TW404955B - Water-soluble cross-linkable copolymer - Google Patents

Water-soluble cross-linkable copolymer Download PDF

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Publication number
TW404955B
TW404955B TW086102323A TW86102323A TW404955B TW 404955 B TW404955 B TW 404955B TW 086102323 A TW086102323 A TW 086102323A TW 86102323 A TW86102323 A TW 86102323A TW 404955 B TW404955 B TW 404955B
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Taiwan
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copolymer
water
vinyl
acid
weight
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TW086102323A
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English (en)
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Kohlhammer Dr Klaus
Koegler Dr Gerhard
Peter Dr Ball
Monika Schwemmer
Walter Dobler
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Wacker Chemie Gmbh
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    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
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    • C08F212/02Monomers containing only one unsaturated aliphatic radical
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Description

404955 A7 B7 五、發明説明(1 ) 本發明相蘭於若干水溶性可交聯共聚物,其製備方法 及用途。 具有離子基之水溶性聚合物(所諝之聚電解質)業經公 開甚久。該等物質像聚合物,在該等聚合物中,羧酸鹽基 或磺酸鹽基等離子基换由化學鍵與聚合物之主鍵牢固地鍵 結在一起。因此通常會形成良好之水溶性及極為待殊之流 變學性能、水性介質中之高黏度。 該等聚電解質傜由含有離子基之水溶性、乙烯型不飽 和化合物,藉自由基聚合法製得。其實例為:丙烯酸、N-羥甲基丙烯醯胺、丙烯醯胺基-2-甲基丙磺酸(AMPS)及苯 乙烯磺酸。由此法可製得分子量極高之聚合物,該等聚合 物之水溶液,黏度非常高。 歐洲專利EP-B 94898(美國專利US-A 4736005)中曾述 及製備若干種分子量極高(分子量2 1,000,0 00 )之三元共 聚物,該等三元共聚物内包括:30至95¾重量比之二甲基丙 烯醯胺(DMA)、0.1至10¾重量比之N-羥甲基丙烯醯胺(NMA) 及4至50¾重量比之丙烯醯胺基甲基丙磺酸鹽(AMPS),且在 製造原油時可作流變學添加劑。 德國專利DE-A 2618898(美國專利US-A 3965032)僳相 關於若干膠體分散液,該等膠體分散液包括一種水溶性或 水分散性共聚物聚電解質,該聚電解質中含有非離子型疏 水單元(例如:甲基丙烯酸甲基酯)及離子型親水單元(例如 :丙烯醯胺基甲基丙磺酸鹽),且其製備工作像在一可與水 混合之溶劑中以溶液聚合法實施。