1271415 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種高分子顆粒，特別是一種具有中空 結構之高分子顆粒及其製造方法。 【先前技術】 微米級單一散度高分子聚合物顆粒之合成是近年來高分鲁 子學界研究和發展的主要課題之―，@為單—散度微米級顆粒. 可廣泛應用於各種物理、化學以及生物相關之倾，如大型液 晶顯不器之間隔劑、蛋白質的分離、粒徑分佈測定之標準劑以 及色層分析儀管柱的填充材料等；微米級聚合物顆粒若兼具中 空結構則更可作為溶液祕的紐。由於錄製造且具有高孔 隙性和反應性等特質，此類顆粒較傳統的石夕膠更具競爭力，因 此以其作為藥物的麵或填充於各種層析儀管柱等之應用已_ 相當普遍。其中，作為藥物載體用途之聚合物顆粒，若其粒徑 大㈣―，且能控制中空部份所佔之體積，則可於療程中固定 用藥量，達到穩定療效之目的。 目前中空聚合物顆粒無論是在實驗室或工業界均係利用 心浮丰口法合成’然崎獲得顆粒之粒徑分佈很寬廣，即使經 過師選亦很難獲得大小均一之粒徑。爰是，對於合成具有相同 1271415 中工度乂及粒L均勻之微米級高分子聚合細粒係為目前對 於此類聚合顆粒之研究方向。 【發明内容】 鑒於上述之發明背景中’為了克服傳統技術之缺失，本 發明提供一種新的具有中空結構之高分子顆粒及其製造方 法乂符口八有中工度相近以及粒徑均勾之產業需求。 本毛月係藉由種對於單體、交聯劑為良溶劑（㈣ ▲nt)，但對於共聚合體為不良溶劑（p〇〇r s〇i刪）之稀釋 劑，以製造出具有中空結構之高分子顆粒。由於單體與交聯劑 之聚合與交聯聚合反應係於粒徑均—之粒種中進行，所以能夠 製造出粒徑均-之高分子難。料，添加魅的稀釋劑與調 整聚合製㈣猶時間以便於㈣高分子雌之巾空結構與 外殼厚度’並藉此調整高分子顆粒之中空度。因此，本發明能 符合經濟上的效益與產業上的利用性。 一根據以上所述之目的’本發明揭示了—種具有中空結構 之高分子顆粒，此高分子顆粒包含—中空部分與一具有丙稀酸 醋共聚合體之外殼。本發明亦揭示了—種具有巾空結構之高分 子顆粒的製造方法，其係藉由一種對於單體、交聯劑為良溶劑 (g〇〇d S〇Went)，但對於共聚合體為不良溶齊丨](poor solvent) 7 1271415 之稀釋劑，以製造缸述之巾㈣份與外殼結構。 【實施方式】 本發明在此所探討的方向為—種具有中空結構之高分子 顆粒及其製造方法。為了錄底地瞭解本伽，將在下列的描 述中提出詳盡的製程步驟及其配方。_地，本發_施行並 未限定於高分子領域之技藝者所熟f的特殊細節。另一方面， 眾所周知的配錢製程麵絲财於細節巾，崎免造成本 發明不必狀關。本發_較佳實施例會詳細描述如下，然 而除了這麟細描狀外，本發明射以廣泛地施行在其_ 實施例中，且本發_範财受限定，細錢的專利範圍為 準。 、、、 本發明之一第一實施例揭露一種具有中空結構之高分子 顆粒，此高分子顆粒包含一中空部分與一具有丙烯酸酯共聚合 體(copolymer)之外殼，此丙烯酸酯共聚合體係藉由一具有一個 雙鍵之丙烯酸酯（單體）與一具有至少二個雙鍵之丙烯酸酯（交 聯劑）所聚合而成，其中，上述之具有一個雙鍵之丙烯酸酯係 為下列族群中之一者或其任意組合：2-羥乙胺基丙烯酸酉旨 (2-hydroxyethyl methacrylate ，HEMA)、丙烯甲酯 (Methylacrylate)、丙烯酸乙酯（Ethyl acrylate)、丙烯酸丁酯 (Brtylacrylate)、丙稀酸辛|旨（Octylacrylate)、甲基丙烯酸甲 1271415 酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸異丁酯、 甲基丙烯酸丁酯、甲基丙烯酸二甲胺乙酯、羥乙基丙稀酸脂 (Hydroxyethyl Acrylate，HEA )、經丙基丙稀酸脂 (Hydroxypropyl Acrylate，ΗΡΑ)、苯乙婦（Styrene)與酷酸 乙烯（VinylAcetate);上述之具有至少二個雙鍵之丙烯酸酯係 為下列族群中之一者或其任意組合··乙二醇二曱基丙烯酸酯 (ethylene glycol dimethacrylate，EGDMA)、1，3 butylene glycol dimethacrylate (BGDMA)、l，4-butane diol diacrylate (BDDA )、春 1,6-hexane diol diacrylate (HDDA) ' hexanediol dimethacrylate (HDDMA )、neopentylglycol diacrylate (NPGDA)、 trimethylolpropane triacrylate ( TMPTA )。當具有一個雙鍵之丙 烯酸酯與具有至少二個雙鍵之丙烯酸酯之總重量係為固定 時，具有至少二個雙鍵之丙烯酸酯的添加量越多，則本發明所 挺供之具有中空結構之高分子顆粒的結構會越接近球形。例 如：當上述之具有一個雙鍵之丙烯酸酯為2_羥乙胺基丙烯酸酯鲁 (HEMA) ’ I具有至少二個雙鍵之丙烯酸酯為乙二醇二甲基 丙烯酉夂知（EGDMA)’則乙二醇二甲基丙稀酸酯（EGDMA) 的添加量約大於2邊乙胺基丙烯_旨⑽MA)的2.5祕， 以使待具有巾空結構之高分子顆粒的結構接近辆彡。另外，當 具有-個雙鍵之_酸§旨與具有至少二個雙鍵之丙烯酸酯之 總重量增加時，則本發明所提供之具有中空結構之高分子顆粒 1271415 的外殼厚度隨之增加。 參♦第一圖所示，本發明之—第二實施例揭露一種具有 中空結構之衫子難_造方法，錢，精—粒種製造程 序110，其係藉由一分散聚合法合成粒徑均-之聚苯乙烯顆粒 以作為-粒種115A ’其中，上述之粒種製造程序⑽更可包 含下列步驟：首先，混合—苯乙料體、乙醇與—第二穩定劑 以形成-第五溶液，其中，上述之第二穩定舰為下列族群中 之一者·聚乙烯基烷酮(p〇tyvinylpyrr〇lid〇ne，pvp)、聚乙烯醇 (polyvinyl alc〇h〇l，PVA)與陰離子型界面活性劑，例如：十 二烧基磺酸鈉（sodium dodecyl sulfonate，SDS);接著，混合 一第一起始劑與乙醇以形成一第六溶液，其中，上述之第二起 始劑係為下列族群中之一者或其任意組合：2,2_偶氮雙異丁晴 (2-2，-azobisisobutyronitrile，AIBN)、過氧化二苯曱醢基 (benzoyl peroxide，BPO)、chloroperoxidase (CPO)、1271415 IX. Description of the Invention: [Technical Field] The present invention relates to a polymer particle, particularly a polymer particle having a hollow structure, and a method of producing the same. [Prior Art] The synthesis of micron-sized single-dispersion polymer particles is the main subject of research and development in high-level Luzi academic circles in recent years--@ is a single-dispersion micron-sized particle. It can be widely used in various physics, Chemical and biological related tilting, such as spacers for large liquid crystal display, separation of proteins, standard reagents for particle size