particle size distribution is narrower than that achieved in conventional suspension polymerization reactions. However, even though the process produces a product with a broad particle size distribution, the complexity of the classification step is increased because it must be in the first polymerization stage. Produced on smaller particles. The Eps fraction produced by conventional and Sergi water processes contains particle size ranges, such as particle diameters that vary by hundreds of microns. This is detrimental to the processing of Eps beads to % expanded polystyrene products. In the flaring polystyrene product formulation, the Eps beads are first pre-expanded to produce free-flowing expanded particles, typically used The temperature is below 1 〇〇. The turbulent flow, which is then sealed in the model, is typically 丨1〇63748-970214.doc 1298330 to 120 C before being sealed in the mold and steamed. The particles are fully expanded and burned. During the burning period, the pre-expanded particles develop the elasticity necessary for the molding process. The particle size distribution in the EPS beads is not simply replicated in the pre-expanded beads, but the size of the square cloth is relaxed and produced. Wide density distribution, because the smaller the EPS beads will be, the less they will expand under the same environment. The larger the beads, the more the storage bin containing the mixture, including small high-density particles and larger low-density particles. The occurrence of sedimentation from smaller, higher density particles results in a non-uniform mixture of pre-expanded particles fed from the storage bin to the mold, thus resulting in a change in the final strength and strength of the weighted product. Thus, the broad particle size distribution of the graded Ep$ beads' thus pre-expanded particles results in difficulty in producing expanded polystyrene products and makes the product quality uneven and difficult to control. It has been found that it is possible to produce substantially monodisperse (i.e., single size) polymer seed particles that can be used in suspension polymerization to produce larger, single, still monodisperse polymer particles, for example, sized for an Ep$ Substantially monodisperse EPS particles for a representative end use. This polymer particle production process is described in World Patent No. WO99/19375. The disclosure of World Patent No. WO99/19375 is incorporated herein by reference. Since the product is essentially monodisperse, no mechanical grading is required, resulting in reasonable savings during production equipment and processing. In addition, no undesired series are produced, which results in a reasonable increase in effective yield and a reduction in waste. In addition, problems associated with a wide range of particle sizes within the graded EPS product are avoided or reduced. 63748-970214.doc 1298330 In the world patent No. WO99/19375, the particle size expansion cycle of the polystyrene particle production process is more time consuming, and it has been found that the method can be accelerated, if at least one expansion cycle, the seed crystal is similar to Europe. Pre-expansion in the method of Uggsda polymerization as described in U.S. Patent No. ep-b-3905 (Sintef) and U.S. Patent No. US-A-4,530,956 (Ugelstad) This disclosure is incorporated herein by reference. The polymer beads can be produced by diffusing a monomer and a polymerization initiator (or catalyst) into the polymer seed crystal in an aqueous dispersion. The seed crystal expands, followed by initiation of a polymerization reaction, such as heating, to activate the initiator to produce larger polymer particles. The maximum volume that is increased due to expansion and polymerization is typically about x5 or less. Later, Professor John Ugst (after pr〇fess〇r
Ugelstad)發現晶種膨脹之能力能夠提高至體積提高χΐ25或 甚至更鬲，倘若在該單體塊用以膨脹晶種前，將較低分子 量和低水溶性之有機化合物擴散於晶種内。該影響係基於 熵而非尤其基於有機化合物之化學本質。聚合弓丨發劑可以 便利地用於本目的。有機溶劑，例如丙酮或部份單體，可 以,用以提高有機化合物擴散於晶種中。此"烏袼斯特聚合 法，其述於例如於歐洲專利第砂各39〇5號（辛德福）和美 國專利第US-A-4530956號（烏格斯特）中，可以用以產生單 分顆粒，必要時進行數個膨脹和聚合階段以達到 粒尺寸。 而稍 在烏格斯特法之簡化型中，提高之膨脹能力可以利 聚物晶種顆粒簡單地達& ’例如其中募聚物重量平 量相當於達到50單體單元或達到5〇〇〇達爾頓。 刀 63748-970214.doc 1298330 因此從本發明之—個觀點 a 捉供一種方法以製供游斗、 顆粒尺寸至少50微米之臂人仏 I備形式 丁 Il a物，較佳至^ 少⑵微米，該方法包括 季又仏h7〇也卡’例如至 (昀得到第一微粒晶種物質 ,^ i 貝（其在一個具體實施例中，形 式直徑不大於50微米，較 形 米）； 个大4〇从未，更佳不大於30微 (b)使用该第一晶種物質，、$ ^ ^ 退仃⑷，予1合反應以產生形 式顆粒大直徑大於該第一 S接 日日種物貝之弟二微粒物質，必要 時，可以使用該第二晶種物質 U切負進仃至少一個進一步之懸浮 ^^合反應’以產生得一種开j 4 p , 種形式尺寸大於50微米之微粒聚合 物’較佳大於7 〇微米，更佳 1大於120¼米，其中在步驟（b) 中形式顆粒直徑增加至少χ2 乂土 王夕X2，較佳x4，更佳至少χ1〇，例 如xl0至xl5 ;且 ⑷將步驟（b)之微粒產物&需要地浸潰並/或熱處理及/或 表面改質； 特徵為至少一個在步驟（b)中完成之懸浮聚合反應，包 括 ⑴形成-種水性分散液，纟包括聚合物晶種物質、分子 量低於5000達爾頓（Dalt〇ns)且在25t：水溶性低於丨〇.2克/公 升之有機化合物（例如聚合引發劑）、安定劑、且視需要有 機溶劑（如丙酮或一部份以下所述之單體）； (ii)容許該有機化合物擴散於該晶種物質中，以產生一 種活化之晶種物質；和 (111)將該活化晶種物質與單體（如苯乙烯）和與一種聚合 63748-970214.doc -11 - 1298330 引發劑接觸，並完成其懸浮聚合反應。 或者在以上方法中步驟（b)中形式顆粒直徑之提高可以 為至少X1.5 ’例如至少χ 1 · §。 在本發明之方法中’晶種和最終產物較佳為實 八 散。 、刀 在本發明之方法中，晶種活化階段（步驟⑴和⑽，較佳 包括產生聚合物晶種之水性分散液，其亦為—種有機化合 物之"水包油（oil-in-water)，，乳液，較佳為如過氧化二苯甲 醯之聚合引發劑。由聚合物晶種採取有機化合物可：利用 使用其中有機化合物可溶之有機溶劑而幫助，例如一種如 酮類（丙酮）’醇類，⑽類等等之溶劑，或更佳一種如苯乙 烯之單體。其中該有機化合物為一種聚合引發劑時，尤指 其中早體係用以作為溶劑0夺，調配步驟⑴較佳在低於引發 劑活化溫度之溫度完成，例如在1〇和65t間之溫度，較佳 在20和55。(：之間，更佳25和5(rc之間，尤其較佳在3〇和45 °c之間。 採取有機化合物後，分散液之溫度較佳提高至聚合引發 劑具活性之程度，例如60至100。(：，較佳70至95艺，更佳 75至90 C，並較佳以水性乳液或單一單體相般添加單體。 關於生產形式尺寸達80微米之顆粒，較佳以水性乳液般添 加單體，關於生產形式尺寸大於4〇微米之顆粒，更尤指8〇 微米以上，尤其是100微米以上（例如達15〇〇微米），以單一 相材料般添加單體較方便。 關於有機化合物和單體，乳液配方較佳使用一種增強混 63748-970214.doc -12- 1298330 成例如’壓力均化器或轉子固定混合器，如 齡彻叫化^，如此乳液滴㈣式直徑低於㈣ 米’更佳低於10微米。 ^ 應；|貝車乂佳包含一種水性相之聚合反應抑制劑， 彳-#卩避免形成新顆粒。使用碘化鉀實質上刪除 、米且/、用途形成本發明之進一步觀點。有鑑於此，本發 明提出-種以懸浮（或分散）聚合反應，較佳播㈣浮（或分 散）聚合反應製備聚合物顆粒之方法，特徵在於水溶性聚 合反應抑制劑’較佳為魏卸，係用於水性相。此能夠在 聚應&開始時添加（即當添加單體時或當單體塊開 始/j力夺）然而，較佳在聚合反應期間添加更多抑制 劑。該水溶性抑制劑可以添加至濃度為例如⑴❹ppm重 量比，較佳3至30重量比。 早體和抑制劑添加較佳以延長期間完成，例如1至15小 時二較佳1至1〇小時，更佳1至8小時，單體添加速率可以 口定仁車又j土於6亥期間提高。此一添加可以以批次方式， 但較佳為連續。添加期間，較佳授拌該聚合反應混合物。 土月方法之至少-個最終聚合循環中，為了聚合階 段終止時降低未反應單體之含量，聚合混合物之溫度較佳 提高例如U)至4(TC，較佳25U5t。溫度提高較佳約〇1 至2.0C/刀鐘’更佳〇2j_1〇t>c/分鐘，聚合溫度較有利維 持高溫’直到分析顯示未反應單體幾乎消失，例如30至 120分鐘。 如上所述之單體較佳以水包油乳液般添加；此乳液較佳 63748-970214.doc -13 - 1298330 包括水’單體，引發劑（例如Trigonox 117和ΒΡΟ)，和界面 活性劑（例如波羅薩馬（p〇1〇xamer)或乙氧化花楸丹酯界面 活性劑’如Tween 20)。 在一個本發明方法之較佳具體實施例中，尤指適於生產 形式顆粒尺寸為50至120微米之顆粒，聚合物晶種活化和 聚合循環包括以下步驟： (A) 形成在水性相包含立體安定劑（例如纖維素醚或如磷 酸鈣之無機化合物（TCP))之聚合物晶種水性分散劑； (B) 將分散液溫度上升至“至^，並使用中等混合於_ 單體（例如苯乙烯）引發劑之溶液中混合，於是形成引發劑 溶液； (c)使引發劑能夠擴散於晶種中，例如3〇至12〇分鐘，較 佳約60分鐘； - (D) 將活化之分散液溫度上升至引發劑活化之溫度（例 _ 如60至95 C，較佳70至90 C )，並添加聚合反應抑制劑（例 如KI)溶液，並連續添加水，單體，安定劑，聚合引發 劑’視需要添加之油溶性聚合引發劑，及抑制劑之乳液；修 (E) 連績添加單體乳液，視需要可以添加更多水溶性抑 制劑一次或多次；且視需要可以 (F) 使聚合反應混合物温度至更高溫，例如卯至1⑽。c， 以耗盡單體（較佳在單體添加完成後）。 此活化和聚合循環可以重複，以產生所需尺寸之聚合 物顆粒。較佳此-循環將包括將顆粒體積提高至少x5。因 此例如幵y式直徑2〇微米之最初聚合物晶種可以便利地在 63748-970214.doc •14- 1298330 二個聚合循環中變形，首先至形式直徑4〇微米其後至形 式直徑80微米。較佳該晶種以此方式從5膨脹至乃微米至 70至90微米（例如在2或3個膨脹循環内），並從7〇至9〇至2〇〇 至2 0 〇 〇微米（例如在2至5個循環内）。 在本發明方法中，步驟（b)可以，但較佳不要包括從晶 種物質移除尺寸太大或太小之顆粒，以便產生實質上單分 散晶種物質。 在本發明方法中使用之懸浮聚合階段總數典型上將達12 個，較佳達8個。典型上從低於5〇微米變為至大於5〇〇微米 將需要一個階段以上，通常為二個或多個，較佳三個或四 個。對於尺寸高於1〇〇微米之晶種而言，每階段顆粒體積 將方便地為至少χ2·74 ,例如至少以，且低於χ6〇，較佳低 於x30，較佳從幻至以5，例如幻至\15。對於尺寸低於^⑼ 微米之晶種而言，每階段顆粒體積較佳在义2.74和乂5〇之 間，例如Χ4至χ40，更佳在χ5和χ3〇之間，尤其較佳從“至 χ15，例如約。 必要時’可以在本發明中使用二種或多種不同形式直徑 之實質上單分散晶種之群數，以產生一種多模數，較佳雙 模數之最終產物，其能夠較筆直地分級，以產生不同實質 單刀政級數，例如，相當於不同最終用途較佳之EPS級 數。 七式顆粒尺寸表示，在顆粒尺寸分佈測定中，其使用如 CJoultei： LS 13 0顆粒尺寸分析器之顆粒尺寸測定裝置，可 债測顆粒之尖峰顆粒尺寸，例如在顆粒尺寸分佈相對於總 63748-970214.doc -15- !29833〇 體積百分比之形式顆粒尺寸。 I實貝上單分散表示對於許多顆粒（例如至少1〇〇，更佳至 少。1000)而言，顆粒之變化係數（cv)低於鳩，例如低於 15=’較佳低於12%，更佳低於11%，甚至較佳低於10%， 更佳不大於約8%。cv係如下測定之百分比 100X標準偏差 cv=~ 其中平均值為平均顆粒直徑，標準偏差為顆粒尺寸之標準 、cv較佳以主要形式計算，即藉由將單模數分佈曲 線合於偵測顆粒尺寸分佈。因此一些低於或高於形式尺寸 之顆粒可以在計算中折扣’其可以例如以約90%之總顆粒 ，可偵測顆粒)為基準’或更多，較佳約95%。此一測 定CV可於Coulter LS 130顆粒尺寸分析器上進行。 各放大階段中晶種和放大顆粒需要之單分散度傾向隨放 ^進行而變化。對於最初和早期階段之晶種而言，高度單 分散性是需要的，且產物之分級亦可能是需要的。因此， 通常倘若聚合階段之產物CV為約25%，則較佳將經分級以 便其後階段產生CV低於25%之晶種，較佳低於2〇%。關於 形式尺寸低於15〇微米之晶種，cv尤其較佳低於5%。cv 尤其較佳低於5。/。。關於形式尺寸大於15〇微米之晶種， 較佳為約10%或更低。 