具體言之,所述及之共 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) K . I ^^^1 i ^^^1 T~^ 1 丨穿-5 - - (請先閱讀背面之注意事項再填寫本頁) 經濟部中央標準局舅工消費合作社印製 404955 A7 B7 五、發明説明(2 ) 聚物,其包括之超量疏水成分為2: 1至6: 1。 歐洲專利EP-A 629650(美國專利US-A 5278222)及歐 洲專利EP-A 67 1 435曾述及若干水溶性及非水溶性、具有 疏水單體單元之聚合物,其中15至80¾重量比或30至50«重 量比之單體含有磺酸鹽基,像用作噴乾水性聚合物分散液 時之噴灑助劑。 含有高量可交聯水溶性單體單元[例如:羥甲基丙 烯醯胺(NMA)]之水溶性聚合物,原則上以呈水溶液形態者 為佳,以便用作塗料組成物之結合劑或黏合劑。另一可能 之用途偽作為水性聚合物分散液之分散剤。NMA含量高之 水性聚合物,其分子量較高,因而其水性溶液之黏度亦將 高。水溶性丙烯酸化合物(例如:丙烯酸或N -羥甲基丙烯醒 胺)通常像用作交聯劑,實際上具有極高之聚合度,由於 可形成較高之黏度,駸重影鬱其廣泛用途。以水溶性單體 為主之聚罨解質之另一缺點是:該等聚電解質經常與一聚 合物分散液不相容而且聚電解質水性溶液容易自聚合物分 散液中分離出來形成一漿液。 所以本發明之目標僳提供若干水溶性可交聯聚電解質 ,即使水溶性共單體之含量甚高,其分子量仍相對的甚低 ,而且用作水性聚合物分散液之添加劑時,對分散相之親 和力甚高並具有較佳之表面活化性能。 驚奇的是,經發現藉將N-羥甲基丙烯醛胺與含有磺酸 基或磺酸鹽基之丙烯酸化合物施以共聚合作用,可獲致非 常低之分子量。更驚奇的是,亦曾發現藉助於僅少量疏水 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ^1. — ..... --'i —^1 I - - - —I -I -----1 n - - - —II - !| - - (請先閱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製 經濟部中央標準局員工消費合作社印製 A7 R7 404955- 五、發明説明(3 ) 共單體之共聚合作用可獲致非常低之表面張力及較低之黏 度。 本發明相關於分子量S500,000之水溶性可交聯共聚物 ,其中包括: a) 20至953;重量比之單體單元,該等單體單元含有磺酸 基或磺酸鹽基, b) 4至80¾重量比之單體單元,該等單體單元含有N -羥甲 基或烷氣基甲基及 c) 0. 1至203!重量比之疏水性單體單元,該等單體單元像 選自一個族群,該族群包括:非水溶性、乙烯型不飽 和化合物及引發劑基或調節剤分子之疏水端基, 其中!S重量比含量係以共聚物總重童為基準,而且(假若適 當)可能有高達50¾重量比〔以單體單元a)之重量含量為基 準〕含有磺酸/磺酸鹽之單體單元由含有羧基之單體單元 d) 或含有醛胺基之單體單元e)所取代。 較為合意之水溶性可交聯共聚物其分子量S 500,000 者,其中包括: a) 30至873!重量比之單體單元,該等單體單元含有磺酸 基或磺酸鹽基, b) 12至60¾重量比之單體單元,該等單體單元含有N-羥 甲基或N-烷氣基甲基及 c) 1至10¾重量比之疏水性單醴單元,該等單體單元傜選 自一値族群,該族群包括:非水溶性、乙烯型不飽和 化合物及引發劑基或調節劑分子之疏水端基, 本纸張尺度適用中國國家標準(CNS ) A4規格(210 X 297公釐) ^n- ^n> m .^1^1 If^i ^^1 1^1 ^ij * -9 (請先閱讀背面之注意事項再填寫本頁) A7 B7 --404955— 五、發明説明(4 ) 其中!I:重量比含量愾以共聚物總重量為基準。 最合意之水溶性可交聯共聚物其分子量S500,000者, 其中包括: a) 70至87!«重量比之單體單元,該等單體單元含有磺酸 基或磺酸鹽基, b) 12至25%重量比之單體單元,該等單體單元含有N-羥 甲基或N-烷氣基甲基及 c) 1至5!«重量比之疏水性單體單元,該等單體單元係選 自一傾族群,該族群包括:非水溶性、乙烯型不飽和 化合物及引發劑基或諝節劑分子之疏水端基, 其中!《重量比含置像以共聚物總重董為基準。 