distribution measurement, and filling materials for chromatographic column; micron-sized polymer particles have a hollow structure It can be used as a solution for the secret of the solution. Due to the nature of recording and high porosity and reactivity, such particles are more competitive than traditional Shiqi gum, so it has been used as a drug surface or in various chromatograph columns. universal. Among them, as the polymer carrier for the drug carrier, if the particle size is large (four), and the volume occupied by the hollow portion can be controlled, the dosage can be fixed in the course of treatment to achieve a stable therapeutic effect. At present, hollow polymer particles are synthesized in the laboratory or in the industry by the heart-floating method. The particle size distribution of the particles obtained by Ranzaki is very wide, and even if it is selected by the teacher, it is difficult to obtain a uniform particle size. The trick is to synthesize micron-sized polymeric fine-grained fines having the same working degree of 1271415 and uniformity of particle L as the current research direction for such polymeric particles. SUMMARY OF THE INVENTION In view of the above-mentioned background of the invention, in order to overcome the deficiencies of the conventional technology, the present invention provides a novel polymer particle having a hollow structure and a method for producing the same, and the method has the same working degree and the particle size Industrial demand. The hair of the hair is made by using a diluent which is a good solvent for the monomer and the crosslinking agent ((4) ▲ nt), but is a poor solvent for the copolymer (p〇〇rs〇i deleted) to produce a hollow structure. Polymer particles. Since the polymerization and crosslinking polymerization reaction of the monomer and the crosslinking agent are carried out in the particle size-average particle size, it is difficult to produce a polymer having a uniform particle diameter. The material is added with the glaze diluent and the polymerization process (4) to facilitate the (four) polymer female towel empty structure and shell thickness ' and thereby adjust the hollowness of the polymer particles. Therefore, the present invention can meet economical efficiency and industrial applicability. According to the above objects, the present invention discloses a polymer particle having a hollow structure comprising a hollow portion and an outer shell having a acrylate vinegar copolymer. The invention also discloses a method for producing a polymer particle having a hollow structure, which is a good solvent (g〇〇d S〇Went) for a monomer and a crosslinking agent, but is poor for a copolymer. A diluent of 7 1271415 to make a cylinder (four parts) and a shell structure. [Embodiment] The invention is directed to a polymer particle having a hollow structure and a method for producing the same. In order to understand Benja, a detailed process step and its formulation will be presented in the following description. _ Ground, this hair _ implementation is not limited to the special details of the skilled person in the field of polymer. On the other hand, the well-known money-making process is rich in details, and it is not necessary for the invention to be used. The present invention will be described in detail below, but in addition to this detailed description, the