本發明方法之個別聚合階段特徵在於在不同反應器室 進行’但添加更多單體且希望亦添加更多懸浮較質。j 佳連續添加更多單體直到添加所需之單體量。此添加亦， 以以固定速率，但更佳添加速率隨添加進行而提高，添; 63748-970214.doc •16- 1298330 為逐步或階梯式。 本發明方法使用之最初實質單分散聚合物晶種物質可以 =利地以任何方法產生，其產生實質上單分散之聚合物產 ’例如，以在有機溶劑中進行之分散聚合法，或更佳以 美國專利第US-A-4336173號和第US_A_445937g中所述 、斤述之烏格斯達特（辛德福）法。由辛德福法產生之單 刀政聚合物顆粒商業上由挪威迪諾特殊品聚合物公司 (Dyno Specialty P〇lymers AS)^ f , ^ ^ ^ Dynospheres® ^ 典型上形式顆粒尺寸在2至30微米之間。 烏格斯達特法係一種"活化膨脹”法而非懸浮聚合反應， 因為聚合反應僅在所有單體被吸收於起始聚合物晶種中後 :引發。相反地，如此處所述般，在晶種懸浮聚合反應 ，成長之晶種連續地接觸新鮮單體和引發劑。 最初聚合物晶種物質較不佳地可以以產生多分散產物之 方法產生’例如’傳統之懸浮聚合法，其後將多分散產物 尺寸分離以產生一種實質上單分散顆粒群集。 最初單分散顆粒可以藉由實質上如美國專利第—A· 5 1479Γ號福瑞沙（Mm))中所述之懸浮聚合變形為較大 之實質上單分散聚合物晶種，惟個別聚合階段之數目和持 ，期間係經選擇’以產生所需形式顆粒尺寸之最終實質上 ^分散晶種產物。通常最終晶種產物所需之形式尺寸將符 合-種尺寸，由該尺寸最終懸浮聚合反應產物可以在單— 反應器内’於一個或較不佳於一個以上之聚合階段以需要 之平均顆粒尺寸產纟。㈣對於製造开》式尺寸為柳， 63748-970214.doc -17- 1298330 6:〇，_和13°。微米之醉最終產物珠粒而言，即例如適 用於各種級數之EPS珠粒，最終晶種形式尺^ : 在Π0微米，3職米，_微米和925微米職内。 尤其意外地，能夠維持顆粒之 生之顆粒成長度，例如，從最、I刀月又’不管所發 之多…… 微米尺寸烏格斯達特顆粒 之夕P“又成長，至毫米尺寸之最終產物。 頃發現此多階段成長是有利 J U為t合法架境能夠右 各階段個別最佳化，且1容 ^ ^ /、 4最終成長階段能夠使用傳統 耄米尺寸顆粒在懸浮聚合生產 " 座之方法％境和控制完成。 以烏格斯達特法產生微米、 曰主 ,g 木尺寸最仞晶種之進行較耗時且 叩貝，且時間和花費隨顆粒 ^ , ^ , ^扠同之尺寸急遽地上升。此 4廷特顆粒太小而不能用於產生 商業級EPS顆粒之單階段懸浮 1 口汉應，因此，此類顆教 不能表示用以作為EPS用聚 b類顆拉 > 口物日日種之明顯選用物，部份 由於花費’部份由於期望單分散性將在成長法期間失去。 然而’使。用多階段懸浮聚合反應達成成長法，不僅是實質 上保留單分散性，而且^ & 、 馬格斯達特法之花費亦變少-因 此，1克20微米烏格斯達特產 t 座物此夠變形為約275公斤1300 微米最終產物。 β 現將使用例如苯乙烯聚合♦ 糸統更砰述本發明之方法和產 物。然而，如上所述般，當 _ , _ 田為一種尤其重要之產物 時’該方法可應用於其它聚合物和產物。 所使用之最勒晶種顆粒較佳為聚苯乙_^ μ# 褐法產生之Dyn〇sphere，(迪諾特殊品聚合物公司，挪威里 63748-970214.doc 1298330 勒斯壯（Lillestr0m))，尤其較佳為形式尺寸介於〇5至5〇微 米間之顆粒，尤指5至30微米’最佳約1〇_2〇微米。或者， 彼等可以是以標準乳液聚合步驟所產生之尺寸分別之聚苯 乙稀顆粒，例如形式尺寸為〇.〇5至1〇微米，或形式尺寸達 2〇微米之聚苯乙婦顆粒’更佳α1〇微米，由在有機溶劑 内之分散聚合反應產生。最初之晶種顆粒其後可以被放 大以在逐步懸浮聚合法中產生形式尺寸達剛〇微米之最 終晶種顆粒，該方法中至少一個階段包括如上所述之活化 階段 '然而一個或多個聚合階段可以實質上如美國專利第# US_A-5147937號中所述般。 美國專利第US-A-5 147937號之方法包括將晶種顆粒之水 性分散液與非水溶性單體或單體混合物，和油溶性自由基 聚合引發劑，或其先質之水性乳液結合，因此，將等於全^ 部最初晶種聚合物重量之單體或單體混合物以此速率於Μ 至120分鐘，較佳6〇至9〇分鐘與分散液結合。該結合較佳 在至少如引發劑或先質被活化之溫度般高之溫度進行，且 將反應混合物維持於引發劑或先質被活化之溫度，直到晶 _ 種頃成長所需之量，直到單體耗盡較適當。其後重複該步 驟，直到達到最終所需之顆粒尺寸。 在本毛月方去中，尤其較佳，將反應混合物之單體含量 維持於不大於在任何既定時間該聚合物含量之20%重量 比’更較佳不大於10〇/〇。 較佳各成長階段將顆粒體積提高1·1χ至ΙΟΟΟχ，例如Ux 至60x’更佳2X至50χ，尤指2乂至3〇#例如3乂至3〇4，更佳 63748-970214.doc -19- 1298330 4x至30x(例如4x至25x，或4x至20x)，最佳6x至25x(例如6x 至15x)。實際階段較佳可以包括體積提高不大於15χ(即提 高不大於1 5倍體積），尤指產生較小顆粒時。 使用之單體可以是純苯乙烯或苯乙烯衍生物，或者可以 是一種苯乙烯和/或苯乙烯衍生物和視需要非苯乙烯系共 單體之混合物，例如傳統之苯乙烯共單體。苯乙烯和苯乙 烯衍生物，如烷基苯乙烯（例如Cl_3_烷基苯乙烯，如〇_甲基 苯乙烯，m-甲基苯乙烯，p_甲基苯乙烯，二甲基苯乙烯， 乙基苯乙烯，乙基-甲基·苯乙烯等等）和_基苯乙烯（例如鲁 P-氯苯乙烯或2,4-二氯苯乙烯），和其它傳統或非傳統苯乙 烯’可以用以產生均聚物或共聚物。然而，通常苯乙浠， 且尤其苯乙烯將較佳為用以從晶種顆粒成長之主要化事實 上為唯一之單體。 在一個本發明方法之尤其較佳具體實施例中，係使用胺 基苯乙烯（尤指4-胺基苯乙烯）作為共單體，尤其較在最終 懸浮聚合階段中。如此，可以直接產生胺官能化顆粒。此Ugelstad) found that the ability of the seed to expand can be increased to a volume increase of χΐ25 or even more, provided that the lower molecular weight and less water soluble organic compounds are diffused into the seed crystal before the monomer block is used to expand the seed crystal. This effect is based on entropy and not on the chemical nature of organic compounds in particular. The polymeric hair styling agent can be conveniently used for this purpose. An organic solvent such as acetone or a part of a monomer may be used to enhance the diffusion of the organic compound into the seed crystal. This "Wuester's polymerization process, which is described, for example, in European Patent No. 39, No. 5 (Sindelford) and US Patent No. US-A-4,530,956 (Ugst), can be used to generate a single The particles are divided, and if necessary, several expansion and polymerization stages are carried out to achieve the particle size. In the simplified version of the Ugast method, the expansion of the expansion ability can be achieved by simply concentrating the particles of the seed crystals, for example, where the weight of the condensed polymer is equivalent to up to 50 monomer units or up to 5 〇〇. 〇 Dalton. Knife 63748-970214.doc 1298330 Thus, from the point of view of the present invention, a method is provided for the production of a hopper, a particle size of at least 50 micrometers, preferably to a minimum of (2) micrometers. , the method includes the season 仏 h7 〇 also card 'for example to (to obtain the first particulate seed material, ^ i shell (which in a specific embodiment, the form diameter is not more than 50 microns, the shape of the rice); 4〇 never, preferably no more than 30 micro (b) using the first seed material, $ ^ ^ 仃 (4), to a combination reaction to produce a form of particles larger than the first S The second particle material, if necessary, can be used to cut at least one further suspension reaction using the second seed material U to produce an open j 4 p particle having a size greater than 50 microns. The polymer 'preferably greater than 7 〇 microns, more preferably 1 is greater than 1201⁄4 meters, wherein in step (b) the form particle diameter is increased by at least χ2 乂土王夕 X2, preferably x4, more preferably at least 〇1〇, for example xl0 to xl5 And (4) impregnating and/or heating the particulate product & step (b) And/or surface modification; characterized by at least one suspension polymerization completed in step (b), comprising (1) forming an aqueous dispersion comprising cerium seed material having a molecular weight of less than 5,000 Daltons (Dalt〇) Ns) and at 25t: an organic compound (eg, a polymerization initiator) having a water solubility of less than 0.2 g/liter, a stabilizer, and an organic solvent (such as acetone or a part of the monomers described below) as needed; (ii) allowing the organic compound to diffuse into the seed material to produce an activated seed material; and (111) the activated seed material with a monomer (such as styrene) and a polymerization of 63748-970214. Doc -11 - 1298330 The initiator is contacted and the suspension polymerization is completed. Alternatively, the increase in the diameter of the form particles in step (b) of the above method may be at least X1.5 'e.g. at least χ 1 · §. In the method of the invention Preferably, the seed crystal and the final product are in the form of a seed. In the method of the present invention, the seed crystal activation stage (steps (1) and (10) preferably comprises an aqueous dispersion for producing a polymer seed crystal, which is also - Organic compound "oil-in-water, emulsion, preferably a polymerization initiator such as diphenylguanidinium peroxide. Organic compounds can be taken from polymer seed crystals: organic compounds in which organic compounds are soluble Helped by a solvent, for example, a solvent such as a ketone (acetone) 'alcohol, (10) or the like, or a monomer such as styrene, wherein the organic compound is a polymerization initiator, especially an early system. For use as a solvent, the compounding step (1) is preferably carried out at a temperature lower than the activation temperature of the initiator, for example, at a temperature between 1 Torr and 65 Torr, preferably at 20 and 55. (Between, more preferably 25 and 5 (between rc, especially preferably between 3 〇 and 45 °c. After taking the organic compound, the temperature of the dispersion is preferably increased to the extent that the polymerization initiator is active, for example 60 to 100. (:, preferably 70 to 95 art, more preferably 75 to 90 C, and it is preferred to add a monomer as an aqueous emulsion or a single monomer phase. Regarding the production of particles having a size of 80 μm, preferably The addition of a monomer in the form of an aqueous emulsion is more convenient for a particle having a size greater than 4 μm in production, more particularly 8 μm or more, especially 100 μm or more (for example, up to 15 μm), and it is convenient to add a monomer as a single phase material. Regarding organic compounds and monomers, the emulsion formulation preferably uses an enhanced blend of 63748-970214.doc -12-1298330 into, for example, a 'pressure homogenizer or a