TW592814B - Double-metal cyanide catalysts for preparing polyether polyols - Google Patents
Double-metal cyanide catalysts for preparing polyether polyols Download PDFInfo
- Publication number
- TW592814B TW592814B TW091119472A TW91119472A TW592814B TW 592814 B TW592814 B TW 592814B TW 091119472 A TW091119472 A TW 091119472A TW 91119472 A TW91119472 A TW 91119472A TW 592814 B TW592814 B TW 592814B
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- TW
- Taiwan
- Prior art keywords
- metal cyanide
- double metal
- cyanide catalyst
- crown
- weight percent
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 44
- 239000002184 metal Substances 0.000 title claims abstract description 44
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920000570 polyether Polymers 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 14
- 229920005862 polyol Polymers 0.000 title claims abstract description 14
- 150000003077 polyols Chemical class 0.000 title claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 24
- 230000000536 complexating effect Effects 0.000 claims abstract description 22
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
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- 150000003839 salts Chemical class 0.000 claims description 14
- 230000002079 cooperative effect Effects 0.000 claims description 11
- 239000002633 crown compound Substances 0.000 claims description 11
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- 150000003673 urethanes Chemical class 0.000 description 1
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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Description
592814 A7 _ B7 五、發明說明(1 ) 登jg之技術頜城 本發明有關一種製備聚醚多元醇用之雙金屬氰化物 (DMC)觸媒,其係將氧化烯加成聚合於具有活性氫原子之 起始化合物上。 5 發明背景 用以將氧化烯加成聚合於具有活性氫原子之起始化合 物上之DMC觸媒係已知。參照例如美國專利第3,4〇4,1〇9 號、第 3,829,505 號、第 3,941,849 號及第 5,158,922 號。 與使用驗金屬觸媒諸如例如驗金屬氫氧化物所製備之聚鍵 10多元醇比較之下,經DMC催化之聚醚多元醇係具有較低 含量之具有末端雙鍵的單官能基聚醚,所謂之,,單元醇,,。~ 使用DMC觸媒製備之聚驗多元醇可用以產製高級聚胺烏 甲酸酯,諸如例如彈料、發泡物及塗料。 土 經濟部智慧財產局員工消费合作社印製 DMC觸媒一般係藉由金屬鹽之水溶液與金屬氰化物 15 鹽之水溶液於有機絡合配位基例如喊存在下進行反應而製 備。典型DMC觸媒製備中,氣化鋅之水溶液(過量)與人 氰基鈷酸鉀係混合以形成懸浮液。之後添加二甲氧基乙俨 (葛來米(glyme))於該懸浮液中。之後濾出DMC觸媒,2 葛來米水溶液洗滌。此種方法所製備之DMC觸媒可由以 20下通式表示
