TW406090B - Aqueous dispersions of olefin copolymers - Google Patents
Aqueous dispersions of olefin copolymers Download PDFInfo
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- TW406090B TW406090B TW085106666A TW85106666A TW406090B TW 406090 B TW406090 B TW 406090B TW 085106666 A TW085106666 A TW 085106666A TW 85106666 A TW85106666 A TW 85106666A TW 406090 B TW406090 B TW 406090B
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Description
經濟部中央樣準局負工消費合作社印装 A7--4Θ6 勝 θ----五、發明説明(1 ) 本發明係有關烯烴共聚物之水性分散液。此等分散掖 可於室溫時為膜形成者,且具有優異的物理及機械性質。 聚烯垤之水性分散液爲此項技6所熟知,雖然無一係 由具有分子量40,000M上之聚烯烴衍生出來。例如《美國 專利第3,734,686號案,Douglas等人揭示具有平均分子鼉 範围為7,000至40,000之聚乙烯顆粒之機械穩定水性乳化 液,此分散液被教示可用於處理地毯。 美团專利第3,418,265»索中,McClain教示含有亞撤 大小之乙烯聚合物顆粒之水性膜形成之乙烯聚合物膠乳可 «由於水中分散乙烯聚合物及琢氧乙烷及瓖氧丙烷之水溶 性嵌段共聚物而製備之。並無有鬭具有分子Λ爲27,000M 上之乙烯聚合物之播定分散液之例子之相鼷報告。 先前所述之許多聚烯烴膠乳實際上並非純的聚烯烴* 而係含有棰性基團,諸如,酸成鹵化物。因此等所謂聚烯 垤膠乳之膜形成性質通常會因此等掻性取代基產生不益影 «,因此極欲製備衍生自不含棰性基圔之較高分子量聚乙 烯之膠乳。若此等膠乳於室溫時爲可膜形成者,其更具價 值。 本發明爲一膜形成之人工膠乳,其包含由乙烯及C3-Ci〇a-烯烴所成共聚物之水性分散掖*該烯垤聚合物之特 撤在於,其具有: a>缺乏極性基囿; b>約1.5至約2.5之聚分散指數; c)至少爲6之丨ικ/Ιβ ί 本紙張尺度逋用中國國家揉率(CNS > A4規格(210X297公釐) 經濟部中央梯準局貞工消费合作社印製 A7 B7___ 五、發明説明(2 )ί〇6090 d)與具有相同I*及聚分散指數之線性烯烴聚合物之表 面熔融斷裂開始時之雎界剪切速率相比,其表面熔 融斷裂開始時之臨界剪切速率至少大於50% ; e>至少45,000之重量平均分子量;及 f)約0.85至約0.9 g/cB3之密度。 另一方面*本發明爲膜形成之水性分散液,其包含具 有窄分子量分佈,沿聚合物主幹具有無規共單體單元分佈 及具有至少75之均勻指數之由乙烯及1:3-(:„(1 -烯烴所成 之共聚物。 出人意外地發現膜形成膠乳可由缺乏極性取代基之烯 垤聚合物製備之。 用K製備本發明水性分散液之烯垤聚合物係爲描述於 美囲專利第3,645,992; 5,272.236;及5,278,272號案所述 之烯垤聚合物。描述於美囲専利第3,645,992«案之此類 烯垤聚合物(其後被稱之為Elston烯烴聚合物),其特徵 在於爲一由乙烯及至少一具有4個或更多值磺原子之其它 α-烯烴(例如,卜丁烯,卜己烯、1-辛烷及1-十八烯) 所成共聚物。諸如乙烯-辛烯-丁烯或乙烯-辛烯、丙烯之 均共聚物亦適於製備本發明之水性分散液。Elston烯垤聚 合物之進一步特擞為如’ 992號專利所述之窄的分子量分佈 及至少75之均勻指數。 美囲専利第5,272,236及5,278,272號茱所述烯坯聚合 物(通稱為實質上線性之烯烴聚合物)為乙烯-C3-C»»ct-烯垤共聚备,其特擻在於具有U高熔融揮性;2>高加工性 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