rotor-fixed mixer, such as age-appropriate ^, such an emulsion drop (four) The diameter is less than (four) meters' better than 10 microns. ^ Should; | Bayer 乂 preferably contains an aqueous phase polymerization inhibitor, 彳-#卩 to avoid the formation of new particles. Use potassium iodide to remove substantially, rice and /, Use forms a further aspect of the invention. In view of the above, the present invention provides a method for preparing polymer particles by suspension (or dispersion) polymerization, preferably by buoyancy (or dispersion) polymerization, characterized in that the water-soluble polymerization inhibitor is preferably unloaded. Used in aqueous phase. This can be added at the beginning of the polymerization & (ie when adding monomer or when the monomer block starts), however, it is preferred to add more inhibitor during the polymerization. The inhibitor may be added to a concentration of, for example, (1) ❹ ppm by weight, preferably 3 to 30 by weight. The addition of the precursor and the inhibitor is preferably completed in an extended period, for example, 1 to 15 hours, preferably 1 to 1 hour, more preferably For 1 to 8 hours, the monomer addition rate can be increased during the period of 6 liters. This addition can be batchwise, but preferably continuous. During the addition, the polymerization mixture is preferably mixed. In at least one final polymerization cycle of the earth-moon process, in order to reduce the content of unreacted monomers at the end of the polymerization stage, the temperature of the polymerization mixture is preferably increased, for example, U) to 4 (TC, preferably 25 U5t. The temperature increase is preferably about 〇 1 to 2.0C/ The clock 'better' 2j_1〇t>c/min, the polymerization temperature is more favorable to maintain the high temperature' until the analysis shows that the unreacted monomer almost disappears, for example, 30 to 120 minutes. The monomer as described above is preferably an oil-in-water emulsion. Addition; this emulsion is preferably 63748-970214.doc -13 - 1298330 including water 'monomers, initiators (such as Trigonox 117 and hydrazine), and surfactants (such as Polo Sama 1amer or B) Oxidized phthalocyanine surfactants such as Tween 20. In a preferred embodiment of the process of the invention, especially suitable for the production of particles having a particle size of 50 to 120 microns, polymer seed activation and polymerization. The cycle comprises the steps of: (A) forming a polymer seed aqueous dispersion agent comprising a stereoscopic stabilizer (for example, a cellulose ether or an inorganic compound such as calcium phosphate (TCP)) in an aqueous phase; (B) raising the temperature of the dispersion to "to ^, and mixed with a solution of medium mixed in a monomer (such as styrene) initiator, thus forming an initiator solution; (c) enabling the initiator to diffuse into the seed crystal, for example 3 to 12 minutes , preferably about 60 minutes - (D) raising the temperature of the activated dispersion to the temperature at which the initiator is activated (for example, 60 to 95 C, preferably 70 to 90 C), adding a polymerization inhibitor (such as KI) solution, and continuously adding water , monomer, stabilizer, polymerization initiator 'addition of oil-soluble polymerization initiator, and emulsion of inhibitor; repair (E) continuous addition of monomer emulsion, if necessary, can add more water-soluble inhibitors once or Many times; and if necessary, (F) the temperature of the polymerization mixture to a higher temperature, for example, to 1 (10). c, to deplete the monomer (preferably after the monomer addition is completed). This activation and polymerization cycle can be repeated to produce polymer particles of the desired size. Preferably this cycle will include increasing the particle volume by at least x5. Thus, for example, the initial polymer seed of the 幵y formula of 2 μm in diameter can be conveniently deformed in two polymerization cycles of 63748-970214.doc • 14-1298330, first to a form diameter of 4 μm and thereafter to a shape diameter of 80 μm. Preferably, the seed crystal expands from 5 to 5 to 90 microns (e.g., within 2 or 3 expansion cycles) and from 7 to 9 to 2 to 20 microns (e.g., Within 2 to 5 cycles). In the process of the present invention, step (b) may, but preferably does not, include removing particles of a size that are too large or too small from the seed material to produce a substantially single-dispersed seed material. The total number of suspension polymerization stages used in the process of the invention will typically be up to 12, preferably up to eight. Typically, from less than 5 microns to more than 5 microns will require more than one stage, typically two or more, preferably three or four. For seed crystals having a size greater than 1 micron, the particle volume per stage will conveniently be at least χ2·74, such as at least, and less than χ6〇, preferably less than x30, preferably from illusion to 5 For example, to illusion to \15. For seed crystals having a size lower than ^(9) microns, the particle volume per stage is preferably between 2.74 and 乂5〇, such as Χ4 to χ40, more preferably between χ5 and χ3〇, especially preferably from Χ15, for example about. If necessary, the number of groups of substantially monodisperse seed crystals of two or more different forms of diameter may be used in the present invention to produce a multimodal, preferably bimodal, final product capable of Graded more straightly to produce different substantive single-practice numbers, for example, equivalent to EPS grades for different end uses. Seven-grain size indicates that in particle size distribution measurements, such as CJoultei: LS 13 0 particle size The particle size measuring device of the analyzer can measure the peak particle size of the particle, for example, the particle size distribution relative to the total particle size in the form of 63748-970214.doc -15-!29833 〇 volume percent. For many particles (eg, at least 1 Torr, more preferably at least 1000), the coefficient of variation (cv) of the granules is less than 鸠, such as less than 15 = 'preferably less than 12%, more preferably less than 11%, Even better 10%, more preferably no more than about 8%. cv is the percentage determined by 100X standard deviation cv=~ wherein the average value is the average particle diameter, the standard deviation is the standard of the particle size, and cv is preferably calculated in the main form, that is, by The single modulus distribution curve is combined to detect the particle size distribution. Therefore, some particles below or above the formal size can be discounted in the calculation 'which can be based, for example, on about 90% of the total particles, detectable particles'. Or more, preferably about 95%. This determination of CV can be carried out on a Coulter LS 130 particle size analyzer. The tendency of monodispersity for seed crystals and magnified particles in each amplification stage varies with the release. High monodispersity is required for seed crystals in the early stages, and product grading may also be required. Therefore, generally, if the product CV of the polymerization stage is about 25%, it is preferred to be classified so as to be thereafter The stage produces a seed crystal having a CV of less than 25%, preferably less than 2%. For seed crystals having a formal size of less than 15 μm, cv is particularly preferably less than 5%. cv is particularly preferably less than 5. About the form size is greater than 15 〇 micro The seed crystals are preferably about 10% or less. The individual polymerization stages of the process of the invention are characterized by 'in addition to more monomer in the different reactor chambers and it is desirable to add