Zn3[Co(CN)6]2 · xZnCl2 · yH20 · z 葛來米 參照例如EP-A 700 949。 以下參考資料揭示使用第三丁醇作為有機絡合配位烏 (本身或與聚鍵結合)之DMC觸媒’其係用以製備聚鍵^ 本紙張尺度適用中國國家標準(CNS)A4規格(210x 297公 592814 A7 B7 五、發明說明(2) 元醇,以進一步降低單元醇之含量·· JP 4145123、U.S· 5,470,813; EP 700 949; EP 743 093; EP 761 708;及 W0 97/40086。此外,此等DMC觸媒於製造聚醚多元醇之用 途係縮短氧化烯與對應之起始化合物之加成聚合反應的導 5 入時間。觸媒活性亦因使用此等DMC觸媒而增加。 然而,仍需要一種活性較技藝界已知之觸媒高而可用 以產製聚醚多元醇之DMC觸媒。 發明概述 本發明DMC觸媒係包含:a)至少一種DMC化合 10 物;b)至少一種有機絡合配位基,其不為冠狀化合物 (coronand);及c)至少一種冠狀化合物(cor〇nand) 〇 本發明DMC觸媒具有高於技藝界已知之觸媒的活 性。 發明描述 15 本發明DMC觸媒係包含:a)至少一種DMC化合 物;b)至少一種有機絡合配位基,其不為冠狀化合物 (coronand);及c)至少一種冠狀化合物(coronancj) 〇 經濟部智慧財產局貝工消费合作社印製 本發明DMC觸媒可視情況包含水,含量以DMC觸 媒總重計由1至10重量百分比為佳。而且,本發明DMC 20觸媒可視情況包含一或多種水溶性金屬鹽,含量以DMC 觸媒總重計由5至25重量百分比為佳。 可使用於本發明之水溶性金屬鹽可由通式⑴表示 M(X)n (I) 其中 -4- 本紙張尺度適用中國國家標半(UsjS)A4規格(210 X 297公爱) 592814 Α7 Β7 五、發明說明(3) Μ 係選自 Zn(II)、Fe(II)、Ni(II)、Mn(II)、Co(II)、 Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(Vl)、Al(III)、 V(V)、V(IV)、Sr(II)、W(IV)、W(VI)、Cu(II);及 Cr(III)(以 Zn(ll)、Fe(II)、Co(II)及 Ni(II)為佳); 5 各個X係相同或相異,以相同為佳,陰離子係選自 鹵基、氫氧根、硫酸根、碳酸根、氰酸根、硫代氰酸 根、異氰酸r根一異硫代氰酸根、羧酸根、草酸根及硝 酸根;且 η係為1、2或3。 10 本發明DMC化合物係為水溶性金屬鹽與水溶性金屬 經濟部智慧財產局員工消费合作社印製 氰化物鹽或金屬氰化物鹽之對應酸的反應產物。可用以製 備本發明DMC化合物之水溶性金屬鹽實例可由通式(I)表 示,其中 Μ 係選自 Zn(II)、Fe(II)、Ni(II)、Μη(ΙΙ)、 Co(II)、Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(VI)、 15 Al(III)、V(V)、V(IV)、Sr(II)、W(IV)、W(VI)、Cu(II);及 Cr(III)(以 Zn(II)、Fe(II)、Co(II)及 Ni(II)為佳)。各個 X 係相同或相異,以相同為佳,陰離子係選自鹵基、氫氧 根、硫酸根、碳酸根、氰酸根、硫代氰酸根、異氰酸根、 異硫代氰酸根 '羧酸根、草酸根及硝酸根。η之值係為 20 1、2 或 3。 可使用於本發明之適當水溶性金屬鹽實例係包括氣化 鋅、溴化鋅、乙酸鋅、乙醯基α羥基異丁酸鋅、苄酸辞、 硝酸鋅、硫酸鐵(II)、溴化鐵(II)、氣化鐵(II)、氣化鈷 (Π)、硫代氰酸鈷(II)、氣化鎳(II)、及硝酸鎳(II)。亦可使 本紙張尺度通用中國國家標準(CNS)A4規格Τ210 X 297公羞) 592814 A7 B7 五、發明說明(4) 用水溶性金屬鹽之混合物。 可用以製備本發明DMC化合物之水溶性金屬氰化物 鹽實例可由通式(II)表示 (Y)aM,( Q(A)C (II) 5 其中 Μ’係選自 Fe(II)、Fe(III)、Co(II)、Co(III)、Cr(II)、 Cr(III)、Mn(II)、Mn(III)、Ir(III) v Ni(II)、Rh(III)、 Ru(II)、V(IV);及 V(V)(以 Co(II)、Co(III)、Fe(II)、 Fe(III)、Cr(III)、Ir(III)及 Ni(II)為佳)且該水溶性金 10 屬氰化物鹽可包含一或多種此等金屬; 各個Y係相同或相異,以相同為佳,且係選自由鹼 金屬離子及鹼土金屬離子所組成之群; A係相同或相異,以相同為佳,陰離子係選自鹵基、 氫氧根、硫酸根、碳酸根、氰酸根、硫代氰酸根、異 15 氰酸根、異硫代氰酸根、竣酸根、草酸根及硕酸根; 且 經濟部智慧財產局員工消費合作社印製 a及b及c係為整數,a、b及c之值係經選擇,使得 該金屬氰化物鹽達到電中性(a以1、2、3或4為 佳;b以4、5或6為佳;且c以具有0之值為佳)。 20 可使用於本發明之水溶性金屬氰化物鹽之實例係包括 六氰基鈷酸(III)鉀、六氰基鐵酸(II)鉀、六氰基鐵酸(ΠΙ) 鉀、六氰基鈷酸(III)鈣、及六氰基鈷酸(ΠΙ)鋰。 較佳之本發明DMC化合物可由通式(IH)表示 -6- 本紙張尺度適用中國國家標準(CNS)A4規格(210x20公麓) 592814 A7 B7 五、發明說明(5 )