舉例言之,適當之單體單元a)是:若干水溶性、乙烯 型不飽和化合物,該等化合物可藉自由基加以聚合且含有 横酸基或磺酸鹽基-S〇3M,其中M = H或一籬金羼、銨或鹼土 金屬之離子。合意之單體單元是:2_丙烯醯胺基-2-甲基丙 横酸(AMPS)、苯乙烯磺酸、磺基烷基(甲基)丙烯酸鹽、磺 基烷基衣康酸鹽,最好在每個案例中具有一(^至(:6-烷基、 及乙烯基磺酸及其銨鹽、鹹金羼鹽或鹸土金屬鹽。最合意 之單體單元是:2-丙烯醯胺基-2-甲基丙磺酸(AMPS)、苯乙 嫌磺酸、磺基丙基丙烯酸鹽、磺基丙基衣康酸鹽及乙烯基 磺酸及其銨、鈉、鉀及鈣之鹽類。 舉例言之,適當之單體單元b)是:若干水溶性乙烯型 不飽和化合物,該等化合物可藉自由基加以聚合且含有N-翔甲基(-NH-CH20H)或其乙醚化之衍生物(-NHCH20R,其中 本纸張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ^^1- —^1- - 8 — - - ^^1 n^— ^^1 ------ . . I^i - - (請先閱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策 A7 A7 經濟部中央標準局員工消費合作社印製 B7 五、發明説明(5 ) -烷基)。合意之單體單元是:N-羥甲基丙烯醯胺 (NMA), N-羥甲基甲基丙烯醯胺(HMMA) , N-(異丁氧甲基) 丙烯醏胺(IBMA)、N-(異丁氣甲基)甲基丙烯醯胺及H-(正-丁氧甲基)丙烯醯胺(NBMA)。最合意之單體單元是:N-羥甲 基丙烯醯胺及N-(異丁氣甲基)-丙烯醯胺。 適當之單體單元c)是:乙烯型不飽和化合物、該等化 合物可藉自由基加以(共)聚合,在23它溫度下水中之溶解 度低於2¾重量比且含有引發劑基或調節劑分子(在每値案 例中超過8傾磺原子)之疏水端基。合意之單體單元是:具 有3锢以上碩原子之丙烯酸或甲基丙烯酸之酯類,如:甲 基丙烯酸甲基酯,乙烯基芳香烴類,如:苯乙烯或乙烯基 甲苯,烯類,如:乙烯或丙烯,乙烯基鹵化物,如:氛乙 烯、及具有2値以上硪原子之脂肪羧酸之乙烯基酯。合意 之調節劑分子端基是十二烷基硫醇之十二烷基。最合意之 單體單元是:甲基丙烯酸甲基酯、苯乙烯、丙酸乙烯基酯 、乙酸異丙烯基酯(乙酸1-甲基乙烯基酯)、琥珀酸乙烯基 酯及具有5至10値碩原子之α -分枝型單羧酸之乙烯基酯, 如:¥6〇¥391?或76〇从3101?。 含有羧基之單體d)較為適當者是:若干水溶性乙烯型 不飽和化合物,該等化合物可藉自由基加以聚合且含有羧 基-C00M,其中M = Η或鹼金屬、銨或鹼土金羼離子。合意 之單體是:丙烯酸、甲基丙烯酸、巴豆酸及衣康酸。含有 醯胺基之單體e)較為適當者是:若干水溶性、乙烯型不飽 和化合物,該等化合物可藉自由基加以聚合且含有醯胺基 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) t^n m In n m n^— • -1° - - (請先閱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製 A7 404955_51 五、發明説明(6 ) -CON H2。丙烯醯胺及甲基丙烯醯胺較為合意,尤以丙烯醯 胺最為合意。 一般言之,此處所諝之水溶性像指在23t溫度下水中 之溶解度至少為10¾重量比。該分子量係平均重量,偽用 凝膠滲透法(GPC)對照苯乙烯-磺酸鈉之標準而測定者。 本發明共聚物之製備,最好在401至80Ό之反應溫度 下於水溶液中用自由基聚合法實施。該聚合作用之實施方 式有三:⑴首先將全部或個別反應混合物之組成分引進反 應器内,©首先引進部分成分,再添加反應混合物之全部 組成分或個別組成分,(3)計置加入法,無需引進初始混合 物。 引發作用之實施僳藉助於可形成自由基之常用水溶性 品劑,其使用量以0.01至3.Οϋί重量比為佳(以單體之總重 量為基準)。該等水溶性品劑之實例是:過硫酸銨及鉀、 過氧化氫及過氣二磷酸鉀、鈉及銨。假若適當,所述自由 基引發劑亦可用習知之方式與0.01至1.0¾重量比(以單體 之總重量為基準)之還原劑加以結合,在此情況下,聚合 作用則可能在較低之溫度下實施。舉例言之,次硫酸甲経 之絵金屬鹽及抗壞血酸均適當。