present invention is widely practiced in its embodiment, and the present invention is limited, and the patent scope of fine money is subject to . A first embodiment of the present invention discloses a polymer particle having a hollow structure, the polymer particle comprising a hollow portion and an outer shell having an acrylate copolymer, wherein the acrylate copolymerization system is An acrylate (monomer) having a double bond and an acrylate (crosslinking agent) having at least two double bonds, wherein the acrylate having a double bond is in the following group One or any combination thereof: 2-hydroxyethyl methacrylate (HEMA), Methylacrylate, Ethyl acrylate, Brtylacrylate, octyl acrylate Octylacrylate, 1271415 methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, butyl methacrylate, dimethylaminoethyl methacrylate, hydroxyethyl Hydroxyethyl Acrylate (HEA), hydroxypropyl acrylate (Hydroxypropyl Acrylate), Styrene and Vinyl Acetate; The acrylate having at least two double bonds is one of the following groups or any combination thereof: ethylene glycol dimethacrylate (EGDMA), 1,3 butylene glycol dimethacrylate (BGDMA) , l,4-butane diol diacrylate (BDDA), spring 1,6-hexane diol diacrylate (HDDA) 'hexanediol dimethacrylate (HDDMA), neopentylglycol diacrylate (NPGDA), trimethylolpropane triacrylate (TMPTA). When the total weight of the acrylate having one double bond and the acrylate having at least two double bonds is fixed, the more the amount of the acrylate having at least two double bonds is added, the more the hollow is provided by the present invention. The structure of the polymer particles of the structure will be closer to a sphere. For example, when the above acrylate having a double bond is 2-hydroxyethylamino acrylate (HEMA) 'I having at least two double bonds, the acrylate is ethylene glycol dimethyl propylene (EGDMA) 'The addition amount of ethylene glycol dimethyl acrylate (EGDMA) is more than about 2.5 cents of 2-ethylaminopropyl propylene (10) MA, so that the structure of the polymer particles to be empty has a structure close to that of the vehicle. . Further, when the total weight of the acrylate having a double bond and the acrylate having at least two double bonds is increased, the thickness of the outer shell of the polymer particle 1271415 having a hollow structure provided by the present invention is increased. Referring to the first figure, the second embodiment of the present invention discloses a method for manufacturing a shirt having a hollow structure, a method for manufacturing a money, fine-grain type, which is synthesized by a dispersion polymerization method. The polystyrene particles are - as the seed species 115A ', wherein the above-mentioned particle production procedure (10) may further comprise the following steps: first, mixing - benzene, ethanol and - second stabilizer to form - fifth a solution, wherein the second stable ship is one of the following groups: polyvinyl ketone (p〇tyvinylpyrr〇lid〇ne, pvp), polyvinyl alcohol (polyvinyl alc〇h〇l, PVA) and an anion a type of surfactant, for example, sodium dodecyl sulfonate (SDS); then, mixing a first initiator with ethanol to form a sixth solution, wherein the second initiator is One of the following groups or any combination thereof: 2,2-azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), chloroperoxidase (CPO) ,
