TW200536872A - Process for hydrogenating unsaturated polymers containing double bonds - Google Patents
Process for hydrogenating unsaturated polymers containing double bonds Download PDFInfo
- Publication number
- TW200536872A TW200536872A TW094101063A TW94101063A TW200536872A TW 200536872 A TW200536872 A TW 200536872A TW 094101063 A TW094101063 A TW 094101063A TW 94101063 A TW94101063 A TW 94101063A TW 200536872 A TW200536872 A TW 200536872A
- Authority
- TW
- Taiwan
- Prior art keywords
- latex
- metal
- colloid
- unsaturated
- polymer
- Prior art date
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- 239000002184 metal Substances 0.000 claims description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims description 20
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- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- YITSIQZHKDXQEI-UHFFFAOYSA-N trichlorogermanium Chemical compound Cl[Ge](Cl)Cl YITSIQZHKDXQEI-UHFFFAOYSA-N 0.000 description 1
- 238000005533 tritiation Methods 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/16—Reducing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
- C08C1/04—Purifying; Deproteinising
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C1/00—Treatment of rubber latex
- C08C1/14—Coagulation
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Description
200536872 九、發明說明: 【發明所屬之技術領域】 本發明關於一種氫化含雙鍵之不飽和聚合物之方法,呈乳 膠形式之不飽和聚合物係於金屬膠體存在下氫化。 【先前技術】 不飽和聚合物(例如不飽和彈性體,例如丙烯腈/丁二晞共 鲁聚物(NBR))形成對應的完全或部分氫化聚合物之氫化反應係 為已知。 透過實例,丁二烯與丙烯腈之共聚物係於工業製程中氫化 為對應的氫化產物,其中所製得的完全或部分氫化聚合物(以 丁二烯及丙烯腈為基底)具有改良的老化安定性、财臭氧性及 低膨潤性。 不飽和聚合物(例如NBR)之商業性氫化反應之一種變體 涉及例如透過乳化聚合物反應使所製得的NBR乳膠凝固,以 鲁及使其自液相(乳清)分離。接著,於複數個製程步驟中,NBR 橡膠經乾燥、溶解於有機溶劑中,以及使用均勻或不均勻氫化 觸媒(部分地)而經氫化。適合的此類觸媒為例如以釕或铑為基 底之威爾金森(Wilkinson)觸媒(以此進行均勻催化作用)或以鈀 /碳為基底之非均勻觸媒。 然而’此程序具有缺點為,所製得的不飽和橡膠必須於分 開的製程步驟中再度地〉谷解於有機溶劑中,俾可接續進行氫化 反應。 200536872 片不飽和聚合物(例如彈性體)之氫化反應之另一種變體涉及 氫化直接地呈乳膠形式之不飽和聚合物,而不須首先分離母橡 膠及再度使其轉於有機溶液巾(為了氫化反應)。