若採用氣化還原引發作用 ,在聚合作用進行期間,氣化邇原催化劑之一種或兩種成 分最好用計量方式加入。 聚合作用之預期酸齡值範圍(通常酸齡值22.5)可依 照習知方式用鹽基或鹼金屬磷酸鹽或鹸金屬碩酸鹽建立之 。為達成預期之分子量,於實施聚合作用期間,可添加常 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) I- n I I I I n n*民 丁 • 'T - - (請先閱讀背面之注意事項再填寫本頁) A7 B7 404955 五、發明説明(7 ) 用之調節劑,例如:硫醇類、醛類及氣烴類。 在一特別合意之具體實施例中,偽將成分a)、b)、c) 及(假若適當)d)及e)之混合物之一部分首先加入反應器内 形成一水溶液,之後再將該初始混合物加熱至反應溫度。 俟達到聚合作用溫度時,再將自由基引發劑及共單體混合 物之其餘部分徐徐計量加入。計置添加作用完成時,將該 批反應物加熱至851C至95它,以完成聚合作用。 在一最合意之具體實施例中,至少一部分含有磺酸鹽 基之共單體a)(通常為5至60S!重童比,以共單體a)之總重 量為基準)及一部分羥甲基-官能共單體b)(通常為5至 60%重量比,以共單體a)之總重量為基準)首先加入反應器 内形成一水溶液,再將共單體a)及b)之其餘部分計量加入。 該等共聚物在使用時最好呈水溶液形態。視用途而異 ,固體含量最好是15至25¾重量比。該等共聚物溶液適宜 用作纺雜界、造紙界及建築界塗料組成物之結合劑或流變 學輔助劑及用作紡織界、造紙界及建築界之黏合劑。舉例 言之,當共聚物水溶液用作不織布之浸漬劑時,替發現其 對溶劑之抗力特佳且潤濕強度甚高。 另一合意之應用場合你使用該等共聚物溶液於毛毯或 不織布等紡纗品之防靜電處理。為達成此目的,可用水溶 液將該等纺織品加以浸漬。另一可能之防靜電處理包括將 共聚物水溶液與結合劑分散液加以混合作為紡纗品黏合之 用。 基於共聚物水溶液之黏度(對聚電解質而言,該黏度 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) —1 I - - m m ^^1 I - ^^1 -- -I—I , 'T t J (請先閱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製 404955 ^丨丨l| ,海正 五、發明説明(8 ) 1年 卜\ η 補心 經消部中央榡準局負工消費合作社印製 特別的低)及由疏水軍元所誘導出之更多表面活化性旌· 本發明之共聚物亦更加特別瘇宜於安定聚合物水性分散液 或聚合物水性乳化液。 K精於此項技術者罾知之方式將乙烯型不飽和單體加 以自由基聚合作用,能使聚合物水性乳化液及聚合物水性 分敗液可以使用。在聚合作用中可以使用之若干單體(單 獨使用或以混合物方式使用)之實例是:飽和c2至c1()-羧 酸之乙烯基醋.如:乙酸乙烯基_、月桂酸乙烯基_及維 耳塞提酸乙烯基_ ;甲基丙烯酸及丙烯酸與脂族(^至(:8-酵類,如:甲基丙烯酸甲酯、丙烯酸乙酶、丙烯酸丁_及 丙烯酸乙基己基_ ;烯類,如••乙烯及丙烯;乙烯基芳香 烴,如:苯乙烯;及乙烯基鹵化物,如:氣乙烯。 本發明之共聚物可首先引進,或在聚合作用之前或期 間,K其水溶液之形態作為一保謹膠暖計量加入;通常使 用量為1至15;!:重悬比(K軍應之最為基準另一種方式是 :在聚合作用業已终止之後,該等共聚物之水溶液亦可依 照上述之使用量加入聚合物乳化液或聚合物分敗液內β另 一用途是:在聚合物分敗液實施噴乾邊程中,使用本發明 共聚物之水溶液作為噴獾輔助劑。 利用下列諸實驗例可對本發明作進一步之說明。 比較例1 : 約16Χ濃度之AMPS-NMA聚合物溶液之製備: 單髓計量液之製備:首先將468公充之水引進一癯當之 計量器内,並依序將下列物霣溶解在水內:83.1公克瀝度 -10 - 本紙張尺度遶川中闽ft!家橾呤(CNS ) Λ4^ ( 21〇X297/>« ) (請先閲讀背面之注意事項再填寫本頁)