Mx[M,x,(CN)y]z (HI) 其中 Μ係如通式(I)所定義; M’係如通式(II)所定義;且 5 X、X’、y及z係為整數,且經選擇,使得DMC化合 物存在電中性。 較佳係 —一 x=3, x’ = l,y 且 z=2’ ; M=Zn(II)、Fe(II)、Co(II)或 Ni(II);且 10 M,=Co(III)、Fe(III)、Cr(III)或 Ir(III) 〇 可使用於本發明之DMC化合物實例係包括六氰基鈷 酸(III)鋅、六氰基銥酸(III)鋅、六氰基鐵酸(ΙΠ)鋅、及六 氰基鈷酸(III)鈷(II)。可使用於本發明之DMC化合物的其 他實例可參照例如美國專利第5,158,922號,其教示係以 15提及方式併入本文中。本發明中以使用六氰基鈷酸(III)鋅 為佳。 本發明有機絡合配位基係已知且描述於以下參考資料 經濟部智慧財產局員工消费合作社印製 中:美國專利第5,470,813號 '第5,158,922號、第 3,4〇4,109 號、第 3,829,505 號、及第 3,941,849 號,其教 20 示係以提及方式併入本文中,及ΕΡ 700 949、ΕΡ 761 708、JP 4145123、ΕΡ 743 093、及 W0 97/40086。本發明 有機絡合配位基以具有可與DMC化合物形成絡合物之雜 原子諸如氧、氮、磷或硫之水溶性有機化合物為佳。可使 用於本發明中之有機絡合配位基的實例係包括例如醇類、 本紙張尺度通用中國國蒙g(CNS)A4規格(21〇 x 297公釐了 592814 A7 B7 五、發明說明(6) _、賴、醚類、s旨類、酿胺類、_、腈類、硫化物 類及其混合物。祕有機絡合配位基係為水溶性脂族醇類 諸如乙醇、異丙醇、正丁醇、異丁醇、第二丁醇、及第三 丁醇。以第三丁醇特佳。 101520 經濟部智慧財產局貝工消費合作社印製 可使用於本發明之適當冠狀化合物(cor〇nand)係包括 單環冠狀化合物諸如冠n雜料取代之㈣(例如氮 雜-冠狀化合物、硫雜-冠狀化合物或娘雜_冠狀化合物); 球狀化合物;環狀化合物,包含雜芳族構建方塊諸如呋 喃、噻吩或吡啶(例如聯六吡啶);及包含酮基、羧酸酯基 或羧酸醯胺基以作為環(例如諾拿克辛(n〇nactin)或唯林諾 黴素(valinomycin))中予體部位之環狀化合物。以使用冠 醚為佳。以使用具有包含3 i 2G個氧原子之環系統的冠 醚更佳,兩相鄰氧原子各藉由長度為2至6個碳原子之橋 鍵鍵結。脂族或芳族環可縮合於該冠醚之中心環系統上。 該冠醚可具有官能基諸如胺基、羥基、羧基或硝基。 未經取代冠醚之實例係包括[12]_冠_4_(1,4,7,1〇_四氧 雜%十一烷),[15>冠_5-(1,4,7,10,13-五氧雜環十五炫); [18]-冠-6-(1,4,7,10,13,16_六氡雜環十八燒);[21]_冠-7-(1,4,7,10,13,16,19-七氧雜環二--烧);及[24]-冠 (1,4,7,10,13,16,19,22-八氧雜環二十四烷)。具有縮合於中 心環系統上之環系統的冠醚實例係包括笨并[15]_冠-5 ;二 笨并[18]-冠-6 ;二己環併[18]-冠-6 ;及二笨并[30]_冠-1〇。具有附加官能基之冠醚實例係包括2-羥甲基[12]-冠-4 ’ 2-經甲基[18]-冠-6 ; [18]-冠-6-2,3,11,12-四緩酸;4-胺 • 8-枣紙張尺度適用+國國家榡準(CNS)A4規格(21〇 X 297公爱Γ 592814 A7 B7 五、發明說明(7) 基-二笨并[18]-冠-6 ; 2-胺甲基[15]-冠-5 ; 4-甲醯基笨并 [15]-冠-5 ; 4-硝基-苯并[18]-冠-6 ;及全氟[15]-冠-5。其他 實例可參照 89 &c·,ρ· 7017 (1967); 84 如供w· C/zew·,ρ· 16 (1972);及 Gokel 等人 » Macrocyclic Polyether 5 办(1982)。 該DMC觸媒中之DMC化合物含量以DMC觸媒總 重計可由20至90重量百分比,以由25至80重量百分比 為佳。該DMC觸媒中有機絡合配位基之含量以dmC觸 媒總重計可由0.5至30重量百分比,以由1至25重量百 10分比為佳。該DMC觸媒中冠狀化合物(cor〇nand)含量以 該DMC觸媒總重計可由1至80重量百分比,以由1至 4〇重量百分比為佳。 本發明DMC觸媒可藉元素分析、熱解重量分析法或 離子性表面活性或界面活性化合物内容物之萃取移除及後 15 續之重量測定而進行分析。 