此程序係揭示於wo 00/09576及w〇 〇1/55223中。然而, ,程序之缺點為氫化反應係於胼或肼予體化合物存在下或於 氧化劑(例如過氧化氫)存在下以及於某些添加劑存在下進行。 由於於氧化劑存在下以胼操作需要特殊的安全性預防措施,故 所述之氫化反應需要相當高水準的成本及就裝置方面而論之 不便利性(以經濟為代價)。再者,氫化反應需要胼及氧化劑。 此反應係透過凝膠作用而完成。然而,為了防止或降低凝膠作 用,額外的製程措施是必要的,此同樣地係以經濟為代價。 亦已知者為乳膠形式之不飽和聚合物於水溶性威爾金森 觸媒存在下之氫化反應。此程序亦具有缺點為所生成的氫化聚 合物之某程度的凝膠作用出現,此造成影響氫化產物之品質減 損G月參照例如办h少,2〇〇2,25 (5),311· C/zew⑻rj;⑽of rec/mo/ogy,1995,68(2),281 及 US 6084033) 〇 【發明内容】 因此,本發明之目的係提供一種氫化不飽和聚合物之經濟 方法,其可依技術上簡單的方式進行,同時具有良好的產品品 質(就氫化或部分氫化的聚合物而論)。 本發明k供一種鼠化含雙鍵之不飽和聚合物之方法,其特 徵在於首先於呈乳膠形式之不飽和聚合物存在下於還原條件 6 200536872 下製備金屬膠體,接著氳化所生成的含谬體之乳膠混合物,之 後自乳膠分離該金屬膠體以及分離所生成的聚合物乳^。 可藉本發明之方法氳化之含雙鍵之不飽和聚合物的實例 包含自共軛二烯合成者(均聚合物)或自1%至5%重量丘軛二 及95%至99%重量含乙烯基基團之單體合成者(共聚合物):此 軛,烯的實例包含如下:U_丁二烯、2,3_二甲基丁二烯、異^ 一烯及1,3-戊二烯。含乙烯基基團之不飽和單體的特例為腈化 鲁合物(例如丙烯腈及甲基丙烯腈)、含乙絲基團之芳族化合物 (例如苯乙烯、鄰-烷基苯乙烯、間-烷基苯乙烯、對-烷基苯乙 烯,例如甲基苯乙烯)及二乙烯基苯。可另外提到之芳族二烯 基化合物為例如二異丙烯基苯、不飽和羧酸及羧酸酯(例如丙 烯酸、曱基丙埽酸、巴豆酸、馬來酸、丙稀酸甲醋、丙稀酸乙 酯、丙烯酸丁酯、丙烯酸2_乙基己酯及甲基丙烯酸曱酯)、乙 稀基吼咬及乙烯基酯(例如醋酸乙晞基酯)。 可提到之較佳不飽和聚合物為聚丁二烯、聚異戊二烯、苯 鲁乙烯-丁二烯共聚物(SBR)、丙烯腈-丁二稀共聚物_&卜天然 橡膠、丁二烯·異戊二烯橡膠及丁二烯、丙烯腈及丙烯酸丁醋 或丙烯酸之三元聚合物。極特佳者為丙稀骑_丁二稀共聚物 (NBR)。 如所提到,不飽和聚合物係呈乳膠形式氮化。上述不飽和 聚合物之對應的乳膠之製法係為熟習本技藝人士之常識。對應 的不飽和聚合物之乳膠形式代表可含有已知及習知含量之已 知乳膠添加劑(例如乳化劑及安定劑)之聚合物的水性乳液。此 一聚合物乳膠(例如NBR乳膠)之製法係以通用形式揭示於例 200536872 如 C/zem rec/mo/· 1963, 36, 1(由 w· Hoffmann 著)及其中 所述之文獻中。 就本發明之方法而論,以水性乳液為基準,欲氳化之聚合 物乳膠的濃度係為1%至50%重量,較佳為1〇%至3〇%重量。 如上述,重要的是金屬膠體係於呈乳膠形式之不飽和聚合 物存在下製得,且接著所生成的含膠體之乳膠聚合物經氫化。 此處之私序係於聚合物乳膠存在下,進行金屬鹽類或金屬 春絡合物成為金屬膠體之還原轉化作用,視情況使用表面活性物 質(例如表面活性劑)或者使用膠體安定物質(例如聚乙烯基吡 略烧酮)。 就所用之表面活性劑而論,透過實例可提到者為兩性甜菜 鹼(A)(例如3-N,N-(二甲基十二烷基胺基)丙烷磺酸酯)、陽離子 型表面活性劑(B)、脂肪醇聚二醇醚(c)、聚氧基伸乙基_碳水化 合物脂肪烧基醋⑼、陰離子型表面活性劑⑹(例如芳基烧基確 酸及/或烷基%酸及其鈉鹽以及長鏈烷基硫酸酯,例如十二烷 基硫酸鈉及飽和和不飽和脂肪酸的鹼金屬鹽)以及兩性糖表面 活性劑(F)。 以橡膠固形物為基準,可使用含量為約1〇/〇至1〇〇/〇重量之 膠體安定物質及/或表面活性劑,亦可能使用表面活性劑混合 物0 一種有利的變體涉及首先溶解金屬鹽及/或金屬絡合物於 水中,以及使用對應的表面活性劑及/或膠體安定物質,將水 溶液引入不飽和聚合物之存在的乳膠中,且接著添加還原劑。 8 200536872 通常係於溫度約20至70°C(較佳為20至30°C)下進行將金屬鹽 及/或金屬絡合物的水溶液引入乳膠中。 為了避免當製備金屬膠體時乳膠凝固,於界定的pH範圍 内操作是重要的。有利的pH範圍為約3至6,較佳為4.5至5。 就金屬鹽或金屬絡合物而言,使用以來自元素週期表之第 VIIIB族的金屬為基底者以及以諸如釕或铑等金屬為基底者是 可能的。金屬鹽或金屬絡合物亦可用作彼此之混合物。 所用之金屬鹽可以以下通式表示:
