A7 B7 鯉濟部中央椟準局員工消費合作社印^ 五、發明説明（1 ) 本發明係關於一種製備低分子量的乙烯基單體和順丁烯二賤單 體的（嵌段）共聚物之方法。 乙晞基單體和順丁烯二酸單體（通常包括笨乙烯和順丁晞 —故肝）的低分子量共聚物（LW_Sma)係用於多種不同目 的的應用。著名的係其可作爲染料分散劑、黏度調節劑、 互適劑'乳化劑、保護膠體及其類似物。其是否可使用， 而如果可以的話，有效性有多少皆非常地依共聚物的分子 量和分子量分佈而定。 因此’明顯地要努力發展。可在苯乙烯和順丁烯二酸酐 共聚合時控制分子量的方法。1968年發表的BE 710138揭 不一種藉由在150 _ 270 °C下使單體共調節聚合而製造LW-SM A之方法，其使用特殊調聚體（作用如同竺轉移劑的溶 劑）、不加入形成自由基的活化劑並且僅受熱的影響。美國 專利3,45 1，979 (1969)揭示一種在175 _ 25〇°C下的聚合方法 其中分子量係藉由使用單環烴做爲溶劑來控制，而該單環 烴有一個具有6個碳原子之核心（例如茴香素和對-伞花 烴）。於丨970年發表的DE_〇S_193〇217中，提出藉由在溶 液或沉澱聚合方法中使用特殊羥基烷基硫醇來製造lw_ SMA。美國專利4，180,637(1979)揭示—種溶劑聚合方 法，其中LW-SMA係藉由使用單價銨金屬陽離子的氫 氧化物或親核性鹽來製成。最後），DD_A 2594〇8(i988)揭 種在4〇-1〇(rc下的溶劑聚合方法，其tLW_SMA係 藉由使用係爲硫代碳酸之衍生物的鍵轉移劑來製迭。 | 頃注意到在過去此藝的所有這些方法中广曾推萬活性溶 _____-4- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ； . ί ^-- * Ψ (請先閱讀背面之注意事項再填寫本頁jA7 B7 Printed by the Consumers' Cooperatives of the Central Bureau of Standards and Quarantine of the Ministry of Economic Affairs of the People's Republic of China ^ V. Description of the Invention (1) The present invention relates to the preparation of (block) copolymers of low molecular weight vinyl monomers and cis-butadiene monomers. method. Low molecular weight copolymers (LW_Sma) of ethenyl monomers and maleic acid monomers (usually including stupid ethylene and maleic acid—so liver) are used for many different applications. It is well-known for its use as a dye dispersant, viscosity modifier, mutual compatibility agent, emulsifier, protective colloid, and the like. Whether it can be used, and if so, how effective it is depends very much on the molecular weight and molecular weight distribution of the copolymer. So it ’s obviously going to work hard. Method for controlling molecular weight during copolymerization of styrene and maleic anhydride. BE 710138, published in 1968, discloses a method for manufacturing LW-SM A by co-regulating polymerization of monomers at 150 _ 270 ° C. It uses special telomers (solvents that act like Zhu transfer agents). Free radical-forming activators are added and are only affected by heat. U.S. Patent 3,45 1,979 (1969) discloses a polymerization method at 175-25 ° C in which the molecular weight is controlled by using a monocyclic hydrocarbon as a solvent, and one of the monocyclic hydrocarbons has 6 carbons. Atomic core (such as anisin and p-cymene). In DE_OS_193〇217, published in 970, it was proposed to make lw_SMA by using a special hydroxyalkyl mercaptan in a solution or precipitation polymerization method. U.S. Patent No. 4,180,637 (1979) discloses a solvent polymerization method in which LW-SMA is made by using a hydroxide or a nucleophilic salt of a monovalent ammonium metal cation. Finally), DD_A 2594〇8 (i988) discloses a solvent polymerization method at 40-10 (rc), and its tLW_SMA is made by using a bond transfer agent which is a derivative of thiocarbonic acid. | It is noted that in all of these methods in the past, Guangxu has promoted the active solvent _____- 4- This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm);. Ί ^-* Ψ (please first Read the notes on the back and fill out this page j
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/A A7 B7 五、發明説明（2 ) Μ (具有鏈轉移活性的溶劑）抑或特殊鏈轉移劑（C T A)。但 足，根據所知’活性溶劑通常並不使用，因爲其會污染因 而產生之聚合物或者將需要昂貴的將其從該聚合物中除去 的乾燥步驟《另外，含有硫或金屬的CTA之使用限於可忍 跫此種原子存在的應用。在此方面，想要提出的係包括含 有硫之CTA的LW-SMA可能有變色、討厭的氣味及/或加 速老化等缺點。 P.于' 這些缺點以外，頃發現這些方法中沒有一個可正確斷 定因而產生之聚合物的分子量。通常，需要使用試誤法來 找出某種反應條件下反應物的必須濃度。不須贅言，改變 万法參數之—（例如，溫度，在達到最佳反應器產量的努力 時）將係使方法再度成爲最佳，以獲得具有想要的分子量的 L W - S Μ A所必須的。此種連續的最佳化不僅需要時間和努 力’並且亦會產生不符規格的廢品。 另外，當某種用途要求不同性質時，過去此藝的L w _ S ΜA不容易進—步修改。尤其在互適化的範疇中，許多的 用途常常需要帶有僅部份符合已知LW-SMA之性質的化合 物。因此’需要可容易修改的L W - S Μ A。 〜另外，於習用的造方法中爲大眾所热知地， $乙缔和順丁烯二酸酐單體會強烈的選&更迭型式的共聚 、用這疋說如果單體係以1 :: 1,莫耳比率以外的比率進 料（依方法條件而定），那麼過f的箪體會先形成更迭共聚 *人，’’；後再形成單質聚合物（因而產生二種難以分離的不同 聚口扣，並且其中僅有一種具有想要的性/質/j。如果剩餘的 本纸張尺度顏中ϋϋ家縣（CNS) (21GX二) ：--.---{裝-- * ' (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央#準局員工消費合作社印製 kl B7 五、發明説明（3 單體沒有單質聚合，那麼該單體的轉化速率將會相當低並 且其會污染已形成的共_聚物。這二種結果皆不是想要的。 目前，驚奇地發琬一種新的聚合方净，其中大大地克服 了缺點。頃發現僅有一種型式的共聚物形成（和單體比率無 關），並且LW-SMA的分子量非常接近於可容易計算出的 理論値，因此貫質上減少達到最佳條件的努力，同時可得 具有想…要之性質的嵌段共聚物。 本方法之特徵爲使用特殊型式的分子量控制劑，稱爲起 始劑。所使用之起始劑最好有式1}之構造： (请先閲讀背面之注意事項再填寫本I ) 装_ C、 R--〇 I) 訂 經濟部中央標準局員工消費合作社印家 其中： ♦ R表示一個基，其有至少一個碳原子並且係那種能起 始未飽和單體之自由基聚合作用的自由基R :-♦至多五個以Xi-Xe表示的基爲相同良不同的線型或支 鏈、經取代過或未經取代過（環狀）烷基及/或二個或 多個X ! - X 6基可键合以形成包括._ c N c _部份的構造” ♦互補基X 1至X6係官能基，其個別選自包括經取代過戒 未經取代過芳香基、氰基、硝基、二核^氧膦基、 -6 - 表纸張尺度適用中國國家榇準（CNS ) A4規格（2丨〇><297公釐） i In 經濟部中央標準局員工消費合作社印裝 五、發明説明（4 R 〇-、R 0C(0)-、R’C(〇)〇…R’c(〇)〇c(〇)·、 R R NC(〇)_、r c(0)NR’-、R,c(〇)NR,c(〇)和 R C ( 0 )-，其中每一個R ’個自係氫或經取代過或未經 取代過烴基，或者，另可選用地，_cXiX2X^^_ CXjXsX6表示經取代過或未經取代過的芳香基。 1基R·個別地可係烷基、芳香基、烷芳香、芳烷基及， 或環k基。經取代過或未經取代過的烴基最好含有少於3 〇 個的原子，更佳係少於i 5個。 當在本又中使用時，用語，，起始劑，，定義爲可藉由熱分解 作用起始和控制聚合反應的化合物，該反應中可視需要存 在加速劑。在熱分解作用中，起始劑必須能形成二個自由 基碎片，其中之一必須有優越的使聚合反應起始之傾向， 即藉由和單體分子形成穩定的共價鍵，因此將自由基轉移 给孩單體，然而如此藝中已知的，另一個自由基碎片主要 係安疋的自由基。較佳的化合物係具有式丨）構造的。咸信 分解作用中形成的碳在中心之自由基起始聚合作用，然而 硝基氧化物自由基作用如同安定的自由基，其終止成長中 的鏈。不管本發明被這樣的理論限制，更相信在聚合溫度 下’終止反應係可逆的’因此單體可插入最後的單體單元 和起始劑的硝基氧化物部份之間。這表元這些型式的化合 物不同於使成長中的鏈終止並接著起始另一新鏈的正規鍵 轉移劑。 .、 頃注意到較佳的起始劑説明於同一申請者的國際申請書 字號PCT/EP 97/〇5〇〇9。但是，其中4揭示這些化合物 表紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） - - ----- n . 