Tert-butylhydroperoxide ( t-BuPO )、過硫酸銨（ammonium persulfate，APS )、過琉酸飾(potassium persulfate，KPS)與 cumene hydroperoxide (CHP)。最後，混合第五溶液與第六溶液 並進行一聚合反應以形成粒徑均一之聚苯乙烯顆粒，並藉此形 成粒種115A，其中，此聚合反應係於一富含惰性氣體之操作 環境中所執行，其中，上述之惰性氣體更包含氮氣，而其操作 溫度範圍約為50°C至7〇°C。 1271415 在本實施例中，於粒種製造程序110完成後，進行一第 一混合程序120，其係藉由混合粒種115A、一乳化劑與水以 形成一第一溶液125A，其中，上述之乳化劑更包含陰離子型 界面活性劑，例如：十二烷基磺酸鈉（s〇dium d〇decyl sulfonate ’ SDS)，並且藉由一第一分散程序13〇均勻分散第 /谷液125A中之粒種115A ’其中，第一分散程序更包 含超音波振盪步驟或攪拌步驟。然後，進行一第二混合程序 140,其係藉由添加一第一起始劑與一助吸收劑至第一溶液參 125A中以形成一苐二溶液145A，其中，第一起始劑係為下列 族群中之一者或其任意組合：2,2-偶氮雙異丁晴(2_2， -azobisisobutyronitrile，AffiN)、過氧化二苯甲醯基(benz〇yl peroxide ， ΒΡΟ) 、 chloroperoxidase (CPO)、 Tert-butylhydroperoxide ( t-BuPO )、過硫酸銨（amm〇nium persulfate，APS )、過石荒酸鉀(potassium persulfate，KPS)鱼 cumene hydroperoxide (CHP)。而助吸收劑係用以腫服該粒種，· 且為下列族群之一··曱苯、苯與丙酮。並且，進行一第一腫脹 程序150以便於腫入第一起始劑至粒種115A中並形成—第一 顆粒155A。上述之第一腫脹程序15〇更包含超音波振盪步驟 或攪拌步驟，其操作時間約大於16小時。接著，進行一第三 混合程序160 ’其係藉由混合一具有一個雙鍵之丙烯酸酯、一 具有至少二個雙鍵之丙烯酸酯、一稀釋劑、乳化劑與水以形成 a 1271415 一第二溶液165A，其中，上述之具有一個雙鍵之丙烯酸酯係 為下列族群中之一者或其任意組合·_ 2_羥乙胺基丙烯酸酯 (2-hydroxyethyl methacrylate ，HEMA)、丙烯甲酿 (Methylacrylate )、丙稀酸乙酯（Ethyl acrylate )、丙烯酸 丁酉旨 (Brtylacrylate)、丙烯酸辛酯（〇ctyiacryiate)'甲基丙稀酸曱 酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸異丁酯、 甲基丙烯酸丁酯、甲基丙浠酸二曱胺乙酯、羥乙基丙稀酸脂 (Hydroxyethyl Acrylate，HEA )、羥丙基丙稀酸脂 _ (Hydroxypropyl Acrylate，ΗΡΑ)、苯乙烯（Styrene)與醋酸 乙烯（VinylAcetate);上述之具有至少二個雙鍵之丙烯酸酯係 為下列族群中之一者或其任意組合：乙二醇二甲基丙烯酸酯 (ethylene glycol dimethacrylate ^ EGDMA ) > 1?3 butylene glycol dimethacrylate (BGDMA) > 1,4-butane diol diacrylate (BDDA ) > l56-hexane diol diacrylate (HDDA) ^ hexanediol dimethacrylate (HDDMA )、neopentylglycol diacrylate (NPGDA)、_ trimethylolpropanetriacrylate (TMPTA)。另外，稀釋劑對於具 有一個雙鍵之丙烯酸酯與具有至少二個雙鍵之丙烯酸酯為良 溶劑，但對所聚合而成之共聚合體為不良溶劑，以便於形成中 空結構；而且稀釋劑係為下列族群之一：甲苯、笨、正己烧、 辛烷與丙酮，當稀釋劑係為曱苯時，則其添加量約大於具有一 個雙鍵之丙烯酸酯與具有至少二個雙鍵之丙烯酸酯之總重 12 1271415 量，以形成完整之中空結構(如第二圖中之22⑺。另一方面， 本發明所提供之具有中空結構之高分子顆粒的中空度 (porosity)係隨著稀釋劑的添加量增加而增加。其次，進行 一第四混合程序170，其係藉由混合第二溶液145A與第三溶 液165A以形成一第四溶液175A。然後，進行一第二腫脹程 序180以便於腫入具有一個雙鍵之丙烯酸酯、具有至少二個雙 鍵之丙烯酸酯與稀釋劑至第一顆粒155A中並形成一第二顆粒 155B。此外，上述之第二腫脹程序18〇更包含超音波振盪步鲁 驟或攪拌步驟，其操作時間約大於16小時。另一方面，上述 之具有一個雙鍵之丙烯酸酯與具有至少二個雙鍵之丙烯酸酯 之總添加1範圍約為粒種H5A重量的2倍至40倍。 在本實施例中，於第二腫脹程序18〇完成後，進行一第 一分散程序190,其係藉由添加一第一穩定劑於第四溶液175A 中以穩定第二顆粒155B，並避免第二顆粒155B相互間聚集， 其中，上述之第-穩定劑係為下列族群中之一者··聚乙稀基烷⑩ 嗣_yvinylPy_d_，PVP)、聚乙烯醇（p〇lyvinyl alc〇h〇1， PVA )與陰離子型界面活性劑，例如：十工⑥基績酸納（ dodecyl suifonate ’ SDS )。接著，進行一聚合製程2〇〇以使得 第一顆粒155B中所含之具有一個雙鍵之丙烯酸酯與具有至少 二個雙鍵之丙烯酸酯進行交聯聚合反應以形成一丙烯酸酯共 聚合體，並藉此形成一第三顆粒155c，其中，上述之丙烯酸 13 1271415 s旨共聚合體形成該第三顆粒155C之外殼。此外，上述之聚合 製程200更包含一加熱程序，其操作溫度約為5(TC至9(TC。 當上述之第三顆粒155C仍具有上述之具有—個雙鍵之丙稀酸 醋與具有至少二個雙鍵之丙烯酸醋時，隨著加熱程序的操作時 間增加’則第三顆粒155C之外殼的厚度越厚。上述之加熱程 序係於-富含惰性氣體之操作環境中所執行，其中，上述之惰 性孤體更包含氮氣。另—方面，其餘未反應之具有—個雙鍵之 丙烯酸醋、未反應之具有至少二個雙鍵之丙稀酸醋、聚苯乙稀籲 及稀釋劑係分佈於第三顆粒以c之内部。最後，進行一溶出 私序210以移除第二顆粒155c所含之稀釋劑、助吸收劑、聚 苯乙稀、未反應之具有—個雙鍵之丙烯_旨、未反應之具有至 少二個雙鍵之丙烯_、未反應之第—紗劑、丙烯酸醋寡聚 物、第一穩定劑、乳化劑及其他雜質’以形成具有巾空結構之 高分子顆粒155D。上述之溶出程序21〇更包含一内部萃取步 驟與-清洗步驟’其中，内部萃取步驟係藉由—萃取液以移除φ 第二顆粒155C崎所含之該稀釋劑、該助吸賴、聚苯乙婦、 未反應之具有一個雙鍵之丙烯酸酯、未反應之具有至少二個雙 鍵之丙稀酸醋、未反應之第一起始劑及2_經乙胺基丙稀酸醋_ 乙二酵二甲基丙稀酸轉聚物’而萃取液之種類更包含甲苯或 苯，且上述之溶出程序21〇的操作溫度約為1〇〇。〇至12〇。〇， 其操作時_大於36小時。其:欠，上述之清洗步驟係藉由一 1271415 清洗液以移除第三顆粒155c所含之第一穩定劑、乳化劑及其 他雜質’以形成具有中空結構之高分子顆粒155D。上述之清 洗液之種類更包含甲醇。 參考第二圖所示’第二圖係為一具有中空結構之高分子 11粒形成_示意圖：（A)反應蝴，麵後之聚苯乙稀線 性咼分子粒種内部充滿了具有一個雙鍵之丙烯酸酯、具有至少 -個雙鍵之__旨、起糊及稀獅，並形成—球形物。（B) 開始進行聚合製程，触劑、具有—個雙鍵之丙烯_旨與具有 至少二個雙鍵之丙稀_旨反應生絲合物。由於所生成的丙烯 酸酉旨共聚合體她水’所以縣合體會向_接近連續相 (水相）S向移動，因此大部份生成的躲合體會存在於聚苯 烯矛連、、貝相的界面’相對來說，聚苯乙稀和稀釋劑因為比較 親油’所以會往雛_針，在顆_部形成濃度梯度，且 由於在表層稀_含量非常稀少，使得存在於連續相和分散相 ㈤目）之間的聚合物會被析出，於是便形成一層殼層。 