本發明DMC觸媒可為結晶、部分結晶或非晶型。結 晶度一般係藉由粉末X-射線繞射計分析。 經濟部智慧財產局貝工消费合作社印製 本發明DMC觸媒以包含六氰基鈷酸(ΙΠ)鋅、第三丁 醇及冠狀化合物(coronand)為佳。 20 本發明DMC觸媒一般係於水溶液♦製備,藉由至少 一種金屬鹽(以通式(I)表示為佳)與至少一種金屬氰化物鹽 (以通式(II)表示為佳)在至少一種有機絡合配位基(以非冠 狀化合物(coronand)為佳)及至少一種冠狀化合物(coronand) 存在下進行反應而進行。 -9- 本紙張尺度適用肀國國家標準(CNS)A4規格(ΪΙΟ X 297公釐j 592814 A7 B7 五、發明說明 此製備中,超過理想配比量(以金屬氰化物鹽之莫耳 數量計係至少50莫耳百分比)金屬鹽(例如氣化鋅)係與金 屬氰化物鹽(例如六氰基鈷酸鉀)於有機絡合配位基(例如 第三丁醇)存在下進行反應。形成包含DMC觸媒(例如六 5氰基鈷酸鋅)、水、過量金屬鹽及有機絡合配位基之懸浮 液。 該有機絡合配位基或存在於金屬鹽及/或金屬氰化物 鹽之水溶液中,或係於製備DMC觸媒之後直接添加於該 懸浮液中。一般使用過量之有機絡合配位基ό該水溶液與 10有機絡合配位基之混合物以劇烈攪拌為佳。所形成之懸浮 液一般係使用艰狀化合物(coronan(j)進行處理。冠狀化人 物(coronand)較佳係與水及有機絡合配位基混合使用。。 該DMC觸媒係藉已知技術諸如離心或過濾而自懸浮 液單離。本發明較佳具體實例中,所單離之DMC觸媒係 15使用有機絡合配位基之水溶液洗滌(例如藉由再懸浮,之 後以過濾或離心進行更換單離)。水溶性副產物例如氣化 钟係藉由使用有機絡合配位基之水溶液洗務,而自所單離 之DMC觸媒移除。 經濟部智慧財產局員工消费合作社印製 洗蘇水溶液中有機絡合配位基之量以洗滌水溶液總重 20計介於20及80重量百分比之間為佳。較佳係添加冠狀化 合物(conmand)於洗滌水溶液中。該洗滌水溶液中冠狀化 合物(conmand)之含量以洗滌水溶液總重計係由〇5至5 重量百分比。 該DMC觸媒以洗務一次以上為佳。此可藉由重複前 -10- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)-------- 592814 A7 ----- B7 五、發明說明(9) 述洗務水溶液方法而達成。然而,使用非水性洗滌溶液進 行進一步之洗滌操作為佳。該非水性洗滌溶液係包含有機 絡a配位基與冠狀化合物(c〇r⑽ancj)之混合物。 經洗條之DMC觸媒在視情況粉碎之後,在於介於20 5至1〇〇C之間的溫度及介於0.1毫巴至正常壓力(1,013毫 巴)之間的壓力下乾燥。 本發明亦有關一種聚醚多元醇之製備,其係於本發明 DMC觸媒存在下,使氧化烯加成聚合於具有活性氫原子 之起始化合物上。 10 可使用於本發明之氧化稀實例係包括氧化乙烯、氧化 丙烯、氧化丁烯及其混合物。藉烷氧基化所積聚之聚醚鏈 可使用單一單體環氧化物達成,或任意地或嵌段地具有2 或3個不同單體環氧化物。此情況之進一步細節可參照 UHmanns Encyclopadie der industriellen chemie. 1992 年第 15 A21冊第670頁以下。 經濟部智慧財產局員工消费合作社印製 較佳使用於本發明含有活性氫原子之起始化合物係為 數量平均分子量為18至2,000且具有1至8個羥基之化 合物。可使用於本發明之起始化合物實例係包括乙二醇、 雙乙二醇、三(乙二醇)、1,2-丙二醇、1,4-丁二醇、己二 20 醇、雙酚A、三羥甲基丙烷、甘油、異戊四醇、山梨糖 醇、蔗糖、降解澱粉及水。 具有活性氫原子之起始化合物,以使用諸如藉由例如 習用鹼催化而自前述低分子量起始物所製備且係為具有由 200至2,000之數量平均分子量的募聚烷氧基化產物製備 -11 - i紙張尺度適用r關家標準(CNS)A4規格(別X 297公釐) 592814 A7
者為佳。 氧化稀藉由本發明DMC觸媒催化加成聚合於具有活 性氫原子之起始化合物的過程一般係於由2〇至2〇代之 溫度下進行,以由40至18〇t為佳,而由%至i5〇u 5佳。該反應可於W.OOOmoe之總壓力下進行加成 聚合可本體地進行或於惰性有機溶劑諸如甲笨及/或四氮 吱味(THF)中進行》溶劑用量以欲製備之㈣多元醇總重 計一般係由10至30重量百分比。 該DMC觸媒濃度係選擇以於特定反應條件下充分控 10制該加成聚合反應。觸媒濃度以欲製備之聚鍵多元酵之總 重計,一般係介於由〇._5重量百分比至i重量百分比 之範圍内,以0.001重量百分比至01重量百分比為佳, 0.001至0.0025重量百分比更佳。 本發明方法所製備之聚醚多元醇的數量平均分子量係 15介於由5〇〇至100,_克/莫耳範圍内,以1〇〇〇至5〇,_ 克/莫耳為佳,2,000至2〇,〇〇〇克/莫耳更佳。 該加成聚合可連續或不連續(例如分批或半分批方法) 地進行。 