丁 - . /1 -'β ,- {請先閲讀背面之注意事項再填寫本頁) 經濟部中央標準局員工消費合作社印家 A7 B7 五、發明説明（5 ) ~~~ 係特別適合於LW_SMA(嵌段）共聚物之製造，並且藉由使 用這種特殊種類聚合物，所有過去此藝之缺點皆可克服。 根據本發明之聚合方法大概係”假的活聚合方法”該用語 表不其中乙晞屬未飽和單體係藉由至少一種起始劑來聚合 的自由基聚合方法。根據未具限制性理論，在此種方法 中’聚合作用動力尤其係依所使用之起始劑的熱分解速率 而定。__ •方；具有式1)之起始劑，X〖-X6最好不要鍵合形成環狀 構造。另外，每一個ΧγΧ6最好含有30個以下的碳原子。 爲了製造低分子量的起始劑，每一個χ ! _χ6更好含有丨〇個 以下的碳原子。最佳地，至多5個X丨_χ6各別係選自甲基、 乙基、丙基、異丙基、丁基、二級丁基、三級丁基和環己 基。 另外，方法取好含有具有式1 )之起始劑的利用，式1 )之 中的官能基係選自經取代過或未經取代過的芳香基、氰 基、二烷氧膦基、R’c(0)0 -和R'〇c(0)-。芳香基之中， 苯基、甲苯基和萘基係較佳的。更佳的係其中起始劑有氰 基、苯基、R' C (0 ) 0 -或二烷氧膦基的方法。還要佳的係 起始劑具有氰基或私基的方_法。較佳地，這些起始劑可使 用而不會有毒性副產物形成。 严·-〆 起始劑之官能基的非限制性實例更包括曱醚、乙醚、丙 醚'丁醚、聚（蜣基醚）、甲基酮、乙基酮、^基酮、異丙 基酮、丁基酮、異丁基酮、三級丁基酮、二乙氧膦基、乙 氧丙氧膦基 '二丙氧膦基、二丁氧膦基、/二/異丁氧膦基、 ___-8- 本紙張尺度適用中國國家標準（CNS ) A4規格（2丨0X297公釐） [ *n n ϊ - - /1 n - n n - — — — —— —l /λ^ * * (請先閲讀背面之注意事項再填寫本頁) · h 經濟部中央揉準局貝工消费合作社印笨 A7 _____ B7__ 五、發明説明（6 ) -C(0)0CH3、-C^COOC^H^Ci-Cw羧酸酯。 R基可有一個或多個ONC^Xbjc^Xhe)官能，只要每一 個在一個或多個R-0鍵斷裂時形成的r基起始未飽和單體 的自由基聚合作用。另外，R最好不具有聚合性質，即R最 好不包括約4個以上的重覆單元，其係經由—個或多個未 飽和單體的自由基聚合作用而結合的。r最好不含有二個 以上的此種重覆單元。更好的係其中R等於c(Xi 3)或 C (X 4 - 6)的化合物。 製造LW-SMA之方法可在各種溫度下施行，—般的範圍 係5 0至2 0 0 C。聚合溫度更佳係8 〇至15 0 °C。依所選定之 聚合溫度’可選擇有可接受之分解速率的起始劑。例如， 由馬.克維莫雷寇斯（Macromolecules ), 1995, 28 8722-8728，可知抽取電子的官能基的使用將會使R_ 〇鍵安定， 然而給予電子的官能基將會使其不安定。經由該文獻所給 予之訊息和敎導’熟諳此藝者可毫無困難地選出官能基的 適當型式和數量以獲得可用的起始劑。於施行確實的聚人 實驗之前’可先以一種或多種已知方法測定起始劑的半生 期，這是爲了確立其可在何種溫度下使用。 在根據本發明之方法中使用的起始劑量係依因而產生之 想要的LW-SMA的分子量而定。更特定#，根據本發明 之方法產生具有近乎理論値（Mth),之數.目平均分子量的聚 合物，該理論値係由（Μ^.ί1 +[單體·]/[起始劑]換 算而計算得之，其中係重覆單體單元的平均分子量。 對苯乙晞順丁烯二酸酐完全更迭共聚物而/皆， Λ ° Μ a «馬約 -9 - ____ 本紙張尺度適用中國國家標準（CNi) A4規格1 210x297公釐） ^ ~ -----— (請先閲讀背面之注意事項再填寫本頁) 裝. 訂 經濟部中央標準局貝工消費合作社印繁 A7 B7 五、發明説明（7 ) ( 104+98)/2= 101。由於LW-SMA通常被認爲係分子量爲 約1000至約10000道爾頓（Dah〇n)的聚合物，這是説，所 使用之起始劑莫耳量理想地係單體莫耳量的约〇 1至〇 〇1 倍。事貫上，聚合系統中，起始劑莫耳量係在單體莫耳量 的0.15至0_ 〇〇 1倍之間改變。起始劑莫耳量更佳係單體莫耳 量的0.12至0.008倍。 通常-在根據本發明之方法中聚合的乙晞屬未飽和單體爲 笨乙烯和順丁烯二酸酐。但是，根據本發明之方法並不限 於僅使用此二種單體的方法。除了順T,二酸纤以外，亦 可使用其它順丁烯二酸單體，像檸康酐、衣康酐、順丁埽 一酸、S馬酸、檸康酸、衣康酸、帶有Cl_Ci8_元醇的該 酸之半醋類（例如，順丁烯二酸曱酯和順丁晞二酸二級丁 自曰）順丁晞一酸酿亞胺 '檸康酷亞胺、衣康酿亞胺及/或 這些單體與，視需要選用之順丁烯二酸酐的混合物。類似 地邵份的）笨乙埽可被其它乙烯基單體取代，像α -烯 ’匕_兴戊—晞：丁二烯；丙烯腈；氯乙晞；有機酸之乙缔 醋’例如’乙酸乙晞酯和硬脂酸乙烯酯：（烷基）（甲基）丙 缔酸或其之酯類，例如，甲基丙烯酸甲酯：乙烯基膦酸或 其之酿類：乙烯基吡啶：乙烯基烷基醚類，例如_，乙烯基 甲基醚和乙烯基異丁基醚：以及其它乙基芳香族化合物 或其之衍生物’例如，笨乙晞膦酸、'笨乙晞膦酯、乙烯基 曱苯、乙烯基二甲苯、2,4_二曱-基笨乙晞、2,5_二氣笨乙 缔、2-曱基·4-氯苯乙烯等等。最好至少有笨乙烯和順丁 缔一 Sk奸用於根據本發明之方法中。更佳地，順丁晞二酸 本紙張纽適财⑽) (請先閱讀背面之注意事項再填寫本頁) 裝- 訂 A7 B7 經濟部中央樣準局負工消費合作社印掣 -11 - 五、發明説明（8 奸牙苯乙晞—者之含量爲最终聚合物的至少10重量％。最 佳的係產生含有至少3 〇% w/w苯乙缔和順丁烯二酸酐之 L W - S Μ A的方法。 方法中—種型式單體之間的莫耳比率係不重要的。與所 使用之比率操關，本來就只有一種型式的聚合物形成。如 果一種單體過量使用，那麼依該單體之構造而定其將會在 万法的較後步驟中單質聚合形成個別的嵌段，當二種型式 單體皆存在時，該嵌段係附於較先步驟中形成的聚合物 上這與，例如，習用之分批聚合方法相反，在分批聚合 方法中過量單體形成不附於較先形成之共聚物上的單質聚 合物。因此，在先形成之聚合物的分子比率不等於進料單 sa的單體比率之情形中，本發明之方法將產一種嵌段共聚 物，其帶有—個或多個具有苯乙晞-順丁缔二酸酐更迭構造 心嵌段和—個具有不同構造（依所使用之單體型式和比例而 疋）之嵌段。爲了獲得有想要之性質的L w - S Μ A，所以乙 婦基單體對順丁烯二酸單體的比率最好係在〇 6至5的範 圍’而0· 8和3之間的比率係更佳。由於附於苯乙缔-順丁晞 二酸奸更迭共聚物上的苯乙烯嵌段係容易形成的，所以最 好使用與順丁埽二酸酐相比係稍微莫耳過量的苯乙晞。 若如此須要’爲製造具有由一種或多種 於新單體導入後存在的單體所構成之嵌段的嵌段共聚物， 那麼在50% w/w以上（最好係9〇〇/。w/w以上XLW-SMA單 體已經反應後，將新單體導入聚合系統内係可能的。何種 型式之嵌段會形成將大大地依所存在之輩體，的共聚合作用 t紙張尺度適用中國國家標準（CNS ) A4*t格（210X297公釐 • 裝 I -I I.一.. - ϋ» I— —_J;, ' * -(請先閲讀背面之注意事項再填寫本頁) 」 一 A7 B7 五、發明説明（9 參數而定3此種步驟可重覆以製造分子中有三種或多種不 同型式欣段的嵌段共聚物。新加入的單體最好係選自上述 的乙稀基單體。此種嵌段共聚物之構造對過去此藝之L汲_ sm，a而言係不可能的’因爲習用方法中的聚合反應係由鍵 轉和’歧化或化合等反應所終止咸信在根據本發明之方法 中，如可又中曾指出的，起始劑之硝基氧化物部份保留在 聚〇物鏈的一個末端並五當單體導入時使得此種單體可再 插入。在下一個嵌段形成之前，LW-SMA嵌段最好有至少 5個（軼佳係1 〇個以上）單體單元（隨便何種型式單體）的化 合長度。 _ _ ，然根據本發明之方法可以各種方式施行，例如，以大 塊诸π 、札液或溶劑等聚合法，但以溶劑聚合法係較佳 的更佳的方法爲其中之溶劑係不具反應性的溶劑聚合 法，這是説因而產生之聚合物的所有末端基的5%以下係由 溶劑部份構成。該溶劑聚合法中，單體的總濃度可在非常 廣泛的範圍内變化並且僅受限於反應器效率和單體（及所形 成之聚合物）在溶劑中的溶解度。更特定言之，單體/聚合 物之溶解度將依溶劑之型式'溫度和所使用之單體型式及 比率而定。少於丨0體積％ (% v/v)的單體濃度通常被認爲係 不經，的，然而超過85%v/v的濃度通常1產生黏度/容解 度門L因此，車父佳的單體濃度，芩2 0 -.6 5。/〇 v / v ,以溶劑 和單體之總體積爲基準。 可在根據本發明之方法中使用的溶劑包括，但不限於， 醚類，例如，二噁烷和四氫呋喃：酮類^例如，丙酮、甲 ： · ^裝------訂 (請先閲讀背面之注意事項再填寫本頁) - 經濟部中央標準局貝工消费合作社印裝 -12 經濟部中央標準局貝工消費合作社印製 A7 B7 五、發明説明（10 ) 基乙基嗣及其類似物：g旨類，例如，乙酸乙酯和乙酸甲氧 基丙酯：芳香族溶劑類，例如，曱苯和二曱苯：像二甲替 甲si胺和硝基丙烷等產物：以及其之混合物。 g 在根據本發明之方法中，可使用更多添加物，例如，習 用之產生自由基的種類，其包括有機過氧化物、偶氮-引發 劑和u v -引發劑：安定的自由基··以及鏈轉移劑。當在方 法中使用時，亦可使用使形成自由基種類之分解作用催化 的加速劑、添加劑。另外，若如此須要，像染料、安定 劑、膠體、填料等輔藥可在聚合作用閹始或進行時加入， 只要其不會介人聚合方法中。另可選用&，輔藥係在聚合 作用後加至聚合物（溶液）中。 在根據本發明之方法中使用的起始劑可以各種習用之方 法製成’像在’例如 ’ j Chem. Soc·，1954, 1920-1924)中 说明的。反應物和反應條件被選定，以致於在合成期間二 個附於氮原子上的以碳爲中心之自由基中的至少—個會帶 有官能基其係藉由選擇帶有以碳爲中心之自由基前身的官 能基之一個或多個的適當濃度而非常輕易地達成。帶有不 含後之自由基的官能基最好係藉由一種或多種適當的偶 氣、C - C或其它起始劑（例如，具有高脱羧速率的二醯基過 氧化物）的分解作用而得之。依起始劑之I途而定，最好係 僅與一種型式的帶有一氧化氮（N 〇)氣體的以碳爲中心之自 由基（含有官能基）反應。 ‘-, 另可選用地’根據本發明之化合物可藉由在熱的影響之 下或帶有以碳爲中心之自由基的亞硝基化合.