Mn+(A)m, 其中 Μ為自第VIII B過渡族(根據門德列夫)之金屬,尤其是自第10 族(IUPAC)之金屬以及铑及釕。Ni、Pd' Rh及Ru為特佳, Ni為極特佳, 籲A為有機或無機陰離子,尤其自基團R-COCT,其中R=氫、甲 基、乙基、丙基、鹵素(例如F、Cl、Br、I)、絡合陰離子 (例如 NCV、S042' α〇4-、bf4-、pf6-、C>T),且 m及n係為考量離子電荷,經選擇使得中性化合物生成之變數。 金屬驗金屬鹽類或酸類含有符合下式之絡合陰離子: [Mn+(A)m]k_, 200536872 其中 Μ為自弟VIII B過渡族之金屬 金屬以及姥及釕。極特佳者為t疋自第W族(IUPAC)之 其 Ni, 1 Pd、Pt、Rh 及 Ru,尤 子,尤其自基團 基乙基、丙基、4素(例如F 其中R=氫、曱 (例如NO,、S〇42-、Cl〇4_、抑4、押玢、1}、絡合陰離子 m、η及k係為考量離子雷 4 6、CN·),且 成之變數。?電何,經選擇使得金屬絡合陰離子生 特佳者為以下金屬_及金屬絡合物: =銘:硝酸銘、演化銘、過氯酸 ' 、過氯酸鎳、羧酸鎳、曱酸銲、-辛酿鎳、硝酸鎳、 铑、m 漠⑽、三氯化鍺、氣化ΐ 氡化Γ 三氣化釕、氯化六氨娜)、氯化六氨
==_〗)、二氣她、六氯酸;、 四羲:酸鈉、四氣鈀酸鈉、四氣銘酸鈉、四氨四C ’極特佳者為六氣倾、嫩酸 四氣銳酸鈉、二氯化把、氣_。可單獨且可_=駿 200536872 所欲混合物使用金屬鹽類及/或金屬絡合物 當二?:Γ形物為基準,金屬鹽類及/或金屬絡合物通 吊係以約_克至5克(較佳為克至1〇克)之用量使用。 传方法而論,所用之金屬鹽類及7或金屬絡合物 _1訂’㈣2°至赋範_之溫度 乂 -至70c),還原地轉化為金屬膠體。 ,馬=還原劑之實例包含氫、絡合氫化物(尤其氫化鈉)、 二心合物(例如胼及肼水合物)、經基胺及其鹽類,但 ^疋月井及其鹽類。可用之另外的還原劑包含有機化合物,例 =類及/或醇類,較佳為乙駿、㈣、乙基醇及/或曱基醇。 =而亦可提及者為驗金屬甲酸鹽。此外,於膠體安定物質存 下使V、田刀散的基底金屬(例如鋅粉)引起貴金屬之還原作 =,以形成安定的踢體是可能的。膠體安定物質,例如聚乙烯 =比,烧酮或聚抓乙烯基吼洛烧酮务二甲基胺基乙基甲 基丙烯酸SI),其本身亦為有效的還原劑。 〜,,的還原劑包含如下:氫、絡合氳化物(例如NaBH4)、 羥,銨氣化氫、胼及胼水合物、曱醛及乙醛、曱酸及曱酸鈉、 鋅各尤其氫、硼氫化鈉及胼水合物。亦可以彼此任一所欲混 合物使用還原劑。 亦可能於現存的氬氣氛圍存在下進行還原劑之添加。 取一田已製備聚合物乳膠與金屬膠體之適當混合物時,不飽和 ♦ 口物經氫化。此氫化反應係於壓力在約0.1至100巴之範圍 11 200536872 内(較佳為1至m L ^ 常處於約25至1〇 ’ 1、佳為1至15巴)進行。氫化溫度通 於氫化反 較佳為25至7〇°C。 混合物至約2〇Ί上物去除金屬。此係藉添加反應 使乳膠凝S]而⑽-糟者於氧化條件下添加絡合劑)及接著 ㈣屬為金屬鹽於液相(乳清)卜 絡合_二°屬:至===屬 合物之齡物紐、f料麵)或所述絡 此等絡合劑通㈣以_/克至;;5 f 物為基準’ 之用量使用。 克(車乂佳為〇.1克至1.0克) 以下係較佳用作絡合劑者:ed 如葡萄_)’例如檸檬酸、酒石酸、3 :乳酸、糖酸(例 SCN- ^ CN- . F-), 混合物使用。 地及以彼此之任一所欲 適合的氧化劑較佳為氣狀氧化劑, 然亦可_其他氧化n其 ,可。透過實例’亦可能使用稀俩=t丨 乳膠分離金屬。於此電化學方法4=;,自聚合物 自聚合物⑽分離金屬膠體(具有較高比^者為使用離心機於 為藉由例如水溶性絡合劑或選擇性 特別適合的方法 磷烧、冠謎及/或離子交換樹脂)之可如石黃酸化三苯基 性相者。 可將金屬膠體轉化為水 12 200536872 於自氫=的聚合物乳膠去除金屬後,以習知方式(例如藉 凝固作用、藉添加乙醇、藉添加鎂鹽或藉冷卻)分離氫化產物 的乳膠。 當然亦可能以習知方式使乳膠沉殿以及經由例如過濾而 自水性相分離沉澱的聚合物。 