more suspension to the quality. More monomer until the required amount of monomer is added. This addition is also increased at a fixed rate, but the rate of addition is increased with the addition; 63748-970214.doc • 16-1298330 is stepwise or stepped. The initially substantially monodisperse polymer seed material used in the process of the invention can be advantageously produced in any manner which produces a substantially monodisperse polymer, for example, in a dispersion polymerization process carried out in an organic solvent, or more preferably The Ugstadt (Sindelford) method described in U.S. Patent No. US-A-4,336,173 and U.S. Patent Application Serial No. The singular polymer pellets produced by the Sindelphi method are commercially available from Dyno Specialty P〇lymers AS^ f , ^ ^ ^ Dynospheres® ^ typically in the form of particles between 2 and 30 microns. . The Ugstadt Act is a "activated expansion" rather than a suspension polymerization because the polymerization is initiated only after all of the monomers have been absorbed into the starting polymer seed: instead, as described herein In the seed suspension polymerization, the grown seed crystal continuously contacts the fresh monomer and the initiator. Initially, the polymer seed material may produce a 'for example' conventional suspension polymerization method in a manner that produces a polydisperse product. The polydisperse product is then size separated to produce a substantially monodisperse particle cluster. The initially monodisperse particles can be suspended by polymerization substantially as described in U.S. Patent No. A. 5, 1479, Fressa (Mm). Deformed into larger substantially monodisperse polymer seeds, but the number and duration of individual polymerization stages are selected to produce the final substantially dispersed seed product of the desired form of particle size. Typically the final seed product The required form size will be in accordance with the size from which the final suspension polymerization product can be in a single reactor or in less than one polymerization stage. The average particle size required for calving. (iv) For the manufacture of the size of the willow, 63748-970214.doc -17-1298330 6: 〇, _ and 13 °. Micron drunk final product beads, ie for example Various grades of EPS beads, the final seed form size ^: in Π0 μm, 3 job meters, _micron and 925 micron. Especially surprisingly, the particles can be maintained in length, for example, from the most I knife month and 'no matter how much it is made... The micron-sized Ugstedt particles eve P" grows again, to the final product of the millimeter size. It is found that this multi-stage growth is beneficial to the fact that JU can be individually optimized for each stage of the right frame, and the final growth stage of 1 capacity ^ ^ /, 4 can use the traditional glutinous rice granules in the suspension polymerization production method. % environment and control completed. The use of the Ugsstadt method to produce micron, bismuth, and g-size seed crystals is more time-consuming and mussel, and the time and cost rise sharply with the size of the particles ^, ^, ^. The 4 ting granules are too small to be used for the production of commercial grade EPS granules in a single-stage suspension. Therefore, such cultivating cannot be used as a polyb-type granule for EPS. The obvious choices, in part due to the expense of 'partially due to the expectation of monodispersity will be lost during the growth process. However, 'made. The multi-stage suspension polymerization is used to achieve the growth method, which not only retains the monodispersity in essence, but also reduces the cost of the ^ & Magstad method - therefore, 1 gram of 20 micron Ugstedt t-seat This is deformed to about 275 kg of a 1300 micron final product. The method and product of the present invention will now be further described, for example, using styrene polymerization. However, as described above, when _ , _ field is a particularly important product, the method can be applied to other polymers and products. The most used seed crystal particles are preferably Dyn〇sphere produced by polystyrene _^ μ# brown method (Dino Special Polymers, Norwegian 63748-970214.doc 1298330 Lillestr0m) Particularly preferred are particles having a form size between 〇5 and 5 〇 microns, especially 5 to 30 microns' optimally about 1 〇 2 〇 microns. Alternatively, they may be polystyrene particles of the size produced by the standard emulsion polymerization step, for example, polystyrene particles having a size of 〇. 5 to 1 〇 micron, or a size of 2 〇 micron. More preferably, α1 〇 micron is produced by dispersion polymerization in an organic solvent. The initial seed particles may thereafter be enlarged to produce a final seed particle having a form size up to 〇 micron in a stepwise suspension polymerization process, at least one of which includes an activation phase as described above. However, one or more polymerizations The stage can be substantially as described in U.S. Patent No. # US-A-5,147,937. The method of US Pat. No. US-A-5 147 937 comprises combining an aqueous dispersion of seed particles with a water-insoluble monomer or monomer mixture, and an oil-soluble free radical polymerization initiator, or a precursor aqueous emulsion thereof. Thus, a monomer or monomer mixture equal to the total weight of the initial seed polymer is combined with the dispersion at this rate for from 120 minutes, preferably from 6 to 9 minutes. Preferably, the bonding is carried out at a temperature at least as high as the temperature at which the initiator or precursor is activated, and the reaction mixture is maintained at a temperature at which the initiator or precursor is activated until the amount of crystal growth is required until Monomer depletion is more appropriate. This step is then repeated until the final desired particle size is reached. It is especially preferred in the present invention to maintain the monomer content of the reaction mixture at no more than 20% by weight of the polymer content at any given time, more preferably no more than 10 Å/Å. Preferably, each growth stage increases the particle volume by 1:1 to ΙΟΟΟχ, for example, Ux to 60x' is preferably 2X to 50χ, especially 2乂 to 3〇#, for example, 3乂 to 3〇4, more preferably 63748-970214.doc - 19-1298330 4x to 30x (eg 4x to 25x, or 4x to 20x), best 6x to 25x (eg 6x to 15x). Preferably, the actual stage may include a volume increase of no more than 15 Torr (i.e., an increase of no more than 15 times the volume), especially when smaller particles are produced. The monomer used may be a pure styrene or styrene derivative, or it may be a mixture of a styrene and/or styrene derivative and optionally a non-styrene-based co-monomer such as a conventional styrene comonomer. Styrene and styrene derivatives, such as alkyl styrene (such as Cl_3_alkyl styrene, such as 〇-methyl styrene, m-methyl styrene, p-methyl styrene, dimethyl styrene, Ethyl styrene, ethyl-methyl styrene, etc.) and styrene (for example, Ru P-chlorostyrene or 2,4-dichlorostyrene), and other conventional or non-conventional styrenes can Used to produce a homopolymer or copolymer. However, usually phenelzine, and especially styrene, will preferably be the only monomer used to grow from seed particles. In a particularly preferred embodiment of the process of the invention, an amine styrene (especially 4-aminostyrene) is used as the comonomer, especially in the final suspension polymerization stage. In this way, amine functionalized particles can be produced directly. this