經濟部智慧財產局貝工消费合作社印製 因為其較高之活性,本發明DMC觸媒可於低濃度 20 (以欲製備之聚謎多元醇為百萬分之25份數或更低)下使 用。製備聚胺基甲酸酯時,若聚醚多元醇係於本發明 DMC觸媒存在下製備,則可省略自聚醚多元醇移除DMC 觸媒之步驟’而不對形成之聚胺基甲酸酯的產物品質造成 負面影響。參照 Kunststoffhanrihnrh. Vol.7, -12- 本纸張尺度適用中國國家標本(CNS)A4規格(210 X 297公楚) 592814 Α7 Β7 五、發明說明(11) 尸0/少『以/^阳,1993年第3版第25至32頁及第57至67 頁。 以下實施例僅用以說明本發明。熟習此技藝者已知可 在本發明精神及申請專利範圍内進行許多變化。 5 實施例 實施例1 包含順式-二環己環并[18]-冠-6之DMC觸媒的製備: 於劇烈攪拌下,將9毫升7.4重量百分比六氰基鈷酸 10 钟水溶液添加於15毫升11·8重量百分比氣化鋅水溶液、 13毫升第三丁醇與0.4克順式-二環己環并[18]-冠-6之混 合物中。形成之沉澱物以10毫升第三丁醇與30毫升水之 混合物洗滌,並過濾。之後添加20毫升第三丁醇於過濾 殘留物中,再次過濾。過濾之後,觸媒於50°C減壓(1〇毫 15 巴)下乾燥至定重。 元素分析、熱解重量分析及萃取:鈷= 12.9重量百分 比;鋅=25.7重量百分比;第三丁醇==6·0重量百分比;順 式·•二環己環并[18]-冠-6=14.6重量百分比。 經濟部智慧財產局員工消费合作社印製 實施例2 20 包含順式-二環己環并[18]-冠-6之DMC觸媒的製備: 於劇烈攪拌下,將9毫升7.4重量百分比六氰基鈷酸 鉀水溶液添加於15毫升11.8重量百分比氣化鋅水溶液、 13毫升第三丁醇、1毫升12重量百分比之乙酸與0.4克 順式-二環己環并[18]-冠-6之混合物中。形成之沉澱物以 -13- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消费合作社印製 592814 _B7 五、發明說明(12 ) 10毫升第三丁醇與30毫升水之混合物洗滌,並過渡。之 後添加20毫升第三丁醇於過濾殘留物中,再次過濾。過 濾之後,觸媒於50°C減壓(10毫巴)下乾燥至定重。 元素分析、熱解重量分析及萃取:鈷= 10.4重量百分 5 比;辞=25·3重量百分比;第三丁醇=4.8重量百分比;順 式-二環己環并[18]-冠-6=24.2重量百分比。 實施例3 包含順式-二環己環并[18]-冠-6之DMC觸媒的製備: 於劇烈攪拌下,將26·1毫升1.84重量百分比六氰基 1〇 姑酸溶液添加於15毫升11.8重量百分比氣化辞水溶液、 13毫升第三丁醇、1毫升12重量百分比之乙酸與〇·4克 順式-二環己環并[18]-冠-6之混合物中。形成之沉澱物以 10毫升第三丁醇與30毫升水之混合物洗條,並過遽。之 後添加20毫升第三丁醇於過濾殘留物中,再次過濾。過 15 濾之後,觸媒於50°C減壓(1〇毫巴)下乾燥至定重。 元素分析、熱解重量分析及萃取:鈷= 1〇·5重量百分 比;鋅= 19·7重量百分比;第三丁醇=4.9重量百分比;順 式-二環己環并[18]**冠-6=15.2重量百分比。 實施例4 2〇 包含順式-二環己環并[24l·冠之DMC觸媒的製備: 於劇烈攪拌下,將6毫升7·4重量百分比六氰基鈷酸 鉀水溶液及5毫升4.8重量百分比之六氰基鐵酸(ΠΙ)鉀水 溶液添加於15毫升11.8重量百分比氣化鋅水溶液、13 毫升第三丁醇、與0.4克順式-二環己環并[24]-冠-8之混 -14- 本紙張ϋϋ-用中國國家標準(CNS)A4規格<210x297公--
592814 Α7 Β7 五、發明說明(13) 合物中。形成之沉澱物以10毫升第三丁醇與30毫升水之 混合物洗滌,並過濾。之後添加20毫升第三丁醇於過濾 殘留物中,再次過濾。過濾之後,觸媒於50°C減壓(1〇毫 巴)下乾燥至定重。 5 元素分析、熱解重量分析及萃取:始=7.3重量百分 比;鐵=3.7重量百分比;鋅=25.5重量百分比;第三丁醇 =5.2重量百分比;順式-二環己環并[24]-冠-8=21.7重量百 分比。 實施例5 10 包含順式-工環己環并[18]-冠-6之DMC觸媒的製備: 於劇烈攪拌下,將4.5毫升7.4重量百分比六氰基鈷 酸鉀水溶液及5毫升7·2重量百分比六氰基鐵酸(III)鉀水 溶液添加於15毫升11.8重量百分比氯化鋅水溶液、13 毫升第三丁醇及0.4克順式-二環己環并[18]-冠-6之混合 15 物中。形成之沉澱物以30毫升水洗滌,並過濾。之後添 加20毫升第三丁醇於過濾、殘留物中,再次過濾。過遽之 後,觸媒於50°C減壓(10毫巴)下乾燥至定重。 經濟部智慧財產局員工消费合作社印製 元素分析、熱解重量分析及萃取:鈷=6.2重量百分 比;鋅=25.9重量百分比;鐵=5.9重量百分比;第三丁醇 20 =5·9重量百分比;順式-二環己環并[18]-冠-6=16.7重量百 分比。 