隨耆聚合製_操作_，殼層厚度也隨之增加。另外， 2聚合製程後’齡内部仍存«苯乙烯線性高分子、殘餘 雙鍵之丙物、殘餘具有至少二個雙鍵之丙二 tr體及稀釋劑驗朗混合溶液，藉由溶出程序移除顆 /敎1本乙_性高分顿齡驗 結構之高分子難。 L具有中空 15 1271415 在上述本發明之實施例中皆藉由一種對於單體、交聯劑 為良溶劑（good solvent)，但對於共聚合體為不良溶劑（p〇〇r solvent)之稀釋劑，以製造出具有中空結構之高分子顆粒。由 於單體與交聯劑之聚合與交聯聚合反應係於粒徑均一之粒種 中進行，所以能夠製造出粒徑均一之高分子顆粒。另外，添加 適量的稀釋劑與調整聚合製程的操作時間以便於控制高分子 顆粒之中空結構與外殼厚度，並藉此調整高分子顆粒之中空 度。因此，本發明能符合經濟上的效益與產業上的利用性。 綜合以上所述，本發明揭示了一種具有中空結構之高分 子顆粒，此高分子顆粒包含一中空部分與一具有丙烯酸酯共聚 合體(HEMA-EGDMA copolymer)之外殼。本發明亦揭示了一種 具有中空結構之高分子顆粒的製造方法，其係藉由一種對於單 體、交聯劑為良溶劑（good solvent)，但對於共聚合體為不良 溶劑（poorsolvent)之稀釋劑，以製造出上述之中空部份與外 殼結構。 顯然地，依照上面實施例中的描述，本發明可能有許多 的修正與差異。因此需要在其附加的權利要求項之範圍内加以 理解，除了上述詳細的描述外，本發明還可以廣泛地在其他的 實施例中施行。上述僅為本發明之較佳實施例而已，並非用以 限疋本發明之申睛專利範圍；凡其它未脫離本發明所揭示之精 神下所完成的等效改變或修飾，均應包含在下述申請專利範圍 16 1271415 内。 【圖式簡單說明】 第一圖所示係為根據本發明之一第二較佳實施例中，具有中空 結構之高分子顆粒的製程流程圖；與 第二圖所示係為根據本發明之一第二較佳實施例中，具有中空 結構之高分子顆粒的形成機制示意圖。 【主要元件符號說明】Tert-butylhydroperoxide (t-BuPO), ammonium persulfate (APS), potassium persulfate (KPS) and cumene hydroperoxide (CHP). Finally, the fifth solution and the sixth solution are mixed and subjected to a polymerization reaction to form polystyrene particles having a uniform particle size, thereby forming a seed species 115A, wherein the polymerization reaction is carried out in an inert gas-rich operating environment. Executed, wherein the inert gas described above further comprises nitrogen, and the operating temperature ranges from about 50 ° C to 7 ° C. 1271415 In the present embodiment, after the particle production process 110 is completed, a first mixing process 120 is performed by mixing the seed particles 115A, an emulsifier and water to form a first solution 125A, wherein the above The emulsifier further comprises an anionic surfactant, for example, sodium decyl sulfonate (SDS), and uniformly dispersed in the / Valley 125A by a first dispersion procedure 13 The seed species 115A' wherein the first dispersion procedure further comprises an ultrasonic oscillation step or a stirring step. Then, a second mixing step 140 is performed by adding a first initiator and a helper absorbent to the first solution ginsing 125A to form a bismuth solution 145A, wherein the first initiator is in the following groups. One or any combination thereof: 2,2-azobisisobutyronitrile (AffiN), benzyl peroxide (ΒΡΟ), chloroperoxidase (CPO), Tert- Butylhydroperoxide (t-BuPO), ammonium persulfate (APS), potassium persulfate (KPS) fish cumene hydroperoxide (CHP). The auxiliary absorbent is used to swollen the seed, and is one of the following groups: benzene, benzene and acetone. Also, a first swelling procedure 150 is performed to facilitate swelling of the first initiator into the seed 115A and to form the first particle 155A. The first swelling procedure 15 described above further comprises an ultrasonic oscillation step or a stirring step, the operation time of which is greater than about 16 hours. Next, a third mixing procedure 160' is performed by mixing an acrylate having a double bond, an acrylate having at least two double bonds, a diluent, an emulsifier and water to form a 1271415 a second Solution 165A, wherein the acrylate having a double bond is one of the following groups or any combination thereof. 