物之著名反應/ A A7 B7 5. Description of the invention (2) M (solvent with chain transfer activity) or special chain transfer agent (C T A). However, as far as is known, 'active solvents are generally not used because they can contaminate the resulting polymer or will require expensive drying steps to remove it from the polymer. Additionally, the use of sulfur- or metal-containing CTA Limited to applications that can tolerate the existence of such atoms. In this regard, LW-SMAs that include sulfur-containing CTA may have disadvantages such as discoloration, unpleasant odor, and / or accelerated aging. P. In addition to these disadvantages, it was found that none of these methods can correctly determine the molecular weight of the resulting polymer. In general, trial and error is required to find the necessary concentration of reactants under certain reaction conditions. Needless to say, changing one of the process parameters—for example, temperature, when trying to achieve optimal reactor yields—will be necessary to make the process optimal again to obtain LW-S Μ A with the desired molecular weight. of. This continuous optimization not only requires time and effort ', but also produces out-of-specification waste. In addition, when a certain application requires different properties, it is not easy to further modify the L w _ SMA in the past. Especially in the field of compatibility, many uses often require compounds with compounds that only partially meet the properties of the known LW-SMA. Therefore, 'W L-S Μ A, which can be easily modified. ~ In addition, in the conventional manufacturing method, it is well known to the public that the $ ethylene and maleic anhydride monomers will strongly select & alternate-type copolymerization. Let us say that if the single system starts with 1 :: 1, feed at a ratio other than the Mohr ratio (depending on the method conditions), then the carcass over f will first form alternating copolymers * '', and then form a simple polymer (thus producing two different polymers that are difficult to separate) Buckle, and only one of them has the desired sex / quality / j. If the remaining paper size is Yanzhong County (CNS) (21GX 二): --.--- {装-* ' (Please read the precautions on the back before filling this page) Order the KL B7 printed by the Ministry of Economic Affairs Central #Associate Bureau Employee Consumer Cooperative V. Description of the invention (3 monomer has no elementary polymerization, then the conversion rate of the monomer will be quite low And it will contaminate the copolymer that has been formed. Neither of these results is desired. At present, it is surprising to develop a new polymerization method, which greatly overcomes the disadvantages. It was found that there is only one type of copolymerization. Product formation (independent of monomer ratio), and the molecular weight of LW-SMA is very close It is close to the theoretical 値 that can be easily calculated, so the efforts to achieve the optimal conditions are reduced, and block copolymers with desired properties can be obtained. This method is characterized by the use of special types of molecular weight control agents, It is called the initiator. It is best to use the structure of formula 1}: (Please read the precautions on the back before filling in this I) _ C, R--〇I) Order the Central Bureau of Standards of the Ministry of Economic Affairs Employee Consumer Cooperative Ink House Among them: ♦ R represents a radical which has at least one carbon atom and is the kind of radical R that can initiate the radical polymerization of unsaturated monomers:-♦ up to five are represented by Xi-Xe The radicals are the same or different linear or branched, substituted or unsubstituted (cyclic) alkyl, and / or two or more X! -X6 radicals can be bonded to form the Structure of c_part "♦ Complementary groups X 1 to X6 are functional groups, each of which is selected from a group including substituted or unsubstituted aromatic group, cyano group, nitro group, dinuclear phosphinyl group, -6- The paper size of the table is applicable to China National Standard (CNS) A4 (2 丨 〇 > < 297 mm) i In Ministry of Economy Printed by the Consumer Standards Cooperative of the Central Standards Bureau V. Invention Description (4 R 〇-, R 0C (0)-, R'C (〇) 〇 ... R'c (〇) 〇c (〇) ·, RR NC (〇 ) _, Rc (0) NR'-, R, c (〇) NR, c (〇), and RC (0)-, where each R 'is an autogenous hydrogen or a substituted or unsubstituted hydrocarbon group, Alternatively, alternatively, _cXiX2X ^^ _ CXjXsX6 represents a substituted or unsubstituted aromatic group. 1 group R · may individually be an alkyl group, an aromatic group, an alkaryl group, an aralkyl group, or a ring k The substituted or unsubstituted hydrocarbon group preferably contains less than 30 atoms, more preferably less than 5 atoms. As used herein, the term, initiator, is defined as a compound that can initiate and control a polymerization reaction by thermal decomposition, and an accelerator may be present in the reaction as needed. In thermal decomposition, the initiator must be able to form two free radical fragments, one of which must have a superior tendency to initiate the polymerization reaction, that is, by forming a stable covalent bond with the monomer molecule, it will be free The radical is transferred to the monomer, however, as is known in the art, another free radical fragment is mainly a free radical. Preferred compounds are those having the formula (i). The carbon formed during the decomposition of Xianxin initiates the polymerization of free radicals in the center, but the nitrooxide radicals act like stable free radicals, which terminate the growing chain. Regardless of the theory being limited by this theory, it is further believed that the termination reaction is reversible at the polymerization temperature so that the monomer can be inserted between the final monomer unit and the nitrooxide portion of the initiator. This indicates that these types of compounds are different from regular bond transfer agents that terminate a growing chain and then initiate another new chain. It is noted that the preferred starter is described in the International Application No. PCT / EP 97/005009 of the same applicant. However, 4 of them reveals that the paper size of these compound tables is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)------- n. Ding-. / 1 -'β,-{Please read the note on the back first Please fill in this page again.) Employee Consumer Cooperatives A7 B7, Central Standards Bureau, Ministry of Economic Affairs. 