,1T 經濟部中央標準局員工消費合作社印聚 404955 ^ 五、發明説明(9 ) 255K之NaOH溶液、0.8 6 6公克氫硫基丙酸(MPA)、159公克之 2-丙烯醯胺基-2 -甲基丙磺酸(AMPS)及106公克濃度45S;之N -羥甲基丙烯睡胺(HMA)水溶液。 於一附有葉式攪拌器、回流冷凝器及適當計量裝置之 3公升實驗室反應器内,首先依序引進下列諸物質:1.24 公斤去離子水、54.4公克鸛度25¾之NaOH溶液、0.8 66公克 MPA、114公克AMPS及55.4公克濃度45¾之NMA水溶液。將初 始混合物加以攪拌並加熱至80Ό。將2.2S;濃度之過硫酸銨 水溶液(APS)計量加入時聚合作用開始,該計Μ添加工作 歴時3小時。APS計量添加工作開始10分鐘之後,將上述單 體計量液計量加入,歷時2小時,之後,使聚合作用在90 Ό溫度下達到完成。冷卻後,用NaOH將該溶液之酸驗值調 整至7。 如此製得之澄清溶液之固體含量為15. U,酸篇值為7 ,黏度為220毫帕斯卡•秒(布魯克費爾德,20轉/分鐘)及 平均分子量為531,000(GPC;對照聚苯乙烯磺酸納之標準) ,5¾濃度水溶液之表面張力為67.5毫牛頓/公尺。 比較例2 : 約16¾濃度之AMPS-NMA聚合物溶液之製備: 單體計量液之製備:首先將468公克之水引進一適當之 計量器内,並依序將下列物質溶解在水内:83.2公克濃度 25¾之NaOH溶液、0.866公克氫硫基丙酸(MPA)、184公克之 2 -丙烯醯胺基-2-甲基丙磺酸(AMPS)及70.9公克濃度45X之 N-羥甲基丙烯醯胺(NMA)水溶液。 -11 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) τι- n^f In —In ......... I- - .^- - - 1 n nn ^^^1 一OJ (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费合作社印製 A7 404^^^_-____ 五、發明説明(10 ) 於一附有葉式携拌器、回流冷凝器及適當計量裝5之 3公升實驗室反應器内,首先依序引進下列諸物質:1. 27 公斤去離子水、55.5公克濃度25¾之NaOH溶液、0.866公克 氫硫基丙酸(MPA)、114公克固體2-丙烯醯胺基-2-甲基丙 磺酸(AMPS)及37公克45J;濃度之N-羥甲基丙烯醯胺(NMA)水 溶液。將該溶液加以攪拌並加熱至80t:。將2.2S;濃度之過 硫酸銨水溶液(APS)計量加入時聚合作用開始,計量添加 工作歴時3小時。APS計量添加工作開始1〇分鐘之後,將上 述單體計量液計量加入,歷時2小時。之後,使聚合作用 在901C溫度下達到完成。冷卻後,用NaOH將該溶液之酸_ 值讕整至7。 如此製得之澄清溶液之固體含量為15.8«,酸鹹值為7 ,黏度為82毫帕斯卡♦秒(布魯克費爾德,20轉/分鐘)及 平均分子量為164,000(GPC;對照聚苯乙烯磺酸納之標準) ,5X濃度水溶液之表面張力為65.1毫牛頓/公尺。 實驗例1 : 約16S!濃度之AMPS-NMA-STY聚合物溶液之製備: ' 單艚計量液之製備:首先將459公克之水引進一適當之 計量器内,並依序將下列物質溶解在水内:81.5公克濃度 25¾之NaOH溶液、0.845公克氣硫基丙酸(MPA)、4.18公克 苯乙烯、180公克之AMPS及69.5公克濃度45S!之NMA溶液。 於一附有葉式掩拌器、回流冷凝器及適當計量裝置之 3公升實驗室反應器内,首先依序引進下列諸物質·· I28 公斤去離子水、54.4公克濃度25!ϋ之NaOH溶液、0.849公克 -12 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部中央標準局—工消費合作社印製 A7 404955_B7___ 五、發明説明(i i ) MPA、 112公克AMPS、36.2公克濃度45¾之HMA溶液及2.62公 克苯乙烯。將該溶液加以攪拌並加熱至8〇υ。將2. 2Χ濃度 之APS水溶液計量加入時聚合作用開始,計量添加工作歴 時3小時。APS計量添加工作開始10分鐘之後,將上述單體 計量液計量加入,歴時2小時。之後,使聚合作用在901C 溫度下逹到完成。冷卻後,用NaOH将該溶液之酸齡值諝整 至7〇 如此製得之澄清溶液之固髏含量為15. 8J«,酸齡值為7 ,黏度為48毫帕斯卡•秒(布魯克費爾德,20轉/分鐘)及 平均分子量為450,000(GPC;對照聚苯乙烯磺酸納之標準) ,5S!濃度水溶液之表面張力為61.6毫牛頓/公尺。 實驗例2 : 用疏水性十二烷端基製備約16S!