A7 406090 B7 五、發明説明(3〉 經濟部中央橾準局貝工消費合作杜印裝 ;3>低於3.5之聚分散指數;4>沿聚合物主幹,每1000傾 碘原子爲0.01至3値長鐽分板;及5>基本上與聚分散指數 無關之熔«流動指數。’ 236號案專利之烯烴聚合物之進一 步特徼爲具有大於4X 10«逹因/公分*之缠熔融斷裂開始 時之睡界剪切應力;且’272雖案專利之烯烴聚合物之進一 步特撖為與具有相同I*及M«/Mn之線性烯烴聚合物之表面 熔融斷裂開始時之雎界剪切速率相比,其表面熔融斷裂時 之雎界剪切速率至少大於50%。 製備水性分散液之實質線性烯垤聚合物可爲C*-C*〇烯 烴之均聚物(例如,乙烯、丙烯、4-甲基-卜戊烯之均聚 物),或其可爲乙烯及至少一C3-C*ea-烯烴,及/或C2-C2n乙烯不飽和單體及/或C*-C18二烯烴之均共聚物。較 佳單雔包含C*-C1Da -烯烴(特別是乙烯、丙烯、異丁烯 、1_ 丁烯、卜己烯、4-甲基-1-戊烯及卜辛烯 > 。其它較 佳單《包括笨乙烯及1,4-己二烯。 實質上線性烯烴聚合物沿聚合物主幹每1000侮硝原子 具有0.01 (較佳爲0.3)至3 (較佳爲1)值長鏈分枝。此 處所定義之長鏈分枝為長度為至少6齒碩原子之鍵•其長 度無法Μ碩NMR光譜術匾別。此長嫌可與聚合物主幹一樣 長。 實質線性烯垤聚合物之聚分敗指數(即,分子躉分佈 ,或重量平均分子量對數平均分子*之比例(Mu/M„)較佳 為1.5至2.5。實質線性烯烴聚合物之熔«流動指數(即, 11〇/12)至少爲5.63,較佳為至少6,更佳為至少7,且 >1.應私3 並可1⑴發‘』 ⑵如. rn2.説明, 人士 Γ 號tt. '>:(; 3· . j ( 詞之 4_由左 蜥不、; 5.發叫. 本紙張尺度適用中圃國家標準(CNS ) A4规格(210X297公釐) 6 406090 Β7 經濟部中央標準局貝工消費合作社印製 五、發明説明(4 ) 基本上與聚分散指數無两,相對而言,傳統聚烯烴顧示熔 «滾動指數對聚分散指數之依賴性。此性質例示於’ 236號 專利之第2圓。 實質線性烯烴聚合物之裂備係詳細描述於’ 236號專利 案。 揭示於’ 272號專利案之烯垤聚合物之密度較佳爲〇·85 g/c»3(更佳為 0.86 g/c»3> 至 0.90 g/c»3(更佳為 0.88 g/c·3) Ο 用於製備水性分散液之實質線性烯烴聚合物之重董平 均分子量較佳為至少45,000 a«u,更佳爲至少60,000 aBu 。分子量係Μ美國專利第5,278,272¾案,第5檷,第56 行至第6欄第20行所述測量之。烯烴較佳係不含棰性基圃 •如乙酸酯、酯、醚、胺、酵、丙烯酸、用基丙烯酸、鹵 素、請、硝酸、破酸鹽、磷酸鹽成被酵等基園;較佳者無 添加極性基圔之後,改良步班。 實質線性烯烴聚合物之膠乳係於穩定及乳化置之適當 界面话性癲存在中製備之。較佳之界面活性爾係如下化學 式所示乙氧基酵鹽·· X-$-0-(CH2-fl|^R))n*-S〇3_Z+ 其中X為C8-C18之線性或分枝烷基,較佳者爲辛基、壬基 、或十二烷基,更佳者爲辛基或壬基,最佳爲壬基;φ為 苯播基,較佳者為對一苯撐基;4至32,較佳為4至12 ;Z為納、鉀或銨,較佳者為銨。某些較佳之乙氧基烷基 酚之硫酸鹽為可購得者,例如,聚(氧-1,2-乙二基)《 -磺 本紙張尺度適用中國國家樣準(CNS > A4規格(210X297公釐) 406090 A7 B7 五、發明说明(5 > 經濟部中央標準局貝工消费合作社印装 基-<u (壬基苯氧基 > 銨鹽。 實質線性烯烴聚合物之水性分散掖可Μ任何適當技術 裂備之,包括美國専利第3,360,599; 3,503,917:4,123,403 ;及5,037,864號案所述。出人意外發現基質或成型上具有 實質上均勻厚度之薄膜可由前述水性分散液製備之。此膜 進一步特撖為缺乏裂化或孔洞。最後,此膜具有有用之物 理性質,例如,高抗張強度,其可於室溫及缺乏棰性取代 基被成形之。 此臃可以任何適當方法製備之,例如,澆縳、凝固或 嗔爾。若膜Μ凝固製備之,通常較佳者俾使用脂肪睃基界 面活性剤,例如,油酸之納鹽。 下列範例僅係用Μ例示銳明,而非用以限制本發明範 圃0 ISJ^LL-乙烯-1-辛烯膠乳之澆》膜 人造隳乳以ENGAGE™ CL 8002乙烯-辛烯彈性體 氏化學公司之商檷名)裂備之,其具有熔融指數為1,密 度為0_87 g/cn3,Iid/U=7.8,重量平均分子量為129,800 ,及ΜΜ/Μη = 2·2。於2公升之反應容器,添加612 g之於551 g 環己烷內含61 g共聚物之乙烯-辛烯共聚物;3.06 g之 RHODAPEX1" C0 436界面活性劑(Rhone Poulenc之商檷名) ;及288 g之水。此等組份使用Gifford-Woods均質化器Μ 一般為10,000 rp·混合10分鑪使其其乳化。0.2 g之DF37 去發泡劑(由Air Products得之)被添加Μ降低發泡。藉由 801C時之旋轉蒸發自乳化液移除環己烷溶薄(。