5. Description of Invention (5) ~~~ It is particularly suitable for the manufacture of LW_SMA (block) copolymers, and by using this special kind Polymers, all the disadvantages of this art can be overcome. The polymerization method according to the present invention is probably a "pseudo-living polymerization method" which means a radical polymerization method in which an ethylenic unsaturated monosystem is polymerized by at least one initiator. According to a non-limiting theory, the ' polymerization kinetics in this method depends in particular on the thermal decomposition rate of the initiator used. __ • Square; with the initiator of formula 1), X 〖-X6 should not be bonded to form a ring structure. In addition, each XγX6 preferably contains 30 or less carbon atoms. In order to produce a low molecular weight initiator, each χ! _Χ6 preferably contains less than or equal to 0 carbon atoms. Most preferably, up to 5 X__x6 are each selected from methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and cyclohexyl. In addition, the method includes the use of a starter having Formula 1). The functional group in Formula 1) is selected from a substituted or unsubstituted aromatic group, a cyano group, a dialkoxyl group, and R. 'c (0) 0-and R'oc (0)-. Among the aromatic groups, phenyl, tolyl and naphthyl are preferred. More preferred are methods in which the initiator is cyano, phenyl, R'C (0) 0-, or dialkylphosphino. Even better are methods in which the initiator has a cyano group or a private group. Preferably, these initiators are used without the formation of toxic by-products. Non-limiting examples of functional groups of the 〆-fluorene initiator include methyl ether, diethyl ether, propyl ether 'butyl ether, poly (fluorenyl ether), methyl ketone, ethyl ketone, alkyl ketone, isopropyl Ketone, butyl ketone, isobutyl ketone, tertiary butyl ketone, diethoxyphosphino, ethoxypropoxyphosphino'dipropoxyphosphino, dibutoxyphosphino, / di / isobutoxyphosphino , ___- 8- This paper size applies to Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) [* nn ϊ--/ 1 n-nn-— — — — — l / λ ^ * * (Please (Please read the notes on the back before filling this page) · h Yin Ben A7, Shellfish Consumer Cooperative, Central Bureau of the Ministry of Economic Affairs _____ B7__ V. Description of Invention (6) -C (0) 0CH3, -C ^ COOC ^ H ^ Ci -Cw carboxylic acid ester. The R group may have one or more ONC ^ Xbjc ^ Xhe) functions, as long as each of the r groups formed when one or more R-0 bonds are broken initiates radical polymerization of the unsaturated monomer. In addition, R preferably does not have a polymerization property, that is, R preferably does not include about 4 or more repeating units, which are combined via radical polymerization of one or more unsaturated monomers. r preferably does not contain more than two such repeating units. More preferred are compounds in which R is equal to c (Xi 3) or C (X 4-6). The method of manufacturing LW-SMA can be performed at various temperatures, the general range is 50 to 2 0 C. The polymerization temperature is more preferably 80 to 150 ° C. Depending on the selected polymerization temperature ', a starter having an acceptable decomposition rate can be selected. For example, from Macromolecules, 1995, 28 8722-8728, it can be known that the use of electron-extracting functional groups will stabilize the R_O bond, but the functional groups given electrons will make them unstable. . With the information and guidance given in this document, the skilled artisan can easily select the appropriate type and number of functional groups to obtain a usable initiator. Before performing the actual gathering experiments, the half-life of the initiator can be determined by one or more known methods in order to establish the temperature at which it can be used. The starting dose used in the method according to the invention depends on the molecular weight of the desired LW-SMA produced thereby. More specifically #, according to the method of the present invention to produce a polymer having a near theoretical 値 (Mth), the average molecular weight of the mesh, the theoretical 値 is based on (Μ ^ .