樓度之AMPS-NMA聚合物溶液 ' 單體計量液之製備:首先將455公克之水引進一適當之 計量器内,並依序將下列物質溶解在水内:80.9公克瀣度 25J!之NaOH溶液、0.843公克MPA、179公克AMPS及68.9公克 濃度45¾之HMA溶液。 調節劑計量液之製備:於一適當計量容器内,將5. 39公克 十二硫醇溶解在48.5公克丙酮中。 於一附有葉式攪拌器、回流冷凝器及適當計量裝置之 3公升實驗室反應器内,首先依序引進下列諸物質:1.21 公斤去離子水、53.9公克濃度25¾之NaOH水溶液、12.1公 克丙酮、0.8 43公克MPA、 111公克AMPS及36.0公克濃度45¾ 之NMA水溶液及1.35公克十二硫醇。將該溶液加以攪拌並 -13 - 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) (請先閲讀背面之注意事項再填寫本頁)
、1T A7 4θ4955---- 五、發明説明(12 ) 加熱至80¾。將2.2¾濃度之APS水溶液計量加入時聚合作 用開始,計量添加工作歴時3小時。A P S計量添加工作開始 10分鐘之後,將上述單體計量液及調節劑計量液計量加入 ,歷時2小時。之後,使聚合作用在90t!溫度下達到完成 。冷卻後,用NaOH將該溶液之酸鹺值調整至7。 如此製得之澄清溶液之固體含量為16.3χ,酸鹼值為7 ,黏度為49.5毫帕斯卡•秒(布魯克費爾德,20轉/分鐘) 及平均分子量為148,000 (GPC;對照聚苯乙烯磺酸鈉之標 準),5S!濃度水溶液之表面張力為63.9毫牛頓/公尺。 實驗例3 : 約16¾濃度之AMPS-NMA-STY聚合物溶液之製備: ‘ 單體計量液之製備:首先將468公克之水引進一適當之 計量器内,並依序將下列物質溶解在水内:83.1公克濃度 25¾之NaOH溶液、0.866公克MPA、8.52公克苯乙烯、173公 克AMPS及70.8公克濃度45¾之NMA溶液。 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) 於一附有葉式攪拌器、回流冷凝器及適當計量裝置之 3公升實驗室反應器内,首先依序引進下列諸物質:1.27 公斤去離子水、55.4公克濃度25¾之NaOH溶液、0.866公克 MPA、111公克AMPS、36.9公克濃度45%之1^&溶液及5.33公 克苯乙烯。將該溶液加以攪拌並加熱至80C。將2.2¾濃度 之APS水溶液計量加入時聚合作用開始,計量添加工作歷 時3小時。APS計量添加工作開始10分鐘之後,將上述單體 計量液計量加入,歷時2小時。之後,使聚合作用在90它 溫度下逹到完成。冷卻後,用NaOH將該溶液之酸齡值調整 -14 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消費合作社印製 A7 --404955-^_ 五、發明説明(13 ) 至7。 如此製得之澄清溶液之固體含量為15.8¾,酸齡值為7 ,黏度為54毫帕斯卡•秒(布魯克費爾德,20轉/分鐘)及 平均分子量為377,00 0 (GPC;對照聚苯乙烯磺酸納之標準) ,5¾濃度水溶液之表面張力為63.7毫牛頓/公尺。 實驗例1至3及比較例1及2内聚合物溶液之表面張 力及黏度詳如表3。表3内之數據清楚地顯示:無疏水基 之聚電解質(比較例1及2)之表面張力及黏度均較含高量 疏水基之聚電解質(實驗例1至3 )者較高。 用途試驗: 用實驗例1内之溶液作為纖維結合劑之試驗: 藉助於一浸軋機,將一黏液短纖維薄纱浸漬於實驗例 1之溶液内,經壓擠之後,於150¾溫度烘乾3分鐘(結合 劑使用量為29.5¾),以此方式浸漬之不織布之強度僳沿橫 向測試。測試依照三種方式進行:⑴乾燥不織布,②水中 儲存1分鐘,(3)異丙醇中儲存1分鐘。為達成此目的,在 每個案例中,三條150公厘長及15公厘寬之不織布帶偽上 下重叠一起來測試。量測之條件是:鉗夾長度為1〇〇公厘, 鉗夾寛度為15公厘,量測速率為100公厘/分鐘。制動力( 亦即量測過程中所逹成之最大張力)記錄作量測值。量測 結果如表1所示。 -15 - 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) ,ιτ A7 4Π4ΡΒΗ_[ 五、發明説明(1 4 ) 表1 乾燥 水中儲存 異丙醇中儲存 制動力[牛頓] 24.7 4.8 23.8 值得驚奇的是:經於異丙醇中儲存後之強度幾乎與乾 燥不織布之強度相當。 用實驗例1内之溶液作為毛毯防靜電處理之試驗: 背面經以30¾濃度之結合劑處理過之針織氈,用0.2¾ 或0.5¾濃度(以結合劑之量為基準)之實驗例1内之溶液噴 灑之,並在150它溫度下烘乾3分鐘。如此處理之毛毯,其 靜電放電半衰期,僳依照德國工業標準DIN VDE 0303第8 節,在不同相對大氣濕度(10!K、303!、50¾)下测得。所用 電壓為10,000伏特,量測溫度為271C。量測結果如表2所 示: 表2 : (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製 大氣濕度 10¾ 30¾ 50¾ 針織氈 >30分鐘 1.5分鐘 9秒 針織氈+0.2¾濃度溶液 >30分鐘 12秒 8秒 針織酕+0.5丨濃度溶液 15分鐘 9秒 1秒 -16 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 404955 五、發明説明(15 ) 本發明之聚合物之防靜電效果導致靜電放電半衰期大 幅縮短。 表3 : 實驗例 單 體成分 a) b) c) 表面張力 黏度 u重量比] [!«重量比] [%重置比] [毫牛頓/公尺] [毫帕斯卡•秒] 比較例1 21.0 NMA 79.0 AMPS -—— 67.5 220.0 比較例2 14.0 NMA 86.0 AMPS --- 66.1 82.0 實驗例1 13.7 NMA 84.4 AMPS 1.9 STY 61.6 48.0 實驗例2 13.7 NMA 84.3 AMPS 2.0 DDM 63.9 49.5 實驗例3 13.5 NMA 82,7 AMPS 3.8 STY 62.9 54.0 經濟部中央標準局員工消費合作社印製 (請先閱讀背面之注意事項再填寫本頁) NMA = N-羥甲基丙烯醯胺;AMPS = 2-丙烯醯胺基-2-甲基丙磺酸 STY =苯乙烯;DDM =十二硫醇 -17 - 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐)

Claims (1)

  1. 404Θ5
    fB8 IC8 “ /nc r? 88-08-30 修正 87-1卜04修正 六、申請專利範圍 1. 一種分子量1,000至500,000間之水溶性可交瞄共聚物 ,其中包括: <請先閱讀背面之注意事項再填寫本頁) a) 30至87¾重量比之單體單元:2-丙烯醯胺基-2-甲基丙 磺酸(AMPS)、苯乙烯磺酸、丙烯酸磺酸基丙基酯、衣 康酸磺酸基丙基酯及乙烯基磺酸K及其銨鹽、納鹽、 鉀鹽及鈣鹽, b) 12至60X重量比之單體單元:N-羥甲基丙烯醛胺及/ 或Ν-(異丁氧甲基)-丙烯豳胺, c) 1至1(U重量比之疏水性單體單元:具有3個以上碳原 子之丙烯酸_或甲基丙烯酸酯,如:甲基丙烯酸甲_ ,乙烯基芳香烴,如:苯乙烯或乙烯基甲苯,烯類, 如:乙烯或丙烯,乙烯基鹵化物,如:氯乙烯,超過 2個碳原子之脂族羧酸之乙烯基酯及引發劑基或調節 劑分子之疏水端基(在每涸案例中具有8個碳原子), 其中χ重量比含量係Κ共聚物總重量為基準。 經濟部智慧財產局員工消費合作社印製 2. 如申請專利範圍第1項之共聚物,其中製備^工作係於 水溶疲中藉自由基聚合法將單體a)、b)、c)加以聚合,反 應溫度為401C至801C,其引發作用係採用可形成自由基之 水溶性品謂,至少一部分含有磺酸鹽基之單體a)〔5至60¾ 重量比,K共單體a)之總重量為基準〕及一部分N-羥甲基-官能共單體b)〔5至60¾重量比,共單體a)之總重量為基 準〕首先引進反應器內成為水溶液,共單體a)及b)之其餘 郤分則計量加入,當溫度到達聚合作用溫度時,自由基引 發劑及共單體混合物之其餘部分則徐徐計量加入,在每個 -18 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) s 404^55 --- 六、申請#利範圍 案例中均係在水溶液中進行,及聚合液之濃度為5至351 3. 如申請專利範圍第1或2項之共聚物,以其水溶液之 形態,係用作坊继界、造紙界及建築界塗料組成物之结合 劑或流變學輔助劑及纺嫌界、造紙界及建築界之黏合劑。 