2-Hydroxyethyl methacrylate (HEMA), Methylacrylate ), Ethyl acrylate, Brtylacrylate, octyl acrylate (〇ctyiacryiate) methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid Isobutyl ester, butyl methacrylate, diammonium methyl methacrylate, Hydroxyethyl Acrylate (HEA), Hydroxypropyl Acrylate (ΗΡΑ), Styrene and Vinyl Acetate; the above acrylate having at least two double bonds is one of the following groups or any combination thereof: ethylene glycol dimethacrylate (ethylene) Glycol dimethacrylate ^ EGDMA ) > 1?3 butylene glycol dimethacrylate (BGDMA) > 1,4-butane diol diacrylate (BDDA ) > l56-hexane diol diacrylate (HDDA) ^ hexanediol dimethacrylate (HDDMA ), neopentylglycol diacrylate (NPGDA) , _ trimethylolpropanetriacrylate (TMPTA). In addition, the diluent is a good solvent for the acrylate having one double bond and the acrylate having at least two double bonds, but is a poor solvent for the polymerized copolymer to facilitate formation of a hollow structure; One of the following groups: toluene, stupid, hexane, octane and acetone. When the diluent is fluorene, it is added in an amount greater than that of an acrylate having one double bond and an acrylate having at least two double bonds. The total weight is 12 1271415 to form a complete hollow structure (such as 22(7) in the second figure. On the other hand, the porosity of the polymer particles having a hollow structure provided by the present invention is added with the diluent. The amount is increased and increased. Secondly, a fourth mixing process 170 is performed by mixing the second solution 145A with the third solution 165A to form a fourth solution 175A. Then, a second swelling procedure 180 is performed to facilitate swelling. An acrylate having a double bond, an acrylate having at least two double bonds, and a diluent to the first particle 155A and forming a second particle 155B. Further, the second swelling is as described above. The program 18 further comprises an ultrasonic oscillation step or a stirring step, which has an operation time of more than about 16 hours. On the other hand, the above-mentioned total addition of an acrylate having a double bond and an acrylate having at least two double bonds The range is about 2 to 40 times the weight of the seed H5A. In this embodiment, after the second swelling procedure 18 is completed, a first dispersion process 190 is performed by adding a first stabilizer to the first The fourth solution 175A stabilizes the second particles 155B and prevents the second particles 155B from aggregating with each other, wherein the first stabilizer is one of the following groups: Polyethylene alkyl 10 嗣 _yvinylPy_d_, PVP ), polyvinyl alcohol (p〇lyvinyl alc〇h〇1, PVA) and anionic surfactants, for example: dodecyl suifonate 'SDS. Next, a polymerization process is performed to cause the acrylate having a double bond contained in the first particle 155B to be cross-linked and polymerized with the acrylate having at least two double bonds to form an acrylate copolymer, and Thereby, a third particle 155c is formed, wherein the above-mentioned acrylic 13 1371415 s copolymer forms the outer shell of the third particle 155C. In addition, the above polymerization process 200 further comprises a heating process having an operating temperature of about 5 (TC to 9 (TC.) when the third particle 155C still has the above-mentioned double-bonded acrylic acid vinegar and has at least In the case of two double-key acrylic vinegars, the thickness of the outer shell of the third