實施例6 包含[18>冠-6之DMC觸媒的製備: 於劇烈攪拌下,將9毫升7.4重量百分比六氰基鈷酸 -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 592814 Α7 Β7 五、發明說明(Η) _水溶液添加於28毫升12·7重量百分比氣化鋅水溶液、 13毫升第三丁醇、1毫升12重量百分比之乙酸及0.4克 [18]-冠-6之混合物中。形成之沉澱物以30毫升水洗滌, 並過濾。之後添加20毫升第三丁醇於過濾殘留物中,再 5 次過濾。過濾之後,觸媒於l〇〇°C減壓(1〇毫巴)下乾燥至 定重。 元素分析、熱解重量分析及萃取:鈷= 1ΐ·〇重量百分 比;鋅=26.2重量百分比;第三丁醇=6·2重量百分比; [18]-冠-6=15.1重量百分比。 10 實施例7 包含[15]-冠-5之DMC觸媒的製備: 於劇烈攪拌下,將27毫升1.79重量百分比六氰基鈷 酸溶液添加於28毫升12·7重量百分比氣化辞水溶液、13 毫升第三丁醇、1毫升12重量百分比之乙酸及0.4克 15 [15]-冠-5之混合物中。形成之沉澱物以30毫升水洗滌, 並過濾。之後添加20毫升第三丁醇於過濾殘留物中,再 次過濾。過濾之後,觸媒於l〇〇°C減壓(1〇毫巴)下乾燥至 定重。 經濟部智慧財產局員工消费合作社印製 元素分析、熱解重量分析及萃取:始==10.7重量百分 20 比;鋅=23.3重量百分比;第三丁醇=5.0重量百分比; [15]-冠-5=11·4重量百分比。 實施例8 包含2-羥甲基[18]-冠-6之DMC觸媒的製備: 於劇烈攪拌下,將9毫升7.4重量百分比六氰基鈷酸 -16- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 592814 A7 B7 五、發明說明(15) 鉀水溶液添加於14毫升12.7重量百分比氣化鋅水溶液、 13毫升第三丁醇及0.4克2-羥甲基[18]-冠-6之混合物 中。形成之沉殿物以30毫升水洗滌,並過遽。之後添加 20毫升第三丁醇於過濾殘留物中,再次過濾。過濾之 5 後,觸媒於100°C減壓(1〇毫巴)下乾燥至定重。 元素分析、熱解重量分析及萃取:鈷= 10.4重量百分 比;鋅=24.7重量百分比;第三丁醇=5.8重量百分比;2-羥甲基[18]-冠-6=12.4重量百分比。 實施例9 10 包含2-羥甲基[18]•冠-6之DMC觸媒的製備: 於劇烈攪拌下,將27毫升1.79重量百分比六氰基鈷 酸溶液添加於14毫升12.7重量百分比氣化鋅水溶液、13 毫升第三丁醇、1毫升12重量百分比之乙酸及0.4克2-羥甲基[18]-冠-6之混合物中。形成之沉澱物以30毫升水 15 洗滌,並過濾。之後添加20毫升第三丁醇於過濾殘留物 中,再次過濾。過濾之後,觸媒於l〇〇°C減壓(1〇毫巴)下 乾燥至定重。 經濟部智慧財產局員工消费合作社印製 元素分析、熱解重量分析及萃取:鈷= 10.1重量百分 比;鋅=20.2重量百分比;第三丁醇=4.2重量百分比;2-20 羥曱基[18]-冠-6=13.4重量百分比。 對照例10 不包含冠狀化合物之DMC觸媒的製備: 於劇烈攪拌下,將9毫升7.4重量百分比六氰基鈷酸 鉀水溶液添加於15毫升11.8重量百分比氣化鋅水溶液與 -17- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 592814 A7 B7 五、發明說明(16) 13毫升第三丁醇之混合物中。形成之沉澱物以10毫升第 三丁醇洗滌,並過濾。之後添加20毫升第三丁醇於過濾 殘留物中,再次過濾。過濾之後,觸媒於50°C減壓(10毫 巴)下乾燥至定重。 5 元素分析、熱解重量分析及萃取:鈷= 15.7重量百分 比;鋅=27.8重量百分比;第三丁醇=7.9重量百分比。 聚醚多元醇之製備 一般方法 10 為測量本發明所製備之觸媒的活性,於保護性氣體 (氬)下將50克聚丙二醇起始物(分子量= 1000克/莫耳)及 20克觸媒導入500毫升高壓反應器中,於攪拌下加熱至 130°C。 在30分鐘内,於2.5巴之壓力下分配置入最多50克 15 之氧化丙烯。30分鐘之後,反應混合物冷卻至室溫,以 氬沖洗而移除氧化丙烯。 該產物係藉由凝膠滲透層析(GPC)所測定之分子量分 佈(重量平均值)而定性。 經濟部智慧財產局員工消费合作社印製 所得之結果列於表1中。 -18- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 592814 A7 B7 五、發明說明(17) 表1 :實施例1至10所製備之觸媒的分子量分佈 觸媒實施例編號 Mw[克/莫耳I 1 2130 2 1970 3 1940 4 2180 5 2020 6 1920 7 1890 8 1910 9 1900 1〇(對照例) 1310 雖已於前文針對詳細描述本發明以供說明,但已知該 細節僅供作說明,熟習此技藝者可在不偏離本發明精神及 5 範圍之情況下進行各種改變,僅受限於申請專利範圍。 經濟部智慧財產局員工消费合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)