4. 如申請專利範圍第1或2項之共聚物,Κ其水溶液之 形態,係用作坊继品之防靜電處理。 5. 如申請專利範圍第1或2項之共聚物,以其水溶液之 形態,係用作安定聚合物水性分散液或聚合物水性乳化液 之保護膠體。 6. 如申請專利範圍第1或2項之共聚物,係用作噴乾聚 合物分散液期間之噴灑肋劑。 -Μ-------------------訂---------線 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 -19 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 404955 ^丨丨l| ,海正 五、發明説明(8 ) 1年 卜\ η 補心 經消部中央榡準局負工消費合作社印製 特別的低)及由疏水軍元所誘導出之更多表面活化性旌· 本發明之共聚物亦更加特別瘇宜於安定聚合物水性分散液 或聚合物水性乳化液。 K精於此項技術者罾知之方式將乙烯型不飽和單體加 以自由基聚合作用,能使聚合物水性乳化液及聚合物水性 分敗液可以使用。在聚合作用中可以使用之若干單體(單 獨使用或以混合物方式使用)之實例是:飽和c2至c1()-羧 酸之乙烯基醋.如:乙酸乙烯基_、月桂酸乙烯基_及維 耳塞提酸乙烯基_ ;甲基丙烯酸及丙烯酸與脂族(^至(:8-酵類,如:甲基丙烯酸甲酯、丙烯酸乙酶、丙烯酸丁_及 丙烯酸乙基己基_ ;烯類,如••乙烯及丙烯;乙烯基芳香 烴,如:苯乙烯;及乙烯基鹵化物,如:氣乙烯。 本發明之共聚物可首先引進,或在聚合作用之前或期 間,K其水溶液之形態作為一保謹膠暖計量加入;通常使 用量為1至15;!:重悬比(K軍應之最為基準另一種方式是 :在聚合作用業已终止之後,該等共聚物之水溶液亦可依 照上述之使用量加入聚合物乳化液或聚合物分敗液內β另 一用途是:在聚合物分敗液實施噴乾邊程中,使用本發明 共聚物之水溶液作為噴獾輔助劑。 利用下列諸實驗例可對本發明作進一步之說明。 比較例1 : 約16Χ濃度之AMPS-NMA聚合物溶液之製備: 單髓計量液之製備:首先將468公充之水引進一癯當之 計量器内,並依序將下列物霣溶解在水內:83.1公克瀝度 -10 - 本紙張尺度遶川中闽ft!家橾呤(CNS ) Λ4^ ( 21〇X297/>« ) (請先閲讀背面之注意事項再填寫本頁) ,1T 404Θ5
    fB8 IC8 “ /nc r? 88-08-30 修正 87-1卜04修正 六、申請專利範圍 1. 一種分子量1,000至500,000間之水溶性可交瞄共聚物 ,其中包括: <請先閱讀背面之注意事項再填寫本頁) a) 30至87¾重量比之單體單元:2-丙烯醯胺基-2-甲基丙 磺酸(AMPS)、苯乙烯磺酸、丙烯酸磺酸基丙基酯、衣 康酸磺酸基丙基酯及乙烯基磺酸K及其銨鹽、納鹽、 鉀鹽及鈣鹽, b) 12至60X重量比之單體單元:N-羥甲基丙烯醛胺及/ 或Ν-(異丁氧甲基)-丙烯豳胺, c) 1至1(U重量比之疏水性單體單元:具有3個以上碳原 子之丙烯酸_或甲基丙烯酸酯,如:甲基丙烯酸甲_ ,乙烯基芳香烴,如:苯乙烯或乙烯基甲苯,烯類, 如:乙烯或丙烯,乙烯基鹵化物,如:氯乙烯,超過 2個碳原子之脂族羧酸之乙烯基酯及引發劑基或調節 劑分子之疏水端基(在每涸案例中具有8個碳原子), 其中χ重量比含量係Κ共聚物總重量為基準。 經濟部智慧財產局員工消費合作社印製 2. 如申請專利範圍第1項之共聚物,其中製備^工作係於 水溶疲中藉自由基聚合法將單體a)、b)、c)加以聚合,反 應溫度為401C至801C,其引發作用係採用可形成自由基之 水溶性品謂,至少一部分含有磺酸鹽基之單體a)〔5至60¾ 重量比,K共單體a)之總重量為基準〕及一部分N-羥甲基-官能共單體b)〔5至60¾重量比,共單體a)之總重量為基 準〕首先引進反應器內成為水溶液,共單體a)及b)之其餘 郤分則計量加入,當溫度到達聚合作用溫度時,自由基引 發劑及共單體混合物之其餘部分則徐徐計量加入,在每個 -18 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
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