TW215106B - - Google Patents

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Publication number
TW215106B
TW215106B TW080107018A TW80107018A TW215106B TW 215106 B TW215106 B TW 215106B TW 080107018 A TW080107018 A TW 080107018A TW 80107018 A TW80107018 A TW 80107018A TW 215106 B TW215106 B TW 215106B
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Taiwan
Prior art keywords
polymer
hydrocarbon oil
mixture
alkyl
polymers
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TW080107018A
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English (en)
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Shell Internat Res Schappej B V
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    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
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    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
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    • C10L1/00Liquid carbonaceous fuels
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    • C10M145/02Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M145/06Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
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    • C10M145/10Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
    • C10M145/12Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
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    • C10M157/04Lubricating compositions characterised by the additive being a mixture of two or more macromolecular compounds covered by more than one of the main groups C10M143/00 - C10M155/00, each of these compounds being essential at least one of them being a nitrogen-containing compound
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    • C10M169/04Mixtures of base-materials and additives
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    • C10L1/192Macromolecular compounds
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    • C10L1/196Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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    • C10L1/00Liquid carbonaceous fuels
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    • C10L1/197Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
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    • C10L1/234Macromolecular compounds
    • C10L1/236Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
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  • Compositions Of Macromolecular Compounds (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Lubricants (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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215106 Λ 6 13 6 五、發明説明(1 ) 經濟部中央標準局β工消费合作社印製 本發明偽有翮一種含有烴油及聚合性添加物之新穎性烴 油姐合物。 例如瓦斯油、柴油、潤滑油及原油等之烴油類,可含有 大量之鐽垸烴。當此等油類在低溫下貯藏、及使用時 •由於這些鍵烷烴之结晶*可能會造成問題。為了因應此 等問埋,通常係將某些聚合物添加於該鍵烷《性烴油内。 對於此一目的非常有用的一類聚合物,像由含有一飆化碳 之線型聚合物所構成•此聚合物中復含有一或多種烯烴, 該烯烴至少部份由每個分子具有至少10僩碳原子之α —烯 烴(Μ下稱之為(:1〇*〇1—烯烴)所構成;於此聚合物中, 一種單元係由一氧化碳產生*另一種單元係由烯烴類產生 ,,彼此大致是呈交替的狀態。對於-上述目的非常有用的第 二類聚合-_物•係由含有一或多種烯烴性不鉋和化合物之聚 合物所形成*此化合物至少部份由丙烯酸烷酯或甲基丙烯 酸烷酯類所構成(Μ下稱之為(Ce*烷16) ·烷基部份至 少具有8個碳原子。同樣地對於上述目的非常有用的第三 類聚合物,係由含有乙烯及一或多種飽和脂族一羧酸之乙 烯酯的聚合物所構成。 申謫人曾進行在鐽烷烴性烴油内使用聚合物作為添加物 • Μ改菩此等煙油在低溫時之性霣的研究*發現上述第一 類聚合物與第二及/或第三類聚合物的混合物•可呈現協 同之活性;按·此等聚合吻本身分別具有降低此等煙油之 傾點(ΡΡ)、獨黏(CP)及/或冷阻塞黏(CFPP)等 等的活性。此一現象意味著*當該聚合物的混合物被使用 CL - 3 - (請先閲請背面之注意事項再填寫本頁) 本紙張尺Α遑用中Η Β家«準(CNS)甲4規格(210X297公龙) 五、發明説明(2) Λ 6 13 6 經濟部中央標準局A工消#合作社印毅 於一定之濃度下時’所獲得之pp、CP及/或CFPP降低效應 ,較將各聚合物箪獨使用於相同濃度之狀況為強;或是意 味著,該混合物可在低濃度下’獲得相同之PP、CP及/或 CFPP降低效應。 是K,本發明係有鼹—種新穎之烴油姐合物,其特徽偽 在: 此烴油姐合物含有《烷烴性烴油’ Μ及作為添加物之: (a)由一氧化碾與一或多種烯烴類所構成之嫌型聚合物•該 烯烴至少部份由—烯烴)所構成;又’於此聚合 物中,一種單元係由一氧化碳產生·另一種單元係由烯烴 類產生,彼此大致偽呈交替之狀態;及另外之一或多種由 ,Μ下二者所選出的聚合物; _ 4»由烯烴-性不飽和化合物所構成之聚合物’此化合物至少 部份由Ce+烷酿所構成,及 (〇由乙烯及一或多種飽和胞族一羧酸之乙烯酯所構成的聚 合物。 由於鐽烷烴性烴油之低溫性霣可由本發明所改菩,因此 說明可躭瓦斯油、柴油、濶滑油及原油進行。使用本發明 聚合物之混合物於鍵烷烴性瓦斯油及原油中時*可獲得非 常好的结果。根據本發明,用於烴油姐合物中之聚合物的 分子量可被忽略•亦即,此分子最可作廣範圏的改變。較 方便使用之聚合物,具有介於ΙΟ3 - ιοβ之重量平均分子 量(iL),特別好的是重量平均分子最介於ίο4 —ι〇β之 間者。用於製供上述(a)中所提及之聚合物的單體C10«a — C L - 4 * 冬紙張尺度遑用中國國家«準(CNS)甲4規格(210x297公釐)一 (請先閲讀背而之注意事項再塡寫本頁) 裝. 線- 215ί〇δ Λ 6 13 6 五、發明説明(3) 經濟部中央標準局3工消费合作社印製 烯烴* K及用於製備上述<b)中所攞及之聚合物的單》Ce* 烷酯 中之 烷基,最好部沒有分枝。C10* α —烯烴及 Ce ♦烷酯中之烷基在出現時·宜能具有低於40届之«原子 ,最好具有低於30個之碳原子。