ί1 + [monomer ·] / [starter] It is calculated by conversion, where it is the average molecular weight of the repeating monomer units. P-phenylene terephthalate maleic anhydride completely replaces the copolymer and all, Λ ° Μ a «Mayo-9-____ This paper size applies to China National Standard (CNi) A4 size 1 210x297 mm) ^ ~ -----— (Please read the precautions on the back before filling out this page) Packing. Ordered by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, India A7 B7, 5 Explanation of the invention (7) (104 + 98) / 2 = 101. Since LW-SMA is generally considered to be a polymer having a molecular weight of about 1000 to about 10,000 Daltons, this means that the molar amount of the starting agent used is ideally the molar amount of the monomer. About 0.001 to 0.001 times. Consistently, the molar amount of the initiator in the polymerization system varies from 0.15 to 0-0.01 times the molar amount of the monomer. The molar amount of the starter is more preferably 0.12 to 0.008 times the molar amount of the monomer. Usually-the ethylenically unsaturated monomers polymerized in the process according to the invention are stilbene and maleic anhydride. However, the method according to the present invention is not limited to a method using only these two monomers. In addition to cis T, diacid, other maleic acid monomers, such as citraconic anhydride, itaconic anhydride, maleic acid, S maleic acid, citraconic acid, itaconic acid, with Cl_Ci8_ol alcohols, such as hemiacetic acid (for example, maleic acid maleate and maleic acid secondary butyl sulfonate) maleic acid monoimide 'citraconimine, itaconic Blends of imine and / or these monomers and optionally maleic anhydride. Similarly, stilbene may be replaced by other vinyl monomers, such as α-ene's-X-pentyl-fluorene: butadiene; acrylonitrile; chloroacetamidine; ethyl acetate of organic acids 'for example' Acetyl acetate and vinyl stearate: (alkyl) (meth) acrylic acid or its esters, for example, methyl methacrylate: vinylphosphonic acid or its derivatives: vinylpyridine: Vinyl alkyl ethers, such as vinyl ether, vinyl methyl ether and vinyl isobutyl ether: and other ethyl aromatic compounds or derivatives thereof such as benzammonium phosphonic acid, benzammonium phosphinate , Vinylbenzene, vinylxylene, 2,4-dioxo-ylbenzylacetophenone, 2,5_difluorobenzylethene, 2-fluorenyl · 4-chlorostyrene, and the like. It is preferred that at least vinyl and cis-butadiene be used in the method according to the present invention. Better yet, maleic acid paper (Newspaper). (Please read the notes on the back before filling out this page.) Pack-Order A7 B7 Printed by the Central Consumer Procurement Bureau, Ministry of Economic Affairs, Consumer Cooperatives-11-5 2. Description of the invention (8) The content of acetophenone is at least 10% by weight of the final polymer. The best system is to produce LW-S containing at least 30% w / w styrene-acrylic acid and maleic anhydride. The method of Μ A. In the method, the Mohr ratio between monomers of different types is not important. Regarding the ratio used, only one type of polymer is originally formed. If one monomer is used in excess, then Depending on the structure of the monomer, it will be polymerized in the later steps of Wanfa to form individual blocks. When both types of monomers are present, the block is attached to the polymer formed in the previous step. This is in contrast to, for example, the conventional batch polymerization method in which excess monomers form a simple polymer that does not attach to a previously formed copolymer. Therefore, the molecular ratio of the previously formed polymer In the case where it is not equal to the monomer ratio of the feed list sa, The method of the present invention will produce a block copolymer with one or more core blocks with phenethylhydrazone-maleic anhydride alternation structure and one with different structure (depending on the type of monomer used and Ratio 疋). In order to obtain L w-S Μ A with desired properties, the ratio of ethynyl monomer to maleic acid monomer should preferably be in the range of 0 to 5 ' The ratio between 0.8 and 3 is even better. Since the styrene block attached to the styrene-maleic acid maleate copolymer is easy to form, it is best to use it with maleic acid. The acid anhydride is a slight molar excess of phenethylhydrazone. If it is necessary to 'make a block copolymer with a block composed of one or more monomers present after the introduction of the new monomer, then at 50% w Above w / w (preferably above 900 / w) After the XLW-SMA monomer has reacted above w / w, it is possible to introduce new monomers into the polymerization system. What type of block will form will depend greatly on Existing generations, copolymerization t Paper size is applicable to Chinese National Standard (CNS) A4 * t grid (210X297 mm • equipment I -I I. 一 ..