類官能化顆粒尤其適用於固體相有機合成，例如，肽和 聚核苷酸和小型有機分子，於分離中，例如於層析法， 作為相容劑。該胺基苯乙烯較有利與苯乙烯系共單體（ 如苯乙烯）以1:2至1:1〇重量比一起使用，尤指至u =比。在此具體實施例中，在聚合法中暴露於有機溶劑 結果為在形成之顆粒中通常存在交聯。 其它可以使用之共單體包括乙稀系不飽和單體，例如 烯酸，甲基丙稀㈣，乙基丙稀㈣，丁基㈣酸醋， 63748-970214.doc -20- 1298330 基丙烯酸，甲基丙烯酸甲酯和甲基丙烯酸乙酯），順丁烯 二酸和其酯類（例如順丁烯二甲酯，順丁烯二酸二乙酯和 順丁烯二酸二丁酯），順丁烯二酸干，反丁烯二酸和其酯 類（例如反丁烯二酸二甲酯和反丁烯二酸二乙酯），乙烯基 單體，和丙烯腈。 非笨乙稀系共單體車父佳將為任何成長階段中添加之聚合 物的0。/。或1至40%重量比。例如，丙烯酸甲基丙烯酸共單 體可以用以作為非苯乙烯系共單體，例如可以使用二甲基 丙烯I伸乙酯（EDMA)，羥乙基甲基丙烯酸酯（HEMA)，丙 烯酸甲酯，甲基丙烯酸縮水甘油酯（GMA)，丙烯酸，丙烯 酸甲酉旨’丙烯酸乙醋，丙烯酸丁醋，甲基丙稀酸，甲基甲 基丙烯酸乙S旨。然❿’可以使用甲基丙烯酸甲醋作為 100%單體。 曰曰種顆粒較佳為一種類似或至少與聚合⑼晶種所使用成 長階段添加之聚合物相容之聚合物。因此，該烏格斯達特 晶種較佳主要為苯乙烯聚合物，尤指在其表面上。 抑除了簡單之乙烯系共單體外，亦能夠使用能夠交聯之共 單體例如一乙烯苯和聚乙二醇二甲基丙烯酸酯。此類可 交聯共單體通常將以較少量使用。 奸適當聚合引發劑之實例包括有機過氧化物，如過氧化二 ，甲醯〆和過氧化月桂醯’㉟g旨類’如過氧苯甲酸三級丁 酉曰和過虱化三甲基乙酸三級丁酯和偶氮化合物，如偶氮雙 5=和偶氮雙二甲基三甲基乙浠腈。這些可以使用傳 又丨丨如相對於單體為〇」至10%，較佳〇 2至4%重 63748-970214.doc 1298330 比），且較佳以於單體或單體混合物中之溶液，或於情性 有機溶劑内添加’如苯，甲苯或二氣丙烷。在使用有機溶 劑之處，此較佳相對於聚合物含量為少量。 較佳使用至少-種油溶性聚合反應抑制劑，其係配置於 單體或單體混合物中以避免在無晶種單體滴液内聚合，因 而新顆粒晶核生成。此一抑制劑較佳具有高分子量(例如 至少300達爾頻）和低水溶性以降低經由水相擴散。該抑制 劑可以例如是一種酚系化合物(如3,5_二·三級丁基_4-羥基 甲笨，1，1-雙（4-羥苯基）環己烷，4,4_亞丁基-雙（3·甲基 一、、及 丁酚）’ 1，3,5-二甲基-2,4,6-參_(3,5-二-三級丁基_4_羥 苄基）苯（Irganox 1330)，2,2，_亞甲基雙（6_三基_ 丁基^ 酚），硫化合物（如二月桂基硫二丙酸醋，4,4，_硫雙甲基· 6-三級丁基-酚)’或胺(如N，N，·二+荅基亞苯二胺和： 苯基異丙基亞苯二胺）。 抑制劑用量較方便相對於該抑制劑為〇·5至1〇%，較佳^ 至5 %重量比。 關於傳統之懸浮聚合，在反應介f中亦較佳包括—種或 夕種安疋劑。尤其在水性晶種懸浮液中較佳包括懸浮安定 劑（即立體安定劑），以及在添加彼等之水性單體乳液中包 括乳液安定劑。適當安定劑之實例包括離子性，乙氧化離 子性’非離子性和聚合物兩親媒性分子’和無機顆粒，例 如水溶性高分子量物質，磷酸鈣（TCP)，纖維素（包括纖維 素醚，如烷基纖維素醚，尤指cw烷基纖維素醚；和羥烷 基烧基纖維㈣，尤指經基々4_燒基基纖維: 63748-970214.doc -22- 1298330 謎，例如經燒基甲基纖維素，如經丙基尹基纖維辛，可取 =例如—…00’多元醇，聚乙稀醇，聚環氣燒 土，和無機物質，如磷酸約和焦鱗酸鎮。較佳以纖維㈣ 和tc:作為懸浮安定劑’尤指生產較大尺寸之聚合物顆 粒。較佳此類安定劑係以相對於任何循環令最初聚合物晶 種之w/w存在，尤指15至55%於纖維素 驗類，安定劑濃度較方便達25% w/w，而關於如—之無 機女疋劑’安定劑濃度較有利達相對聚合物循環内最初晶 種為55% w/w，例如丨至55% w/w，較方便為爪训士。 TCP尤其較佳，因為其能夠使用此類高漢度 境衝擊低。 乳液安^劑可以例如是界面活性劑，例如波羅薩馬 ㈣〇x_r)或其它聚環氧院基’如。此外，可以使 用乳液安定劑，如包含20至15〇個環氧乙炫單元之壬紛_聚 壤氧乙燒’例如Berol 274siUgepalc〇99〇。或者可以使用 ㈣H mb離子界面活性劑。這些安定劑較佳存在單 體乳液中’例如濃度為相對於單體含量〇1至2%，較佳 至1.0%重量比。 較佳在最終聚合階段中使用之懸浮液安定劑為一種益機 固體微粒，如鱗酸鹽（例如磷_)，其能夠即時在清洗步 驟中從產物移除。懸浮U劑通常將使用相對該晶種之 0 · 5至2 5 %重量比。 典型上從較小晶種製備晶種可以在裝錢拌器，入口和 出口淳及溫控之反應器中完成（例如1.5公升至H)公升熱爸 63748-970214.doc -23 - I ' 1298330 反應器）。 將反應器裝填最初或後來階段之晶種，懸浮安定劑，去 離子水，當晶種為小型時（例如低於50微米，尤指低於30 微米），較佳亦裝填如硝酸鈉之水溶性抑制劑。在顆粒成 長早期階段中使用抑制劑之處，此典將以在水中0 001至 0.005%重量比之濃度使用。 此晶種典型上達水性懸浮液之65%重量比，例如1至 60%，較佳10至60%重量比，該安定劑典型上相對於該晶 種為0·5至15%，較佳1至1〇%重量比。 晶種懸浮液之溫度典型上上升至約7〇至1〇〇。(：，較佳Μ 至92%，並添加單體乳液。 單體乳液典型上藉由將油溶性引發劑和油溶性抑制劑 (例如過氧化二苯甲醯和Irgan〇x 133〇)溶於苯乙烯單體（或 單體混合物），並與乳液安定劑之水溶劑混合（例如Βα〇ι 274或Igepal C0 99〇)。油（單體）相較希望製成單體乳液之 30至60%重量比，其係以任何便利之乳化技術製備，例如 使用如Ultra-Turax之轉子固定混合器。 在關於乳化之範圍内，確保單體乳液滴液尺寸小對於較 小晶種是重要的，通常較佳該單體乳液滴液應該小於在任 何既定階段中使用之晶種顆粒。 因此較佳藉由將混合物通過壓力均化器或許多轉子固 疋P自&形成乳液。如此過大滴液之產生便降至最低。戋 者，混合物可以其後通過一系列分離之轉子固定器或重複 循環通過低一轉子固定混合器。 63748-970214.doc -24- 129833〇 一其後將單體或單體乳液便利地連續供入反應器之攪拌懸 净液中，較佳使用可調整之供料速率幫浦。供料速率較佳 ’、持於0.1至2.0克，尤其0·15至10克，更尤指約〇 15至〇·8 ^ ’尤指〇·15至0·6克，單體/小時，以每公克反應器内之 a物即在添加期間供料速率較佳提高。當單體添加完 成時，攪拌反應混合物直到單體耗盡，例如約2小時，或 者以添加追逐劑（chaser)(即一種具高濃度引發劑之單體組 合物）或提高反應器溫度而使聚合反應終止。必要時，可 以使用第二聚合引發劑，其在高於第一之溫度活化。 在此類聚合階段之各終點，顆粒大尺寸較佳經測定（使 用卡爾特（Coulter)計數器），因而計算在任何連續階段中使 用之單體量。 當聚合階段發現產生不希望之大顆粒尺寸分佈時，對於 同一成長階段之性能體積尺寸應該提高。然而，產物依然 可以用於進一步之成長階段，倘若其經分級以移除過小或 過大顆粒。 聚合反應完成後，可以移除放大之顆粒，必要時清洗以 移除不希望之安定劑，引發劑等等。 聚合反應懸浮液之安定度和所產生聚合物之分子量，係 取決於不同方式之變數範圍（例如單體添加速率，抑制劑 濃度’溫度’乳液滴液尺寸，晶種尺寸等等）。 安定性需要避免凝聚。此典型上能夠藉由確定晶種顆粒 中單體濃度不超過约20-25%重量比而確定，更佳不超過約 10至20Λ’尤其較佳其不超過約重量比。避免過量單 63748-970214.doc -25- 1298330 m夠藉由提高引發劑濃度（雖然此降低所形 物之刀子里，聚合物黏度和其玻璃轉移溫度），或降低.. 體添加速率（其提高聚合物分子量和反應時間）而達成。: =瘟基本上忒方法之包作必需平衡引發劑濃度和單體添加 1率’以避免可接受方法時間内之凝集並達成所需之分子 量。 相水含量可以改變而無太大問題，即使懸浮液水含量太 低，可能失去安定性。 類似礼化劑’即乳液安定劑，含量並不嚴苛，即使失去 太低安定性，且即使膠微粒形成太高，因此可能發生細粒 ^成通爷可以操作本發明之方法，產生低於約重量 比細粒。 攸典型上10-20微米Dyn〇spheres®之起點，放大至例如 200至1300微米形式尺寸之全尺寸顆粒典型上可以在$個或 更多階段中完成，例如， 白段1-10至40微米，例如2〇至4〇微米 階段2_40至80微米 階段3-80至250微米，例如8〇至2〇〇微米 階段4-200至650微米，例如2〇〇至4〇〇微米或250至650微 米 階段5et seq.-400至2000微米，例如400至6〇〇微米，或達 1300微米或650至1700微米 為了產生EPS珠粒，PS珠粒必需負載發泡劑，即一種物 質’其並非聚合物之溶劑或者僅將彼等些許膨脹，且沸點 63748-970214.doc -26 - 1298330 低於聚合物之柔軟點，並在周圍溫度為氣體或液體形式， 或者是一種能夠產生氣體之固體。典型上使用一種選擇性 取代知肪知煙，其具有達8個碳原子，較佳3至5個碳原 子，且沸點在_50至+50。(：範圍内，例如丙烷，戊烷，環戊 環丁烷，氯甲烷，氯乙烷，二氯二氟甲烷(或其它就 氯燒（FreGns))，丙稀，丁烯等等。戊燒或丁烧較佳。發泡 劑典型上於最終聚合階段添加，或者添加於最終產物，視 需要可以在回收，清洗，乾燥等等之後。能夠使用發泡劑 混合物。 ^ '、、要夺顆粒亦可以以火談阻滞劑處理，例如六溴環癸 烷或者其可以經表面處理以便以希望之性質連接其它物 質，例如抗靜電添加劑，或官能和反應性化學基。 除了用以製備EPS珠粒外，本發明方法可以用以產生許 · /二匕應用之聚合物珠粒。尤其’可以製備適用於離子交 - =樹脂（例如水純化）之實質單分散顆粒。此類樹脂珠粒通 私將而要一些聚合物基質之交聯度（例如與二乙烯苯），且 在發生珠粒形成後可以衍生，例如以硫酸處理而磺化，以鲁 便產生酉夂性離子父換樹脂珠粒，或將最終階段或一個後來 聚合階段中使用之反應性共單體胺化，例如，Μ基苯乙 稀乂產生驗性離子父換樹脂。此類樹脂之優點在於以重 複使用和+水’在樹脂床中將較不易發生珠粒尺寸分離， 其係導致降低性能之問題。通常關於離子交換用途，珠粒 尺寸將為約100至500微米。 應用之更多實例包括用以作為產生結合化學群集之纟 63748-970214.doc •27- 1298330 貝其中顆粒之實質單分散性賦予使用分裂和混合技術之 群集產生中群集構件之改良分佈1於此剌，除非適當 官能化共單體（例如胺苯乙烯）頃用於生產珠粒，否則該珠 =常將反應而後生產’以植人適於連接群集構件之表面 吕月b度。再者，典型上可以使用尺寸1〇〇至5〇〇微米之珠 粒0 根據本發明生產之珠粒亦可以用以作為油漆之色素或添 加劑（例如取代Ti〇2)，作為隔間（例如於lcd中），作磨摻 降低劑，作為潤，作為細胞之載體，酵素或觸媒，作為持 續釋放調配物之藥物載體，作為過㈣，作為隱形眼鏡， 作為黏合劑添加劑之載體’作為流動標示劑，或者其可以 經熱成形，例如以、诗，> 埏以產生具高孔均勻度之過濾器或 過濾塊。 該顆粒亦可以用以你糸甘+ ， 作為其匕聚合物内之添加劑，尤指聚 烯員如聚乙埽，％丙烯，聚碳酸醋，AM，和聚苯乙烤 ⑼如GPPS和HIPS)。可以添加低分子量之分子以改良流動 性質’例如提高熔融流動指數，或改良分子量分佈。 關於許些用途而言，該顆粒需要多孔度，例如當彼 等係用以作為觸媒或酵素載體時。此可以較簡單地以控制 =合物基質之交聯度’及在最終階段或—個其後來聚合階 &中所使用之早體乳液包括波若敬⑽㈣(例如甲苯， 戊烧或任何其它揮發性或氣體產生劑，其不與聚合物反 應）而達成。 在希望可以負載多决 戰夕孔顆粒處，例如以藥物，觸媒，酵素 63748-970214.doc -28- 1298330 等等 則條件為將更多聚合物層密封於 放0 負載中或延持其釋 多孔顆粒不僅可以用以作Λ恭辦 .^ ^ ’亦作為H，聚合膜 寺專之控制多孔性來源。 將此處參考之所有資料併入本文供參考。 現將進一步參考以下非呢备丨&每 ^ 非限制性實例以及附圖說明本發 明，其中： 圖式簡單說明 圖1表示反應混合物溫度相對於主 又祁對於時間之圖，並指出在實 例2中添加不同試劑之階段· R - 、⑷心丨白杈，圖2表不在實例2中整個時間 之早體添加。 實例1 於反應器裝填公斤具55公斤2〇微米聚苯乙稀 DynospheW之水性料液，18公斤纖維㈣（難⑽ κ_(預溶於水中）和1600公斤水。以4〇 rpm授摔懸浮液並 以1/2小時加熱至40°C。 於ίο公升谷為中，使用傳統螺旋紫作為授掉器，將1〇 公斤過氧二苯甲醯（75%水溶液）溶於1〇公斤苯乙烯中。完 全溶解後，將此裝填反應器中。將懸浮液保持於机 時’其後以1-1/2小時上升至8〇t：。 /❿口 385么斤苯乙烯，3.0公斤過氧化苯甲醯（75%水溶 液）3〇分鐘，製備苯乙烯單體。其後添加77〇公斤水和丨^ 公斤Tween 20安定劑，將混合物乳化並以8小時，以速率 90.75 a斤/小時’ 115.09公斤/小時，133·5公斤/小時， 63748-970214.doc -29- 1298330 146.3公斤/小時，156·2公斤/小時，ι65公斤/小時，173公 斤/小時和177·5公斤/小時各以小時添加於反應器。 在80°C W分鐘後，將反應器裝填5公克溶於12.5公克水 中之KI，在80°C 2小時後，進一步添加15公克溶於37 5克 水中之KI。 聚合反應完成後，將反應混合物保持於80它再2小時。 回收產物並使用卡爾特計數器256分析顆粒尺寸分佈。 形式直徑：39-41微米 CV ： 5-6% 實例2 於反應器裝填1929公斤具50公斤40微米實例！之顆粒水 性懸浮液，1 1公斤纖維素醚（Methocel K100)(預溶於水中） 和1863公斤水。將纖維素醚預溶於水中。 以40rpm攪拌懸浮液並以1/2小時加熱至4〇t：。 將0.25公斤過氧二苯甲醯（75%水溶液）溶於1〇公斤苯乙 浠中。將懸浮液/乳液保持於4 〇。〇 1小時，其後以1 1 /4小 時上升至80°C。 混合385公斤苯乙烯，770公斤水，1.66公斤Tween 20 女疋劑’ 0.4公斤Trigonox和3.0公斤過氧化二苯甲醯（750/。 水溶液）。將此乳化並以8小時，以90.75公斤/小時（1小 時），115.09公斤/小時（1小時），133 5公斤/小時（1小時）， 146·26公斤/小時（1小時），156.14公斤/小時（1小時）， 165·38公斤/小時（1小時），173.04公斤/小時（1小時）和 177.50公斤/小時（1小時）之速率添加於反應器。其後將反 63748-970214.doc 1298330 應混合物以1 1 0 C加熱2 1 / 4小時，維持於1 1 〇 °c 1小時，然 後冷卻。在開始添加單體乳液時，和其後2小時添加5克於 50克水中之KI。 回收產物並分析顆粒尺寸分佈。 形式直徑：79-81微米 CV ： 5-6% 實例3 於反應器裝填1359公斤具70公斤Dynoseeds 40(即40微米 單尺寸化聚苯乙烯晶種，可取自迪諾特殊品聚合物公司） 之水性懸浮液。以40rpm攪拌懸浮液。 將磷酸鈣（TCP)14公斤，Nacconol G90(烷基芳基磺酸 酯）0.039公斤直接裝填於反應器中，並將懸浮液加熱至4〇 〇C。 於玻璃反應器中將2.8公斤過氧二苯甲醯（75%水溶液）溶 於20公斤苯乙烯中。在40。(：將聚合反應器之此溶液稱入反 應器中。將懸浮液保持於4(TCH、時，其後小時上升至 80〇C 0 將470公斤苯乙烯，5·5公斤過氧化苯甲醯（Bp〇)(75%水 溶液）混合1小時。當反應器溫度為8〇〇c時，將此苯乙烯 /BPO溶液以固定速率於5小時添加於反應器。 3小時後，在80°C將反應器裴填1〇公斤磷酸鈣和〇〇28公 斤 Nacconol G90 〇 裝填苯乙烯/BPO完成後，將溫度保持於8(Γ(：再之小時。 殘餘單體含量為約3%。 63748-970214.doc 31· 1298330 回收產物並分析。 