藉由施Μ — ί 背 之 注 項» 本紙張又度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央橾準局負工消費合作社印装 A7___!Z_五、發明説明(6 ) 部份真空至膠乳並持續加熱,使所形成之人工謬乳濃縮至 30%之固髅》 應乳頼粒大小(其係 MCoulter Counter Multisizer lie分析)爲0.9撖米,且74%之顆粒爲小於1.25撖米。 200 丨之膠乳被倒至清潔玻璃基材上,且以拉伸棒使 其分散均勻。於室温使膠乳Μ室氣乾燥之。膠乳乾燦時, 形成粘結膜。留在基材上之膜於6〇υ熱處理5分鐘以趨除 殘留之水份。然後使其冷卻至室租。所形成之膜具有1600 psi之抗張強度,100%之270棋置,及1270%之百分延長 率。 範例2-乙烯-1-辛烯謬乳之澆縳膜 人工膠乳以範例1所述由乙烯-辛烷共聚物裂備之, 該共聚物具有熔融指數為11,密度爲0.887 g/c·3,11〇/ h爲7.8,重It平均分子量爲60,000 ,且乙烯/辛烯比例 為2.1:1,且係依’272號專利茱所教示者裂備之。所形成 之膜具有2200 psi之抗張強度,100炻之460 psi棋量,及 1300%之百分延長率。 {請先3:旛背面•之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
Claims (1)
- 4060ί Α8 Β8 pQ D8 Γ --------- --— if * ^ 广;τ: 六、申請專; 1- 第85106666號專利再審查案申請專利範圍修正本 修正日期:89年6月 1. 一種形成膜之人工膠乳’其包含一乙稀與c ^ Π20 Λ -歸 烴之共聚物的水性分散液,該烯烴聚合物之特徵在於 具有: 、 a) 缺乏極性基團; b) 自1.5至2.5之多分散指數; c) Ιι〇/Ι2至少為 6 ; d) 與具有相同I2及多分散指數之線性烯烴聚合物之表 面熔融斷裂開始時之臨界剪切速率相比,其表面 嫁融斷裂開始時之臨界剪切速率至少大於50% . e) 至少45,000之重量平均分子量;及 f) 0.85至 0.9 g/cm3之密度; 其中該共聚物係為乙稀-1-辛稀、乙稀丁稀、乙稀_ 1-己婦或乙婦-4-甲基-1-戍婦共聚物。 2. 如申請專利範圍第1項之形成膜之人工膠乳,其中該 共聚物具有0.86至0.88之密度。 3. 如申請專利範圍第2或2項之形成膜之人工膠乳,其 中該共聚物為乙烯-1-辛烯共聚物。 4. 如申請專利範圍第3項之形成膜之人工膠乳,其中該 分散液係以如下化學式所示乙氧酚之硫酸鹽所穩定 之: X-0-0-(CH2-CH2-0)n-S03-Z+ 其中’又為C6-C18之線性或分枝烷基;φ為苯撐 本紙張尺度適用中國國家榡準(CNS)〜祕(21〇><297公着) (請先閲讀背面之注意事項再填寫本頁) *1T 文 經濟部智慧財產局員工消費合作社印製 A8 B8 _406090_^ 六、申請專利範圍 基;η為3至32;且Z為鈉、鉀或銨。5.如申請專利範圍第4項之形成膜之人工膠乳,其係於 室溫形成膜》 (請先閱讀背面之注意事項再填寫本頁) 、1Τ 經濟部智慧財產局員工消費合作社印製 -11- 本紙張尺度逋用中國國家標準(CNS ) Α4規格(210Χ297公釐) 4060ί Α8 Β8 pQ D8 Γ --------- --— if * ^ 广;τ: 六、申請專; 1- 第85106666號專利再審查案申請專利範圍修正本 修正日期:89年6月 1. 一種形成膜之人工膠乳’其包含一乙稀與c ^ Π20 Λ -歸 烴之共聚物的水性分散液,該烯烴聚合物之特徵在於 具有: 、 a) 缺乏極性基團; b) 自1.5至2.5之多分散指數; c) Ιι〇/Ι2至少為 6 ; d) 與具有相同I2及多分散指數之線性烯烴聚合物之表 面熔融斷裂開始時之臨界剪切速率相比,其表面 嫁融斷裂開始時之臨界剪切速率至少大於50% . e) 至少45,000之重量平均分子量;及 f) 0.85至 0.9 g/cm3之密度; 其中該共聚物係為乙稀-1-辛稀、乙稀丁稀、乙稀_ 1-己婦或乙婦-4-甲基-1-戍婦共聚物。 2. 如申請專利範圍第1項之形成膜之人工膠乳,其中該 共聚物具有0.86至0.88之密度。 3. 如申請專利範圍第2或2項之形成膜之人工膠乳,其 中該共聚物為乙烯-1-辛烯共聚物。 4. 如申請專利範圍第3項之形成膜之人工膠乳,其中該 分散液係以如下化學式所示乙氧酚之硫酸鹽所穩定 之: X-0-0-(CH2-CH2-0)n-S03-Z+ 其中’又為C6-C18之線性或分枝烷基;φ為苯撐 本紙張尺度適用中國國家榡準(CNS)〜祕(21〇><297公着) (請先閲讀背面之注意事項再填寫本頁) *1T 文 經濟部智慧財產局員工消費合作社印製