-ϋ »I— —_J ;, '*-(Please read the precautions on the back before filling out this page)” A7 B7 V. Description of the invention (depending on 9 parameters 3 such steps) It can be repeated to produce block copolymers with three or more different types of Xin segments in the molecule. The newly added monomer is preferably selected from the above-mentioned ethylene monomers. The structure of this block copolymer is in the past It is impossible for Yizhi to draw sm, a because the polymerization reaction in the conventional method is terminated by reactions such as bonding and disproportionation or compounding. In the method according to the invention, such as It is noted that the nitrooxide portion of the initiator remains at one end of the polymer chain and that such monomers can be reinserted when monomers are introduced. Before the next block is formed, the LW-SMA block preferably has a compound length of at least 5 (more than 10 in Yijia) monomer units (any type of monomer). _ _ However, the method according to the present invention can be carried out in various ways, for example, polymerization methods such as bulk π, solution, or solvent, but the solvent polymerization method is better and better because the solvent system is not reactive. The solvent-based polymerization method means that less than 5% of all the terminal groups of the resulting polymer are composed of a solvent portion. In this solvent polymerization method, the total concentration of monomers can vary over a very wide range and is limited only by the efficiency of the reactor and the solubility of the monomers (and the polymers formed) in the solvent. More specifically, the solubility of the monomers / polymers will depend on the type of solvent 'temperature and the type and ratio of monomers used. Monomer concentrations of less than 0% by volume (% v / v) are generally considered to be non-existent, however, concentrations above 85% v / v usually produce a viscosity / tolerance gate L1. The monomer concentration, 芩 2 0 -.65. / 〇 v / v, based on the total volume of solvent and monomer. Solvents that can be used in the method according to the present invention include, but are not limited to, ethers, for example, dioxane and tetrahydrofuran: ketones ^ For example, acetone, methyl formaldehyde: --- order (please first Read the notes on the back and fill in this page)-Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-12 Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the Invention Substances: g, for example, ethyl acetate and methoxypropyl acetate: aromatic solvents, for example, toluene and dibenzobenzene: products like dimethylformamide and nitropropane: and others mixture. g In the method according to the invention, more additives can be used, for example, the types of radicals that are conventionally used to produce, which include organic peroxides, azo-initiators and UV-initiators: stable free radicals ... And chain transfer agents. When it is used in the method, an accelerator or an additive that catalyzes the decomposition of radical species can be used. In addition, if so required, adjuvants such as dyes, stabilizers, colloids, fillers and the like may be added at the beginning or at the time of polymerization as long as it does not interfere with the polymerization process. Alternatively, & can be added to the polymer (solution) after polymerization. The starter used in the method according to the present invention can be prepared by various conventional methods 'as described in, for example,' j Chem. Soc., 1954, 1920-1924). The reactants and reaction conditions were selected so that at least one of the two carbon-centered free radicals attached to the nitrogen atom would have a functional group during the synthesis by selecting a carbon-centered radical A suitable concentration of one or more of the functional groups of the free radical precursors is very easily achieved. The functional group with a free radical is preferably decomposed by one or more suitable azo, C-C or other initiators (for example, difluorenyl peroxide with a high decarboxylation rate) And get it. Depending on the route of the initiator, it is best to react with only one type of carbon-centered free radical (containing functional groups) with nitric oxide (NO) gas. ‘-, Alternative land’ The compounds according to the present invention can be reacted under the influence of heat or by a nitrosyl compound with a carbon-centered free radical.
尽紙張尺度通用中國國家標準（CNSU^Tri0x297,^T — . ί裝 訂 L· r ' -(請先1讀背面之注意事項再填寫本頁) - - 經濟部中央標準局貝工消费合作社印製 A7 B7 五、發明説明（11 ) 而製成，如由T.柯拉薩（Kolasa),A.契米克（chimiak)和A. 把托瓦斯杞（Kitowski)在 J. Prakt. Chem·, 1975, 3 17, 252 -256中説明的》 本發明將藉由下列之實例而進一步例舉説明。 實驗 除另外説明外，下列實例中使用之化學品皆爲試藥級。 笨乙烯係由貝克（Baker)(貝克P A級）所供應。在使用之 前’藉由鹼性氧化鋁（Ah 〇3)塔的處理而除去笨乙烯的抑 制劑。甲基異丁基酮（MIBK)係由佛路卡（Fluka)，培卡1 克斯（Perkad〇X®)AIBN(2,2，-偶氮雙[.異丁腈])，路西苴爾 (Lucidol®)(75%過氧化二苯醯、25%水）所供應，而所使 用之起始劑係由阿克竹諾貝爾（Akzo Nobel)所供應或依所 提供之文獻中列出的方法合成。 單體成爲聚合物的轉化作用係以習用之方法，藉由使用 氣苯做爲内標準的單體之氣體層析（GC)分析來測定。 聚合物之數目平均分子量（Μη)、重量平均分子量（Mw) 和分散度（D)係以習用之方法，藉由使用tHF做爲duent的 粒子大小凝膠色層分析法來分析。使用聚苯乙烯樣本做爲 校準標準。 … 藉由在正戊烷中的沉澱作用..而將聚合_溶液中分離出 來，然後接著在5 〇。(：之眞空烤壚中乾燥(2 〇 _丨00小時）成恆 重。 ’：·- 聚合物偶合而有300或400 ΜΗ/Η和100 MHz13C NMR的 進一步特徵。 .〆 (請先閱讀背面之注意事項再填寫本頁) 裝. 