結果··The functionalized particles are especially useful for solid phase organic synthesis, for example, peptides and polynucleotides and small organic molecules, in separation, for example as chromatography, as a compatibilizer. The aminostyrene is advantageously used in combination with a styrenic comonomer such as styrene in a weight ratio of 1:2 to 1:1, especially to u = ratio. In this particular embodiment, exposure to an organic solvent in a polymerization process results in the presence of crosslinks in the formed particles. Other co-monomers which may be used include ethylenically unsaturated monomers such as enoic acid, methyl propylene (tetra), ethyl propylene (tetra), butyl (tetra) vinegar, 63748-970214.doc -20-1298330 based acrylic acid, Methyl methacrylate and ethyl methacrylate), maleic acid and esters thereof (eg, maleic acid methyl ester, diethyl maleate and dibutyl maleate), Maleic acid is dried, fumaric acid and its esters (such as dimethyl fumarate and diethyl fumarate), vinyl monomers, and acrylonitrile. The non-stupid ethylene common monomer will be 0 for any polymer added during any growth phase. /. Or 1 to 40% by weight. For example, an acrylic methacrylic acid comonomer can be used as the non-styrene-based co-monomer, for example, dimethyl propylene I ethyl ester (EDMA), hydroxyethyl methacrylate (HEMA), methyl acrylate can be used. , glycidyl methacrylate (GMA), acrylic acid, acrylic acid methyl ketone 'acrylic acid ethyl vinegar, acrylic acid butyl vinegar, methyl acrylic acid, methyl methacrylate B. Then, methyl methacrylate can be used as a 100% monomer. The cerium particles are preferably a polymer which is similar or at least compatible with the polymer of the late stage addition used in the polymerization (9) seed crystal. Therefore, the Ugsstadt seed crystal is preferably mainly a styrene polymer, especially on its surface. In addition to the simple vinyl-based comonomer, it is also possible to use a cross-linkable co-monomer such as monovinylbenzene and polyethylene glycol dimethacrylate. Such crosslinkable co-monomers will generally be used in smaller amounts. Examples of suitable polymerization initiators include organic peroxides such as oxidized di-methane, formazan and oxidized lauryl hydrazone '35g of the class', such as tertiary benzoic acid, tertiary butyl hydrazine and triterpene trimethylacetate. Butyl esters and azo compounds such as azobis5= and azobisdimethyltrimethylacetonitrile. These may be used as a solution in the monomer or monomer mixture, such as from 10% to 10%, preferably from 2 to 4% by weight of 63748 to 970214.doc 1298330. , or add 'such as benzene, toluene or di-propane in an organic solvent. Where an organic solvent is used, this is preferably a small amount relative to the polymer content. It is preferred to use at least one oil-soluble polymerization inhibitor which is disposed in the monomer or monomer mixture to avoid polymerization in the seedless monomer droplets, so that new particle crystal nuclei are formed. Such an inhibitor preferably has a high molecular weight (e.g., at least 300 dars) and low water solubility to reduce diffusion through the aqueous phase. The inhibitor may, for example, be a phenolic compound (e.g., 3,5-di-tertiary butyl 4-hydroxymethyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4-butylene Base-bis(3·methyl-, and-butanol) ' 1,3,5-dimethyl-2,4,6-paraxyl-(3,5-di-tertiary butyl-4-hydroxybenzyl) Benzo) benzene (Irganox 1330), 2,2, _ methylene bis (6-triyl _ butyl phenol), sulfur compounds (such as dilauryl thiodipropionate, 4, 4, sulphur Base 6-tertiary butyl-phenol)' or amine (such as N, N, · bis + decyl phenylene diamine and: phenyl isopropyl phenylene diamine). The amount of inhibitor is more convenient than this The inhibitor is 〇·5 to 1% by weight, preferably ～5% by weight. Regarding the conventional suspension polymerization, it is also preferred to include a seed or an ampule ampoule in the reaction medium f, especially in aqueous suspension. Preferably, the liquid comprises a suspension stabilizer (i.e., a stereostatic agent), and an emulsion stabilizer is included in the aqueous monomer emulsion to which they are added. Examples of suitable stabilizers include ionic, ethoxylated ionic 'nonionic and polymeric. Amphiphilic molecules' and inorganic particles, such as water-soluble high molecular weight substances Calcium phosphate (TCP), cellulose (including cellulose ethers, such as alkyl cellulose ethers, especially cw alkyl cellulose ethers; and hydroxyalkyl alkyl fibers (IV), especially based on fluorene-based fibers : 63748-970214.doc -22- 1298330 Enigma, such as burnt methyl cellulose, such as propyl fluorenyl octyl, may be = for example - 00 'polyol, polyethylene glycol, poly ring gas burnt soil And inorganic substances such as phosphoric acid and pyrophyllin. It is preferred to use fiber (4) and tc: as a suspension stabilizer", especially to produce larger size polymer particles. Preferably such stabilizers are relative to any cycle Let the initial polymer seed w/w exist, especially 15 to 55% in the cellulose test, the stabilizer concentration is convenient to reach 25% w/w, and the concentration of the stabilizer is higher than that of the inorganic scorpion The initial seed crystal in the relative polymer cycle is 55% w/w, for example, 丨 to 55% w/w, which is more convenient for the claws. TCP is especially preferred because it can be used with such high-impact impacts. The emulsion builder can be, for example, a surfactant such as Polosama (4) 〇x_r) or other polyepoxy bases. Use an emulsion stabilizer, such as a mixture containing 20 to 15 oxime units, such as Berol 274siUgepalc 〇 99 〇, or (4) H mb ionic surfactants. These stabilizers are preferred. In the monomer emulsion, for example, the concentration is 〇1 to 2%, preferably 1.0% by weight relative to the monomer content. Preferably, the suspension stabilizer used in the final polymerization stage is a probiotic solid particle such as squaric acid. A salt (e.g., phosphorus) can be removed from the product immediately in the washing step. The suspending U agent will typically use a weight ratio of from 0.5 to 25 percent relative to the seed crystal. Typically, seed crystals can be prepared from smaller seed crystals in tanks, inlet and outlet ports, and temperature-controlled reactors (eg, 1.5 liters to H) liters of heat dad 63748-970214.doc -23 - I ' 1298330 reactor). The reactor is filled with seed crystals in the initial or later stage, suspension stabilizer, deionized water, when the seed crystal is small (for example, less than 50 microns, especially less than 30 microns), preferably also filled with water such as sodium nitrate Sex inhibitor. Where inhibitors are used in the early stages of particle growth, the code will be used at concentrations ranging from 0 001 to 0.005% by weight in water. The seed crystal is typically present in a 65% by weight ratio of the aqueous suspension, for example from 1 to 60%, preferably from 10 to 60% by weight, and the stabilizer is typically from 0.5 to 15%, preferably 1 relative to the seed crystal. Up to 1% by weight. The temperature of the seed suspension typically rises to about 7 Torr to 1 Torr. (:, preferably Μ to 92%, and add a monomer emulsion. The monomer emulsion is typically dissolved by dissolving an oil-soluble initiator and an oil-soluble inhibitor such as benzoic acid peroxide and Irgan® 133〇. Styrene monomer (or monomer mixture) and mixed with the aqueous solvent of the emulsion stabilizer (for example, Βα〇ι 274 or Igepal C0 99〇). The oil (monomer) is 30 to 60 compared to the desired monomer emulsion. % by weight, which is prepared by any convenient emulsification technique, for example using a rotor-fixed mixer such as Ultra-Turax. In the context of emulsification, it is important to ensure that the monomer emulsion droplet size is small for smaller seed crystals, It is generally preferred that the monomer emulsion drops should be smaller than the seed particles used in any given stage. It is therefore preferred to form the emulsion by passing the mixture through a pressure homogenizer or a plurality of rotors P. & The production is minimized. The latter can be passed through a series of separate rotor holders or repeatedly cycled through the lower rotor fixed mixer. 63748-970214.doc -24- 129833 Monomer emulsion conveniently It is preferred to use an adjustable feed rate pump for continuous feeding into the stirred suspension of the reactor. The feed rate is preferably ', held at 0.1 to 2.0 grams, especially 0. 