本發明之方法生錢化或部分氫化的聚合物,其中約1% 至",,較佳為10%至6〇%原本存在之雙鍵係為氯化形式。因 籲此,氫化度為理論值之約1%至99%,較佳為1〇%至6〇%。 【實施方式】 實施例 實施倒1.1 :遂iNfflR乳嚴查座_下之鎳膠艚么复幻 使NiCl” 6出0 (0.126克,〇 53亳莫耳)與燒基續酸鹽 Μ⑽lat⑧30 (〇.36克)溶解於1G毫升不含氧的氬氣飽和水(ι〇 #毫升)中。接著,以溶液形式(0.5克;於水中為19%重量)添加 料N-乙烯細匕洛炫酮-共_2_二甲基胺基乙基甲基丙稀酸醋)。 伴隨攪拌,逐滴地使此混合物與乳膠(2〇毫升,1927〇/重旦 Perbu腦⑧ NT 3445 W ’ AN 含量為 24%重量,pH $ (Ηα°),二 5%重量MerS〇lat ’係'以橡膠固形物為基準)混合。接著,逐滴 地添加馳叫溶液(0.U克,於%毫升水中)。於反應中元 素錄立即地形成,並且可觀察到嚴重的發泡現象。冰可藉預 先添加石夕酮油(2滴)於乳膠中而減緩。)於約i小時後,已乎加 總量的灿戰’並且製得顏色為灰_黑色之乳膠(此立即地用於 13 1 200536872 氫化反應)。 實施例」—·2(比較)i於NBR乳歷查體之製備(pH⑷ 使NiCb· 6氏0 (0.126克,〇·53毫莫耳)與烷基磺酸鹽 Mersolat® 30 (0·36克)溶解於10亳升不含氧的氬氣飽和水(1〇 毫升)中。接著,以溶液形式(〇·5克;於水中為重量)添加 聚(Ν-乙缔基吼洛炫酮-共-2_ —甲基胺基乙基甲基丙稀酸酯)。 鲁伴隨授摔’逐滴地將此混合物添加於NaBH4溶液(〇 12克,於 50毫升水中)與乳膠(20毫升,19.27%重量Perblman®NT 3445 VP,AN含1為24%重虿,pH 12,約1%重量Mers〇iat,係以 橡膠固形物為基準)之混合物中。於反應中,元素鎳立即地形 成,並且可觀察到嚴重的發泡現象。(此可藉預先添加矽酮油(2 滴)於乳膠中而減缓)。於約1小時後,已添加總量的Nicl2,產 且製彳f顏色為灰-黑色之乳膠(此立即地用於氫化反應)。 • 氳化反應之完成 針對此反應,使用製自哈氏合金Hastelloy C4、經認<通 過50巴(於300°C下之操作壓力最大值為3〇〇巴)、具有磁鐵偶 合的刀片攪拌器之可加熱的〇·3升反應器η 5347。 ” 於真空下,於l〇0°C下乾燥清潔的反應器3小時,並真冷 部,以20巴之氮氣進行洩漏試驗,以及再度排空。 、於將所製得的乳膠溶液(40毫升)引入反應器中,接著伴隨擭 拌’加熱至所欲溫度。 200536872 當已達到所欲溫度時,使反應器裝填10巴之氫氣(之後連 續地計量加入)。於7(TC下進行攪拌(15〇rpm)3小時,接著冷 卻,以及稀釋至總壓力為15巴(具有5巴之氮氣)。接著於〇5 小時期間内將反應器減少至氮氣流為12平方公尺/小時。接著 裝填3巴之氮氣以及減少。重複此操作二次,接著去除乳膠。 實施倒自酸性复金^乳膠去除鎳膊體及f 於氛圍氧氣存在下,藉添加擰檬酸使NBR乳膠中之元素 鎳氧化。於0.5小時之期間内,以檸檬酸濃度〇 5克/毫升, 礼膠與風H氧氣混合,俾提供白色乳膠。當使用較低濃度之稗 檬酸時(0:02克/毫升),達到完全反應所花的時間約6小時。养 ,加(乙醇/乳膠=2])乙醇與老化抑制劑(〇1克卿⑧,於^ 笔升乙醇中)’誘發白色乳膠至凝固。接著,分離橡膠,並且 以U ☆ 50 c真空乾燥烘箱巾乾燥聚合物,並且描纟會特徵。 於=圍乳氣存在下,藉添加KCN使nbr乳膠中之元素錄 乳化。於0.5小時之期間内,以KCN濃度〇1克/毫升,使乳 t與氣混合,俾提供白色乳勝。當使用較低濃度之KCN 克/¾升),達到完全反應所花的 (乙醇f膠=2 : D乙醇與老化抑制_.丨克聊⑧,於ΓοΓΪ 二白色乳膠至凝固。接著,分離橡膠,並且以 水洗。於5GCA空乾燥烘箱中乾縣合物,並且描繪特徵。 15 200536872 a) 衣· No· lNDK孑L膠 聚合物 [M]:(mM) Tp(°〇 氫化度 可溶性分率 ^^ [η]/ Mw/101 (莫耳%) (%重量) (毫并/克) --- 氺 Perbunan® - - - 99.3 146.8 1.288 NT 3445 VP 1 Perbunan® [Ni]: 17.7 65 12 99.2 1806 2.111 NT 3445 VP 實施例1·1 2 Perbunan® [Ni]:35.3 65 13 57,2 121.5 n.a NT 3445 VP 實施例1·1 3** Perbunan® [Ni]: 17.7 65 0 37.3 82.8 n.a NT 3445 VP 實施例1.2 4** 空白試驗 靡 65 0 99.5 153.0 .^^一" 16 1 (HC1)或14,約5%重量Mersolat(以橡膠固形物為基準);20毫升水’氫化時間·· 3小時,H2:10巴;可溶性分率及[抓於THF中);自1H-NMR頻譜(於CCD3中)(400 MHz)測定之氮化度。起始產物;**比較。