、-βCommon Chinese National Standards (CNSU ^ Tri0x297, ^ T —. Binding of L · r '-(Please read the precautions on the back first before filling out this page)--Printed by the Central Laboratories of the Ministry of Economic Affairs A7 B7 V. Invention description (11), such as made by T. Kolasa, A. Chimiak and A. Put Kitowski in J. Prakt. Chem., 1975 The invention described in 3, 252-256 will be further exemplified by the following examples. Unless otherwise stated in the experiments, the chemicals used in the following examples are all reagent grades. Baker) (Baker PA grade). Before use, the inhibitor of stupid ethylene was removed by treatment with a basic alumina (Ah 03) column. Methyl isobutyl ketone (MIBK) was manufactured by Fluka (Fluka), Perkadox® AIBN (2,2, -Azobis [.isobutyronitrile]), Lucidol (75% diphenylhydrazone, 25% water), and the starting agent used was synthesized from Akzo Nobel or according to the methods listed in the literature provided. The monomers became poly The conversion of the compounds was measured by conventional methods using gas chromatography (GC) analysis using gaseous benzene as the internal standard monomer. Number average molecular weight of polymer (Mη), weight average molecular weight (Mw) And dispersion (D) are conventionally analyzed by particle size gel chromatography using tHF as the duent. Polystyrene samples are used as the calibration standard.… Precipitation .. The polymerization solution is separated, and then dried in a 50% (: empty roasting) (200 hours) to a constant weight. ':--Polymer coupling with 300 or Further characteristics of 400 ΜΗ / Η and 100 MHz 13C NMR ... 〆 (Please read the notes on the back before filling this page)
A7 B7 經濟部中央標準局貝工消費合作社印犁 五、發明説明（12 ) 未曾嚐試使產量，最佳·化。 實例1 _ · 起始劑之製備 . . Ν,Ν,Ο -二- (1-氰基-卜甲基乙基）羥胺（（ibn)3n〇)A7 B7 Yin Peng, Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 5. Description of Invention (12) No attempt was made to optimize output. Example 1-Preparation of Starter..., ..N, N, O-bis- (1-cyano-methylethyl) hydroxylamine ((ibn) 3n〇)
\ CN\ CN
χΝ'° V'CNχΝ '° V'CN
CN ·- . 於1500毫升曱苯中的培卡苴克斯（Perkad〇x) AJBNG5 2.7 克’ 0.93莫耳）溶液被攪拌、以氮氣沖洗和加熱至7 6。〇。 一氧化氮流（5升/小時）穿過溶液，並顯現出深綠/藍色色 澤。繼續以7 6 °C加熱2小時、以8 2 °C加熱1小時、以8 8 T： 加熱3 0分鐘、以9 4。(：加熱1 5分鐘以及最後的以！丨9 °C加熱 1 5分鐘以冤成AIBN的芫全分解。藉由以氮氣沖洗反應混 合物而將殘留的一氧化氮除去，此時色澤變成黃色。以旋 轉路發器除去落劑，同時蒸氣蒸館因而產生之溶液以除去 曰1J產物·四甲基丁一腈。接著，將水/產物混合物留置冷卻 至室溫，並使產物沉澱。藉由過濾作用除去該固體、使其 溶解在二氣甲烷中’然後接著以硫酸鎂良岸。溶劑之蒸發 作用給予84·3克（5 8 %)的黃色固體，即（I b N) 3 Ν Ο。 實例2 - 4 : 聚合作用係在250毫升之三頸燒瓶中施行，該燒瓶備有氯 氣入口、回流冷凝器、可經其加入反應杨的，入口以及磁力 -15- 本纸張尺度適用中國國家標準（CNS ) A4規格（2丨0)<297公釐） - . 裝 訂------/A ' * -(請先閲讀背面之注意事項再填寫本萸> - A7 B7 五、發明説明（13 ) 攪拌器。除非另有説明，否則在整個聚合作用期間，氬氣 來回沖洗反應混合物，6 0毫升曱基異丁基酮溶劑（MIBK) 和氬氣一起沖洗並加熱至聚合溫度1 14 °C。當達到該溫度 時，在20毫升MIBK中的9.5克苯乙晞、9.0克順丁烯二酸 酐和不同量的實例1之起始劑的溶液在2個小時内以約0.33 毫升/分鐘的速率加入。之後，使混合物保持在聚合溫度 另外4個小時。獲得下列之結果。 實例 單體上起始劑 之莫耳％ Mth (道耳頓） Mn (道耳頓） 苯乙烯轉化率 (%) 2 4 2760 3200 >99 6.7 1740 2000 >99 4 6.7 1740 2200 98 對實例3而言，於聚合作用期間獲得下列結果。 (請先閲讀背面之注意事項再填寫本！) .裝 經濟部中央橾準局員工消費合作社印裝 時間(小時） 苯乙烯轉化率(％) Μη(道耳頓） 2 34 1750 3 87 1950 4 96 2050 5 99 •一^ 2075 6 >99 . Λ 2050 所得之聚合物係無臭的。 實例5和6 ,4 -16- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X：297公釐） 40033^ A7 B7 •五、發明説明（14 ) 下列之步骤係和實例2-4之説明相同，在2〇毫升ΜΙΒΚ$ 的12.4克苯乙烯、5.8克順丁烯二酸酐和所指示之量的起始 劑之溶液摻入。獲得下列結果α 實例 單體上起始劑 之莫耳％ Mth (道耳頓） (道耳頓） 笨乙埽轉化率 (%) 3.2 2784 3000 \/{JJ 80 6 3.2 2944 3200 85 單質聚苯乙烯的調配物未發現，同時聚合物爲無臭的 f 例 7 - · 使用實例2 - 4所説明之设備，.4 〇毫升μ IB K、2 5 · 8克順丁 烯一 §父酐、2 7. 1克苯乙埽和2 _ 54克實例1之起始劑的混合物 被氬氣沖洗、加熱至1 14 °C並在該溫度下反應6個小時，獲 得下列之結果。 實例 單體上起始劑 之莫耳％ Mth (道耳頓） Mn (道耳頓） 苯乙烯轉化率 (%) _ 7 2 . 5284 6000 >99 n m I - D m m n - n m IK i— n I 丁 • · /*. fv 、-* • r - (請先閱讀背面之注意事項再填寫本頁) · 鯉濟部中央榡準局員工消費合作社印掣 所得之聚合物爲無臭的l . 實例8 重覆實例5。但是，在4小時聚合作用·結束時，使溫度保 持在1 14 C並在2個小時内，將53 4 ^丙烯酸丁酯加至反應 '昆合物内。在使用之前，曾以和純化苯乙烯單體相同的方 法純化丙烯酸丁酯。將丙烯酸丁酯加入之/後，混合物在 尺 張 紙 本 -17- 变適用中國國家標準（CNS>A4胁（2數29^^· 經濟部中央標準局貝工消費合作社印^ 400337 A7 _______B7 五、發明説明（15 ) ^ 114 °C下進一步反應4個小時。 頃發現，雖然以使用折射率和紫外線偵測器的粒子大小 凝膠色層分析法分析顯示僅有單一種聚合物形成，但是有 -50%丙烯酸丁酯聚合了。NMR分析顯示其包括聚丙烯酸丁 酯單元和苯乙烯順丁烯二酸酐單元二者。CN ·-. A solution of Perkadox AJBNG5 2.7 g '0.93 mole) in 1500 ml of toluene was stirred, flushed with nitrogen and heated to 76. 〇. A stream of nitric oxide (5 liters / hour) passed through the solution and showed a dark green / blue color. Heating was continued at 7 6 ° C for 2 hours, at 8 2 ° C for 1 hour, at 8 8 T: for 30 minutes, and at 94. (: Heating for 15 minutes and finally with! 丨 9 ° C heating for 15 minutes to completely decompose the AIBN. The residual nitric oxide was removed by flushing the reaction mixture with nitrogen, and the color became yellow at this time. The rotary agent is used to remove the falling agent, and the solution produced by the steamer is removed to remove the 1J product · tetramethylbutyronitrile. Then, the water / product mixture is left to cool to room temperature and the product is precipitated. The solid was removed by filtration, dissolved in methane methane 'and then followed by a good magnesium sulfate. The evaporation of the solvent gave 84.3 g (58%) of a yellow solid, (I b N) 3 Ν Ο Example 2-4: Polymerization was carried out in a 250 ml three-necked flask equipped with a chlorine gas inlet, a reflux condenser, a reactor that can be added through it, an inlet, and a magnetic force-15-This paper is for China National Standard (CNS) A4 Specification (2 丨 0) < 297 mm)-. Binding -------- / A '*-(Please read the notes on the back before filling in this card >-A7 B7 5 Description of the invention (13) Stirrer. Unless otherwise stated, polymerization throughout During use, the reaction