particles 155C is thicker as the operating time of the heating process increases. The heating process described above is performed in an operating environment rich in inert gas, wherein The above-mentioned inert body further contains nitrogen gas. On the other hand, the remaining unreacted acrylic vinegar having a double bond, unreacted acrylic acid vinegar having at least two double bonds, and polystyrene ringing diluent system Distributed in the third particle to the inside of c. Finally, a dissolution private sequence 210 is performed to remove the diluent, the auxiliary absorbent, the polystyrene, the unreacted propylene having a double bond contained in the second particle 155c. _, unreacted propylene with at least two double bonds, unreacted first yarn agent, acrylic vinegar oligomer, first stabilizer, emulsifier and other impurities 'to form a polymer with a hollow structure Particle 155D. The process 21〇 further includes an internal extraction step and a “cleaning step”, wherein the internal extraction step is performed by extracting the φ second granule 155C, the diluent, the sorbent, the polyphenylene An unreacted acrylate having a double bond, an unreacted acrylic acid vinegar having at least two double bonds, an unreacted first initiator, and 2% ethylamino acrylate vinegar The dimethyl methacrylate transpolymer 'and the extract type further contains toluene or benzene, and the above-mentioned dissolution procedure 21 〇 has an operating temperature of about 1 〇〇. 〇 to 12 〇. 〇, its operation _ is greater than 36 Hour: owing, the above cleaning step is performed by removing a first stabilizer, an emulsifier and other impurities contained in the third particles 155c by a 1271415 cleaning liquid to form a polymer particle 155D having a hollow structure. The type of the cleaning liquid further contains methanol. Referring to the second figure, the second figure is a polymer having a hollow structure, 11 particles are formed. Schematic: (A) reaction butterfly, polystyrene linear 咼 molecule behind the surface The inside of the grain is filled with acrylic acid with a double bond , having at least one double bond, a paste and a lion, and forming a spherical object. (B) starting the polymerization process, the contact agent, the propylene having a double bond, and having at least two pairs The acrylic acid of the bond is the reaction of the raw silk compound. Since the generated acrylic acid is a copolymer of her water, the county complex moves toward the _ close to the continuous phase (aqueous phase) S, so most of the generated hiding bodies will exist. In the interface of polyphenylene spear, and shell phase, relatively speaking, polystyrene and thinner are relatively oleophilic, so they will go to the young _ needle, forming a concentration gradient in the _ part, and due to the thin layer in the surface _ The content is very rare, so that the polymer existing between the continuous phase and the dispersed phase (five) can be precipitated, thus forming a shell layer. With the polymerization process, the thickness of the shell is also increased. After the polymerization process, the internal temperature of the «styrene linear polymer, the residual double bond of the propylene, the residual propyl di-trand and the diluent with at least two double bonds are mixed, and the solution is removed by the dissolution procedure.