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US08/463,150 US5574091A (en) | 1995-06-05 | 1995-06-05 | Aqueous dispersions of olefin copolymers |
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- 1995-06-05 US US08/463,150 patent/US5574091A/en not_active Expired - Lifetime
-
1996
- 1996-05-17 EP EP96920267A patent/EP0830425B1/en not_active Expired - Lifetime
- 1996-05-17 AU AU58624/96A patent/AU5862496A/en not_active Abandoned
- 1996-05-17 WO PCT/US1996/007142 patent/WO1996039465A1/en active IP Right Grant
- 1996-05-17 JP JP9500598A patent/JPH11509240A/ja active Pending
- 1996-05-17 ES ES96920267T patent/ES2155609T3/es not_active Expired - Lifetime
- 1996-05-17 CA CA002220967A patent/CA2220967A1/en not_active Abandoned
- 1996-05-17 MX MX9709343A patent/MX9709343A/es unknown
- 1996-05-17 BR BR9608529A patent/BR9608529A/pt not_active Application Discontinuation
- 1996-05-17 DE DE69612495T patent/DE69612495T2/de not_active Expired - Lifetime
- 1996-05-17 KR KR1019970708817A patent/KR19990022337A/ko active IP Right Grant
- 1996-06-03 AR ARP960102877A patent/AR002198A1/es unknown
- 1996-06-04 TW TW085106666A patent/TW406090B/zh not_active IP Right Cessation
- 1996-08-23 US US08/702,824 patent/US5798410A/en not_active Expired - Lifetime
-
1997
- 1997-12-04 NO NO975641A patent/NO975641L/no not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
NO975641D0 (no) | 1997-12-04 |
NO975641L (no) | 1997-12-04 |
EP0830425A1 (en) | 1998-03-25 |
KR19990022337A (ko) | 1999-03-25 |
AU5862496A (en) | 1996-12-24 |
EP0830425B1 (en) | 2001-04-11 |
WO1996039465A1 (en) | 1996-12-12 |
JPH11509240A (ja) | 1999-08-17 |
MX9709343A (es) | 1998-02-28 |
AR002198A1 (es) | 1998-01-07 |
US5574091A (en) | 1996-11-12 |
BR9608529A (pt) | 1999-06-08 |
DE69612495D1 (de) | 2001-05-17 |
ES2155609T3 (es) | 2001-05-16 |
US5798410A (en) | 1998-08-25 |
DE69612495T2 (de) | 2001-11-22 |
CA2220967A1 (en) | 1996-12-12 |
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