mixture was flushed back and forth with argon, 60 ml of fluorenyl isobutyl ketone solvent (MIBK) was flushed with argon and heated to a polymerization temperature of 1 14 ° C. When this temperature was reached, the temperature in 20 ml of MIBK A solution of 9.5 g of phenethylhydrazone, 9.0 g of maleic anhydride and different amounts of the initiator of Example 1 was added at a rate of about 0.33 ml / min over 2 hours. After that, the mixture was kept at the polymerization temperature for another 4 Hours. The following results were obtained. Molar% of the initiator on the example monomer Mth (Dallton) Mn (Dallton) Styrene conversion (%) 2 4 2760 3200 > 99 6.7 1740 2000 > 99 4 6.7 1740 2200 98 For Example 3, the following results were obtained during the polymerization (please read the precautions on the back before filling in this!). Loading time (hours) for the staff consumer cooperatives of the Central Procurement Bureau of the Ministry of Economic Affairs Styrene conversion (%) Mn (Dawlton) 2 34 1750 3 87 1950 4 96 2050 5 99 • ^ 2075 6 > 99. Λ 2050 The polymer obtained was odorless. Examples 5 and 6, 4- 16- This paper size applies to China National Standard (CNS) A4 (210X: 297 mm) 40033 ^ A7 B7 • V. Description of the invention (14) The following steps are the same as those described in Example 2-4. In 20 ml of MIBK $, 12.4 g of styrene and 5.8 g of butadiene di A solution of the anhydride and the indicated amount of the initiator is incorporated. The following results were obtained: α Moore% of the initiator on the example monomer Mth (Dallton) (Dallton) Conversion of benzamidine (%) 3.2 2784 3000 \ / {JJ 80 6 3.2 2944 3200 85 Elementary polybenzene No ethylene compound was found, and the polymer was odorless. Example 7-· Using the equipment described in Examples 2-4, 4.0 ml μ IB K, 2 5 · 8 g of maleic anhydride, § parent anhydride, 2 7. A mixture of 1 g of phenethylhydrazone and 2 to 54 g of the starter of Example 1 was flushed with argon, heated to 1 14 ° C and reacted at this temperature for 6 hours. The following results were obtained. Molar% of the initiator on the example monomer Mth (Dallton) Mn (Dallton) Styrene conversion (%) _ 7 2. 5284 6000 > 99 nm I-D mmn-nm IK i— n I Ding • · / *. Fv,-* • r-(Please read the precautions on the back before filling out this page) · The polymer obtained from the stamp printed by the Consumer Cooperatives of the Central Government Bureau of the Ministry of Lijin is odorless l. Example 8 Repeat Example 5. However, at the end of the polymerization for 4 hours, the temperature was maintained at 1 14 C and within 5 hours, 53 4 ^ butyl acrylate was added to the reaction mixture. Prior to use, butyl acrylate was purified in the same manner as for styrene monomer. After the butyl acrylate was added, the mixture was changed to a Chinese paper standard on a ruled paper-17- Applicable to the Chinese National Standard (CNS > A4 threat (2 number 29 ^^ · Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs ^ 400337 A7 _______B7 5 Explanation of the invention (15) ^ Further reaction at 114 ° C for 4 hours. It was found that although analysis by particle size gel chromatography using a refractive index and ultraviolet detector showed that only a single polymer was formed, but -50% butyl acrylate polymerized. NMR analysis showed that it included both polybutyl acrylate units and styrene maleic anhydride units.
該嵌段共聚物被認爲非常適於做爲偶合劑。 i匕較實肩A釦R 重覆實例5，但使用3.4%過氧化二笨醯抑或AIBN取代 6.7%起始劑。可是，在這二個情形中，數目平均分子量非 常高於10000的不可溶聚合物快速地形成。This block copolymer is considered very suitable as a coupling agent. The dagger repeats Example 5 more than the solid shoulder A buckle R, but replaces 6.7% of the initiator with 3.4% dibenzyl peroxide or AIBN. However, in both cases, an insoluble polymer having a number average molecular weight exceeding 10,000 was formed rapidly.
比較實例C 除了使用0_ 5莫耳％ AIBN和5莫耳％十二烷硫醇混合（以單 體之總量爲基準）以外，重覆實例2。 由於十一燒硫醇在該聚合作用系統内的鏈轉移活動參數 係未知的，所以若不進一步實驗，將不可能預測因而產生 之聚合物的分子量會是多少。使用該指示，大量的鏈轉移 劑和偶氮起始劑二者被期望可產生非常低分子量的S MA。 但是’當超過99% w/w笨乙烯被聚合時，因而產生之聚合 物的數目平均分子量爲350〇_ ’其較所期望的要高許多。另 外，所得之聚合物有不想要的討厭味道。> . ~ 18 - 本紙張尺度適财目目家標準（CNS ) A4· ( 210X297公楚） - I— - HI I - I - I -I - - -- -'士欠 I- - - I • · i 豸 T® ♦ · * (請先閱讀背面之注意事項再填寫本頁) ·Comparative Example C Example 2 was repeated except that 0-5 mole% AIBN and 5 mole% dodecanethiol were mixed (based on the total amount of monomers). Since the chain transfer activity parameters of undecylmercaptan in this polymerization system are unknown, it is impossible to predict the molecular weight of the resulting polymer without further experiments. Using this indicator, both large amounts of chain transfer agents and azo initiators are expected to produce very low molecular weight SMA. However, when more than 99% w / w stupid ethylene is polymerized, the number of polymers produced thereby has an average molecular weight of 3,500 ', which is much higher than expected. In addition, the obtained polymer had an unpleasant unpleasant taste. >. ~ 18-Standards for this paper (CNS) A4 · (210X297 Gongchu)-I—-HI I-I-I -I----'士 欠 I---I • · i 豸 T® ♦ · * (Please read the notes on the back before filling this page) ·