Claims (1)
- 200536872 十、申請專利範圍: 1·一種氫化含雙鍵之不飽和聚合物之方法,其特徵在於首先於 呈乳膠形式之不飽和聚合物存在下於還原條件下製備金屬 膠體,接著氫化所生成的含膠體之乳膠混合物,之後自乳 膠分離該金屬膠體以及分離所生成的聚合物乳膠。 2·如申請專利範圍第1項之方法,其特徵在於所用的含雙鍵之 不飽和聚合物係為自共軛二烯或自1%至5%重量共軛二烯 及95%至99%重量含乙烯基基團之單體合成者。 3·如申請專利範圍第1或2項之方法,其特徵在於以水性乳液 為基準’用於氫化反應之該聚合物乳膠的濃度係為1%至 5 0%)重量。 4·如申請專利範圍第1至3項之方法,其特徵在於於製備該J 屬膠體期間之pH係於3至6之範圍内。5·如申清專利範圍第1 14項之方法,其特徵在於該金屬膠骨 係使用以來自元素週期表(門德列夫)之第¥111]3族的金屬^ 土底及以釘或铑為基底之金屬鹽類或金屬絡合物製得。 =月專利範圍第1至5項之方法,其特徵在於該含膠體导 二混合物之氫化反應係於壓力在〇·1至100巴之範圍内及g 又於25至1〇〇它範圍内進行。 17 200536872 七、指定代表圖·· (一) 本案指定代表圖為:第( )圖。無 (二) 本代表圖之元件符號簡單說明: 無 鲁八、本案若有化學式時,請揭示最能顯示發明特徵的化學式:
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KR101803989B1 (ko) * | 2010-03-05 | 2018-01-10 | 엔엑스 필트레이션 홀딩 비.브이. | 중공 파이버 멤브레인 |
KR20210035088A (ko) | 2018-07-23 | 2021-03-31 | 아란세오 도이치란드 게엠베하 | 수소화된 니트릴 고무의 제조 방법 및 그의 hnbr 조성물 |
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JPS585304A (ja) | 1981-07-01 | 1983-01-12 | Asahi Chem Ind Co Ltd | 水添重合体の製造方法 |
US4801643A (en) * | 1987-03-30 | 1989-01-31 | Hercules Incorporated | Small particle size non-surface active protective colloid-stabilized latexes derived from monomers of high aqueous phase grafting tendencies |
US4994528A (en) * | 1989-12-14 | 1991-02-19 | The B. F. Goodrich Company | Composition of and a method for preparing high-temperature oil-resistant elastomers from hydrogenated butadiene-acrylate copolymers |
US5470906A (en) * | 1993-12-27 | 1995-11-28 | The Glidden Company | Odor free, air dry, decorative latex paints |
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CN100591698C (zh) | 2010-02-24 |
EP1709086A2 (de) | 2006-10-11 |
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