敎1 This is a difficult polymer for the structure of the B-sex high-scoring age. L has a hollow 15 1271415. In the above embodiments of the present invention, a diluent which is a good solvent for a monomer and a crosslinking agent, but a poor solvent for a copolymer is used. To produce polymer particles having a hollow structure. Since the polymerization and crosslinking polymerization of the monomer and the crosslinking agent are carried out in a particle having a uniform particle size, it is possible to produce a polymer particle having a uniform particle diameter. In addition, an appropriate amount of diluent is added and the operation time of the polymerization process is adjusted to control the hollow structure and the thickness of the outer shell of the polymer particles, thereby adjusting the hollowness of the polymer particles. Therefore, the present invention can meet economic benefits and industrial applicability. In summary, the present invention discloses a high molecular particle having a hollow structure comprising a hollow portion and an outer shell having an acrylate copolymer (HEMA-EGDMA copolymer). The invention also discloses a method for manufacturing a polymer particle having a hollow structure, which is a diluent which is a good solvent for a monomer and a crosslinking agent, but is a poor solvent for a copolymer. To produce the above hollow portion and outer casing structure. Obviously, many modifications and differences may be made to the invention in light of the above description. It is therefore to be understood that within the scope of the appended claims, the invention may be The above are only the preferred embodiments of the present invention, and are not intended to limit the scope of the present invention; any equivalent changes or modifications made without departing from the spirit of the present invention should be included in the following. The patent application scope is 16 1271415. BRIEF DESCRIPTION OF THE DRAWINGS The first drawing is a process flow diagram of a polymer particle having a hollow structure in accordance with a second preferred embodiment of the present invention; and the second figure is shown in accordance with the present invention. In a second preferred embodiment, a schematic diagram of the formation mechanism of the polymer particles having a hollow structure. [Main component symbol description]
粒種製造程序110 粒種115A 第一混合程序120 第一溶液125A 第一分散程序130 第二混合程序140 第二溶液145A 第一腫脹程序150 第一顆粒155A 第三顆粒155C 第二顆粒155BSeed Production Procedure 110 Seed 115A First Mixing Procedure 120 First Solution 125A First Dispersion Procedure 130 Second Mixing Procedure 140 Second Solution 145A First Swelling Procedure 150 First Particle 155A Third Particle 155C Second Particle 155B
具有中空結構之高分子顆粒155D 第三混合程序160 第三溶液165A 第四混合程序170 第四溶液175 A 第二腫脹程序180 第二分散程序190 聚合製程200 溶出程序210 17 1271415 聚苯乙卸粒種南分子〜 稀釋劑一 具有一個雙鍵之丙烯酸酯（單體）Μ 具有至少二個雙鍵之丙烯酸酯（交聯劑）X 丙烯酸酯共聚合體Ρ 18High molecular particle 155D having a hollow structure Third mixing procedure 160 Third solution 165A Fourth mixing procedure 170 Fourth solution 175 A Second swelling procedure 180 Second dispersion procedure 190 Polymerization process 200 Dissolution procedure 210 17 1271415 Polyphenylene bun Kind of South molecule ~ Diluent - Acrylate (monomer) having one double bond acrylate (crosslinking agent) X acrylate copolymer having at least two double bonds Ρ 18