15 to 10 grams, and more particularly 〇15 to 〇·8 ^ ' especially 〇15 to 0.6g, monomer/hour, the feed rate per agram of reactor is higher during the addition period. When the monomer addition is completed The reaction mixture is stirred until the monomer is depleted, for example about 2 hours, or the polymerization reaction is terminated by the addition of a chaser (i.e., a monomer composition having a high concentration of initiator) or by increasing the temperature of the reactor. A second polymerization initiator can be used which is activated at a temperature above the first. At each end of the polymerization stage, the large size of the particles is preferably determined (using a Coulter counter) and thus calculated in any continuous The amount of monomer used in the stage. When the polymerization stage is found to produce an undesirably large particle size distribution, the performance volume size for the same growth stage should be increased. However, the product can still be used for further growth stages, if it is divided To remove too small or too large particles. After the polymerization is completed, the enlarged particles can be removed, if necessary, washed to remove undesired stabilizers, initiators, etc. The stability of the polymerization suspension and the resulting polymer The molecular weight depends on the range of variables in different ways (eg monomer addition rate, inhibitor concentration 'temperature' emulsion droplet size, seed size, etc.). Stability needs to avoid agglomeration. This can typically be determined by determining the seed crystal. The monomer concentration in the granules is not more than about 20-25% by weight, more preferably not more than about 10 to 20 Λ', particularly preferably it does not exceed about the weight ratio. Avoid excessive single 63748-970214.doc -25-1298330 m enough This is achieved by increasing the initiator concentration (although this reduces the polymer viscosity and its glass transition temperature in the knife), or by decreasing the body addition rate (which increases the polymer molecular weight and reaction time). : = 瘟 Basically, the method of the method must balance the initiator concentration and monomer addition rate 1 to avoid agglutination within the acceptable method time and achieve the desired molecular weight. The phase water content can be varied without much problem, and even if the suspension water content is too low, stability may be lost. Similar to the ritual agent's emulsion stabilizer, the content is not strict, even if it loses too low stability, and even if the rubber particles are formed too high, it may happen that the fine granules can operate the method of the invention, resulting in lower than About weight to fine particles.攸 Typically starting at 10-20 micron Dyn〇spheres®, full-size particles that are enlarged to a size of, for example, 200 to 1300 microns can typically be completed in $ or more stages, for example, white segments 1-10 to 40 microns. , for example, 2〇 to 4〇 micron stage 2_40 to 80 microns stage 3-80 to 250 microns, for example 8〇 to 2〇〇 micron stage 4-200 to 650 microns, for example 2〇〇 to 4〇〇 microns or 250 to 650 Micron stage 5et seq.-400 to 2000 microns, such as 400 to 6 microns, or up to 1300 microns or 650 to 1700 microns. In order to produce EPS beads, the PS beads must be loaded with a blowing agent, ie a substance that is not polymerized. The solvent of the substance may only swell slightly, and the boiling point of 63748-970214.doc -26 - 1298330 is lower than the soft point of the polymer, and it is in the form of gas or liquid at ambient temperature, or a solid capable of generating a gas. Typically, a selective substitution is used which has up to 8 carbon atoms, preferably 3 to 5 carbon atoms, and a boiling point of _50 to +50. (: in the range, such as propane, pentane, cyclopentacyclobutane, methyl chloride, ethyl chloride, dichlorodifluoromethane (or other chlorobenzene (FreGns)), propylene, butene, etc. Or butadiene is preferred. The blowing agent is typically added in the final polymerization stage, or added to the final product, optionally after recovery, washing, drying, etc. A blowing agent mixture can be used. ^ ', It may also be treated with a fire retarder, such as hexabromocyclohexane or it may be surface treated to attach other materials, such as antistatic additives, or functional and reactive chemical groups, with the desired properties. In addition to extragranular, the process of the invention can be used to produce polymer beads for the application of bismuth/dihydrazine. In particular, it is possible to prepare substantially monodisperse particles suitable for ion exchange-resin (for example, water purification). Privately, some degree of crosslinking of the polymer matrix (for example, with divinylbenzene), and after the formation of beads, can be derivatized, for example, by sulfuric acid treatment to sulfonate, in order to produce a hydrophobic ion-replaced resin beads. grain, Or amination of the reactive comonomer used in the final stage or in a subsequent polymerization stage, for example, mercaptophenidin produces an ionic ion-replacer resin. The advantage of such a resin is that it is reused and + water' Bead size separation will be less likely to occur in resin beds, which leads to problems with reduced performance. Typically for ion exchange applications, the bead size will be from about 100 to 500 microns. More examples of applications include use as a binding chemical cluster纟 48 48 48 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 纟 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中 其中Ethylene) is used to produce beads, otherwise the beads = will often react and then produce 'the surface of the plant is suitable for joining the surface of the cluster components. In addition, the size can typically be used from 1 to 5 microns. Beads 0 The beads produced according to the invention can also be used as pigments or additives for paints (for example to replace Ti 2 ), as compartments (for example in lcd), as grinding reducers As a carrier of cells, an enzyme or a catalyst, as a drug carrier for a sustained release formulation, as a carrier for a contact lens as a flow labeling agent, or as a flow marker, or as a carrier for a sustained release formulation, for example, Use, poetry, > to produce a filter or filter block with high pore uniformity. The granule can also be used as an additive in its bismuth polymer, especially a polyene olefin such as polyacetam. , propylene, polycarbonate, AM, and polystyrene (9) such as GPPS and HIPS). Low molecular weight molecules can be added to improve flow properties, such as increasing the melt flow index, or improving the molecular weight distribution. For some applications, the particles require porosity, such as when they are used as a catalyst or enzyme carrier. This can be relatively simple to control the degree of crosslinking of the matrix of the compound and the early body emulsion used in the final stage or a subsequent polymerization stage &amp; includes Boruo (10) (four) (eg toluene, pentylene or any other A volatile or gas generating agent that does not react with the polymer) is achieved. In the hope that the multi-decision particles can be loaded, for example, drugs, catalysts, enzymes 63748-970214.doc -28-1298330, etc., the conditions are to seal more polymer layers in the load or to release them. Porous particles can be used not only as a Λ 办. ^ ^ ' Also as H, the polymeric membrane temple specifically controls the source of porosity. All materials referred to herein are incorporated herein by reference. The invention will now be further described with reference to the following non-limiting <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; The stage of adding different reagents in 2 · R - , (4) palpitations, and Figure 2 is not the early addition of the whole time in Example 2. Example 1 The reactor was charged with an aqueous solution of 55 kg of 2 〇 micron polystyrene Dynosphe W, 18 kg of fiber (4) (difficult (10) κ (pre-dissolved in water) and 1600 kg of water. Drop suspension at 4 rpm And heated to 40 ° C in 1/2 hour. In the ίο liters of the valley, using traditional spiral purple as a transfer device, 1 〇 kg of peroxydiphenyl sulfonium (75% aqueous solution) is dissolved in 1 〇 kg of styrene After completely dissolved, this is packed into the reactor. When the suspension is kept in the machine, it will rise to 8-〇t after 1-1/2 hours: / 385 385 jin styrene, 3.0 kg peroxidation Benzoquinone (75% aqueous solution) was prepared for 3 minutes to prepare a styrene monomer. Thereafter, 77 kg of water and 丨^ kg of Tween 20 stabilizer were added, and the mixture was emulsified for 8 hours at a rate of 90.75 a kg/hr. 115.09 kg / h, 133.5 kg / h, 63748-970214.doc -29 - 1298330 146.3 kg / h, 156 · 2 kg / h, ι 65 kg / h, 173 kg / h and 177 · 5 kg / h each Add to the reactor in hours. After 80 minutes at 80 ° C, the reactor was filled with 5 grams of water dissolved in 12.5 grams. KI, after 2 hours at 80 ° C, 15 grams of KI dissolved in 37 5 grams of water was further added. After the polymerization was completed, the reaction mixture was maintained at 80 for 2 hours. The product was recovered and analyzed using a Kart counter 256. Size distribution. Form diameter: 39-41 micron CV: 5-6% Example 2 Filling the reactor with 1929 kg of 50 kg 40 micron example! Aqueous aqueous suspension, 1 1 kg of cellulose ether (Methocel K100) (pre-dissolved In water) and 1863 kg of water. Pre-dissolve the cellulose ether in water. Stir the suspension at 40 rpm and heat to 4 〇t in 1/2 hour: Dissolve 0.25 kg of peroxybenzophenone (75% in water) In 1 kg of phenethyl hydrazine. Keep the suspension/emulsion at 4 Torr for 1 hour, then rise to 80 ° C for 1 1/4 hours. Mix 385 kg of styrene, 770 kg of water, 1.66 kg of Tween 20 female tincture '0.4 kg Trigonox and 3.0 kg dibenzoyl peroxide (750 /. aqueous solution). Emulsify this for 8 hours, to 90.75 kg / hour (1 hour), 115.09 kg / hour (1 hour) , 133 5 kg / hour (1 hour), 146. 26 kg / small (1 hour), 156.14 kg / hour (1 hour), 165.38 kg / hour (1 hour), 173.04 kg / hour (1 hour) and 177.50 kg / hour (1 hour) at a rate added to the reactor. After the reaction, the mixture was heated at 1 10 C for 2 1 / 4 hours, maintained at 1 1 ° ° C for 1 hour, and then cooled. At the beginning of the addition of the monomer emulsion, 5 grams of KI in 50 grams of water was added 2 hours thereafter. The product was recovered and analyzed for particle size distribution. Form diameter: 79-81 micron CV: 5-6% Example 3 Filling the reactor with 1359 kg of 70 kg of Dynoseeds 40 (ie 40 micron single-sized polystyrene seed, available from Dino Specialty Polymers) An aqueous suspension. The suspension was stirred at 40 rpm. 14 kg of calcium phosphate (TCP) and 0.039 kg of Nacconol G90 (alkylaryl sulfonate) were directly charged into the reactor, and the suspension was heated to 4 〇C. 2.8 kg of peroxydibenzazole (75% in water) was dissolved in 20 kg of styrene in a glass reactor. At 40. (: The solution of the polymerization reactor is weighed into the reactor. The suspension is kept at 4 (TCH, hour, and then rises to 80 〇C 0 470 kg of styrene, 5.00 kg of benzoyl peroxide) (Bp〇) (75% aqueous solution) was mixed for 1 hour. When the reactor temperature was 8 ° C, the styrene/BPO solution was added to the reactor at a fixed rate for 5 hours. After 3 hours at 80 ° C After the reactor was filled with 1 kg of calcium phosphate and 〇〇28 kg of Nacconol G90® filled with styrene/BPO, the temperature was maintained at 8 (Γ (after another hour. The residual monomer content was about 3%. 63748- 970214.doc 31· 1298330 Recovered product and analyzed. Results··
形式直徑·· 79.5微米 外觀：存在TCP CV(主波峰）·· 8.9%(卡爾特LS) 分子量：86800 Mw/Mn ·· 2.47 熔融流動速率：150克/10分鐘（2〇〇〇c，3公斤） 實例4 於反應器裝填274公斤具60公斤Dyn〇seeds 4〇(4〇微米單 尺寸化聚苯乙烯晶種）之顆粒水性懸浮液，12公斤Meth〇cei κ-1〇〇之安定劑溶液和和1493公斤水。以4〇卬〇攪拌懸浮 液並加熱至40°C。 在玻璃反應器中將1.47公斤過氧二苯甲醯（75%水溶液） 溶於8.8公斤苯乙烯中。在4〇t將聚合反應器中此溶液趁 入反應器中。將懸浮液保持於4(TC i小時，並在約丄小時 期間上升至80°C。 混合353公斤苯乙烯，5.1公斤過氧化二苯甲醯（75%水溶 液）’ 708公斤水’ 1.52公斤TWeen 20製備苯乙烯單體乳 液。當反應器溫度為8 0 C時將此乳液添以固定速率在$小 時添加於反應器。 10分鐘後，在80°C將反應器裝填5克溶於水中之KI。 3小時後，在80°C將反應器裝填15克溶於水中之ΚΙ。 裝填苯乙浠/ΒΡΟ完成後’將溫度保持於&q ο。再2小時。 63748-970214.doc -32 - 1298330 殘餘單體含量為約1.5 %。 回收產物並分析。 結果： 形式直徑·· 83.3微米 CV(主波峰）：79%(卡爾特LS) 分子量：99700Form diameter · 79.5 micron Appearance: presence of TCP CV (main peak) · 8.9% (Calte LS) Molecular weight: 86800 Mw / Mn · · 2.47 Melt flow rate: 150 g / 10 min (2 〇〇〇 c, 3 Kg) Example 4 274 kg of an aqueous suspension of particles with 60 kg of Dyn〇seeds 4〇 (4 μm micronized polystyrene seed), 12 kg of Meth〇cei κ-1〇〇 stabilizer Solution and 1493 kg of water. The suspension was stirred at 4 Torr and heated to 40 °C. 1.47 kg of peroxydibenzazole (75% in water) was dissolved in 8.8 kg of styrene in a glass reactor. This solution was poured into the reactor at 4 Torr. The suspension was maintained at 4 (TC i hours and rose to 80 ° C during about 丄 hours. Mix 353 kg of styrene, 5.1 kg of benzamidine peroxide (75% in water) '708 kg of water' 1.52 kg TWeen 20 Preparation of a styrene monomer emulsion. The emulsion was added to the reactor at a fixed rate for a period of $hour when the reactor temperature was 80 C. After 10 minutes, the reactor was filled with 5 g of water at 80 ° C. KI. After 3 hours, the reactor was charged with 15 g of hydrazine dissolved in water at 80 ° C. After filling styrene / hydrazine, the temperature was kept at & q ο. 2 hours. 63748-970214.doc - 32 - 1298330 Residual monomer content is about 1.5%. Product was recovered and analyzed. Result: Form diameter · 83.3 μm CV (main peak): 79% (Calte LS) Molecular weight: 99700
Mw/Mn : 2·55 熔融流動速率：100克/10分鐘（2〇〇°c，8公斤） 將實例3和4之珠粒添加於聚丙烯，聚乙烯，聚碳酸酯和 AB S (丙稀晴/聚丁二浠/苯乙稀）之樣品在所有例中添加$ % 重量比珠粒，導致熔融流動指數提高。 實例5 於反應器裝填556公斤具70公斤0}^〇866(^ 40(40微米聚 本乙烯晶種）之水性懸浮液。以4〇rpm擾拌懸浮液。 將磷酸鈣（TCP)和Nacconol G90(烷基芳基磺酸酯）直接裝 填於反應器中，並將懸浮液加熱至4(rc。 於玻璃反應器中將2.8公斤過氧二苯甲醯（75%水溶液）溶 於20公斤苯乙烯中。在4(rc將聚合反應器之此溶液裝填反 應器中。將懸浮液保持於4(TC 1小時，其後以卜】、時上升 至 80°C。 將470公斤苯乙烯，丨.68公斤過氧化苯曱醯（Bp〇)(75%水 溶液）混合1小時。當反應器溫度為8〇t時，將此苯乙烯 /BPO溶液以固定速率於5小時添加於反應器。 3小時後’在80°C將反應器裝填1〇公斤鱗酸妈和〇〇25公 63748-970214.doc -33- 1298330 斤 Nacconol G90 〇 裝填苯乙烯/BPO完成後，將溫度保持於80°C再2小時。 殘餘單體含量為約3.5%。 回收產物並分析。 結果： 形式直徑：81.1微米 CV(主波峰）·· 9.4%(卡爾特LS) 分子量：132000 Mw/Mn ： 2.47 殘餘苯乙烯：3.7% 63748-970214.doc 34-Mw/Mn: 2·55 Melt flow rate: 100 g/10 min (2 ° C, 8 kg) Add beads of Examples 3 and 4 to polypropylene, polyethylene, polycarbonate and AB S (C A sample of smear/polybutylene/styrene) was added in all cases to a weight ratio of beads, resulting in an increase in melt flow index. Example 5 A 556 kg aqueous suspension containing 70 kg of 0}^〇866 (^40 (40 micron polyethylene seed crystal) was charged in the reactor. The suspension was disturbed at 4 rpm. Calcium phosphate (TCP) and Nacconol G90 (alkyl aryl sulfonate) was directly charged in the reactor and the suspension was heated to 4 (rc. 2.8 kg of peroxydibenzazole (75% in water) was dissolved in 20 kg in a glass reactor. In styrene, the solution in the polymerization reactor was charged in the reactor at 4 (rc). The suspension was kept at 4 (TC for 1 hour, followed by bl), and then raised to 80 ° C. 470 kg of styrene, 68. 68 kg of benzoquinone peroxide (Bp〇) (75% aqueous solution) was mixed for 1 hour. When the reactor temperature was 8 〇t, the styrene/BPO solution was added to the reactor at a fixed rate for 5 hours. After 3 hours 'fill the reactor at 80 ° C 1 kg kg scaly mother and 〇〇 25 male 63748-970214.doc -33- 1298330 kg Nacconol G90 〇 filled with styrene / BPO, the temperature is maintained at 80 ° C for another 2 hours. Residual monomer content was about 3.5%. Product was recovered and analyzed. Result: Form diameter: 81.1 μm CV (main peak) · 9.4% (Carter LS) molecular weight: 132000 Mw / Mn: 2.47 Residual Styrene: 3.7% 63748-970214.doc 34-