Claims (1)
- 592814 A8 B8 C8 D8 經濟部智慧財產局員工消費合作社印製 六、申請專利範圍 )vc /:1 5 10 2 15 3 4 20 5 25 7 專利申請案第91119472 ROC Patent Appln. No. 91119472 修正後無劃線之申請蓴利範圍中文本·附件(一) Amended Claims in Chinese - Encl.(D (民國93年4月 ?曰送呈) (Submitted on April 9,2004) 一種雙金屬氰化物觸媒,其包含: a) 至少一種雙金屬氰化物化合物; b) 至少一種非冠狀化合物(coronand)之有機絡合配位 基;及 c) 至少一種冠狀化合物(coronand) 〇 如申請專利範圍第1項之雙金屬氰化物觸媒,其另外 包含水及/或至少一種水溶性金屬鹽。 如申請專利範圍第1項之雙金屬氰化物觸媒,其中該 雙金屬氰化物化合物係為六氰基鈷酸(III)鋅。 如申請專利範圍第1項之雙金屬氰化物觸媒,其中該 有機絡合配位基係為醇、醛、酮、醚、酯、醯胺、 脈、赌、硫化物及/或其混合物。 如申請專利範圍第1項之雙金屬氰化物觸媒,其中該 有機絡合配位基係為第三丁醇。 如申請專利範圍第1項之雙金屬氰化物觸媒,其中該 雙金屬氰化物觸媒中冠狀化合物(coronand)之含量以 該雙金屬氰化物觸媒之總重計係由約1至約80重量 百分比。 一種製備如申請專利範圍第1項之雙金屬氰化物觸媒 的方法,其包括⑷於水溶液中使⑴至少一種金屬鹽 20 - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 91367B 接 592814 經濟部智慧財產局員工消費合作社印製 A8 B8 C8 _D8_ 六、申請專利範圍 與(ii)至少一種金屬氰化物鹽或該金屬氰化物鹽之對 應酸,於(iii)至少一種非冠狀化合物(coronand)之有 機絡合配位基存在下進行反應,以形成懸浮液;及(b) 使用至少一種冠狀化合物(coronand)處理該懸浮液。 5 8、如申請專利範圍第7項之方法,其另外包括:(c)自 該懸浮液單離該雙金屬氰化物觸媒;及(d)洗滌該雙 金屬氰化物觸媒;及(e)乾燥該雙金屬氰化物觸媒。 9、一種製備聚醚多元醇之方法,其係於如申請專利範圍 第1項之雙金屬氰化物觸媒存在下,使氧化烯加成聚 10 合於具有活性氫原子之起始化合物上。 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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KR20060120012A (ko) * | 2003-10-10 | 2006-11-24 | 쉘 인터내셔날 리써취 마트샤피지 비.브이. | 폴리에테르 폴리올의 제조방법 |
ES2298705T3 (es) * | 2004-02-27 | 2008-05-16 | Repsol Quimica S.A. | Catalizadores de cianuros dobles metalicos (dmc) con esteres-corona, procedimiento para su obtencion y aplicaciones. |
US20060058182A1 (en) * | 2004-09-13 | 2006-03-16 | Combs George G | Processes for the preparation of double metal cyanide (DMC) catalysts |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1063525A (en) | 1963-02-14 | 1967-03-30 | Gen Tire & Rubber Co | Organic cyclic oxide polymers, their preparation and tires prepared therefrom |
US3829505A (en) | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
US3941849A (en) | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
JP2653236B2 (ja) | 1990-10-05 | 1997-09-17 | 旭硝子株式会社 | ポリエーテル化合物の製造方法 |
US5158922A (en) | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5470813A (en) | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5712216A (en) | 1995-05-15 | 1998-01-27 | Arco Chemical Technology, L.P. | Highly active double metal cyanide complex catalysts |
US5482908A (en) | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5545601A (en) | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
US5627120A (en) | 1996-04-19 | 1997-05-06 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5714428A (en) | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
DE19906985A1 (de) * | 1999-02-19 | 2000-08-31 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
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2001
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- 2002-08-19 PL PL02367706A patent/PL367706A1/xx not_active Application Discontinuation
- 2002-08-19 JP JP2003525063A patent/JP2005501947A/ja active Pending
- 2002-08-19 MX MXPA04001907A patent/MXPA04001907A/es active IP Right Grant
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- 2002-08-19 HU HU0401744A patent/HUP0401744A2/hu unknown
- 2002-08-19 KR KR10-2004-7002927A patent/KR20040029086A/ko not_active Application Discontinuation
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- 2002-08-19 CA CA002458530A patent/CA2458530A1/en not_active Abandoned
- 2002-08-19 CN CNB028169034A patent/CN1289569C/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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JP2005501947A (ja) | 2005-01-20 |
EP1425333A1 (de) | 2004-06-09 |
US20030050186A1 (en) | 2003-03-13 |
CN1289569C (zh) | 2006-12-13 |
ATE298354T1 (de) | 2005-07-15 |
PL367706A1 (en) | 2005-03-07 |
DE10142746A1 (de) | 2003-03-20 |
CA2458530A1 (en) | 2003-03-13 |
BR0212156A (pt) | 2004-07-13 |
US6586564B2 (en) | 2003-07-01 |
MXPA04001907A (es) | 2005-03-07 |
DE50203464D1 (de) | 2005-07-28 |
CN1671768A (zh) | 2005-09-21 |
WO2003020796A1 (de) | 2003-03-13 |
EP1425333B1 (de) | 2005-06-22 |
HUP0401744A2 (hu) | 2004-12-28 |
HK1083222A1 (en) | 2006-06-30 |
PT1425333E (pt) | 2005-10-31 |
ES2242872T3 (es) | 2005-11-16 |
KR20040029086A (ko) | 2004-04-03 |
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