聚合物之特定分子量· Μ 及製ft聚合物時被用作為覃《之Cu-ct —烯煙及Ce♦烷_ f硬1子的持定數目*主要係由烴油中鍵烷«的性霣所決 定0 於製備上述⑻聚合物時•除了 C1〇+a —烯外•也可 使用諸如乙烯、丙烯、丁烯一〔1〕及環戊烯之碳原子小 於10個的烯烴。用Μ製備上述(ω聚合物之單«混合物•除 了含有一氧化碳之外,埋可含有一種或多種C1〇*ct —烯烴 。根據本發明,可獲得非常良好之·结果的共聚物,其一饀 實例係一-氧化碳/十八烯共聚物一 〔1〕。此外•非常遘 於本發明目的之三聚物的實例是一氧化碳/十四烯一 〔1 〕/十八烯一 〔1〕三聚物。含有一氧化碳及每届分子具 有20— 24涸碳原子之未分枝a —烯烴,也被發現非常遘用 於本發明之聚合物混合物中。 如前所述•有Μ上述⑻中所述之聚合物,較好的是由一 氧化碳與一或多種C1〇*ot —烯烴所構成之聚合物,具有超 遇104之。根據申請人最与對於這些聚合物研究的结果 •發現一種令人注目之製備方法。此—製備方法基本上係 包括:在較离之醞度及壓力,Μ及在含有超《90*積%之 中性溶液的稀釋爾之存在下,使單體與觸媒姐成物接鼸; 此觸媒姐成物中含有族棚金屬及二配位基磷•具有( CL - 5 - (請先閲讀背而之注意事項再塡寫本頁) 本紙張尺度遑用中顧家β準(CNS)1»4規格(210x297公;¢) 五、發明説明(4 ) 經濟部屮央標準局Μ工消t合作社印製 1ϋ2Ρ ) 2R之通式,式中· R1及R2係代表相同或不同之經 選擇性極性取代的胞族氫化二價碳基* R係在橋接兩俚磷 原子處至少含有兩儷碳原子之二價有櫬橋連基。一種較遘 於使用的觴媒姐成物中,相對族V1D金饜之每個克原子•含 有0.75—1.5莫耳之二配位基磷,且R1及R 2同為碳原子數 不超過6個之烷基;此外,相對族VB金屬之每僩克原子, 含有2— 50萁耳之酸的陰醵子·該酸之pKa小於2 ;此外 ,又含有10— 1000荑耳之有櫬氧化劑。特別好的觸媒姐成 物,係由_酸鈀,1 ,3 —雙(二正丁基騮基)丙烷,萘 醺一 〔1,4〕 * Μ及三氟_酸或高氣酸嫌所構成。聚合 物之製備,最好是在30—130 TC之溫度,5— 100 bar之 ,Μ力,5 : 1 — 1 : 5之烯烴相對一氧化碳的荑耳比,Μ 及相對毎-莫耳之待聚合烯烴含有1〇-β— 10_3克原子的族VI 金牖之觸媒姐成物存在的條件下進行。聚合反應最好是在 含有少量非中性液«之稀釋劑中進行。對聚合反應而言特 別好的稀釋劑是四氬呋喃輿甲酵的混合物。 在製備上述乜中所提及之聚合物時,除了 Ce*烷賄之外 •通可使用例如在烷基部份具有少於8個碳原子之丙烯酸 烷酯及甲基丙烯酸烷酯的其他烯烴性不飽和化合物.例如 苯乙烯之烯烴性不飽和芳族化合物•以及例如乙烯基吡啶 類之烯烴性不飽和雜環化合物。用K製備上述(b)中所述之 聚合物的單«混合物,涤可含有一種C»·烷酯•也可含有 多種Ce ♦烷醮。根據本發明•可獲得令人滿意之結果的三 聚物,其實例為:甲基丙烯酸正十二烷酯/甲基丙烯酸正 CL - 6 - (請先閲讀背而之注意事項再填寫本頁) 裝< 線- 本紙張尺度遑用中«家樣準(CNS)甲4規格(210x297公釐) 經濟部t央標準局印製 五、創作説明(s) 十八烷_/2 —乙烯基吡啶三聚物,以及丙烯酸正十八焼 酯/丙烯酸正廿烷酯/丙烯酸正廿二烷酯三聚物。此外· 根據本發明*同樣亦可獲得十分令人滿意之结果的聚合物 •其實例包括:由4 一乙烯基吡啶與烷基部份具有18 — 22俚碳原子之丙烯酸正烷酯的混合物所形成之聚合物·由 烷基部份具有12—15僩碳原子之丙烯酸正烷酯的混合物所 形成之聚合物,以及•由丙烯酸甲酯與烷基部份具有12 — 15届碳原子之丙烯酸正烷醮的混合物所形成之聚合物。 上述(〇中所述之聚合物中·可獲得有利结果之聚合物的 實例,係乙烯與丙酸乙烯酯或釅酸乙烯醮所形成之共聚物 ,特別是乙烯與醋酸乙烯醱所形成之共聚物,尤能獲得良 ,好之结果。此聚合物係可在商業上具有各種分子量及分 子量分布-的狀態購得,有特殊之配方可供現成地添加於烴 油中。’ 根據本發明,於烴油姐合物中·⑻中所述及之一或多種 聚合物,及(b)與(α中所述及之一或多種聚合物•均可出現 。較好的烴油姐合物中·只含有兩種添加物;(a>中所述之 單獨一種聚合物,Μ及(b)輿(〇中所述之單獨一種聚合物。 除了埴些聚合物混合物之外•本發明烴油姐合物堪可含有 諸如抗氧化萷、抗腐蝕劑及金颺活性抑制劑等的其他添加 劑。 根據本發明·聚合物混合物在鏈烷煙性烴油中所含的量 •聚合物在聚合物混合物中的相對比率,係可作廣範園的 變化。較好的是,在毎kg烴油中,含0.1 — 10000 ,特別 CL - 7 - (請先閱讀背面之注意事項再填寫本頁) 裝. 線. 甲 4(210 x 297公釐) 五、創作說明(6 ) 是1 — 10 00 ·8之聚合物混合物。又,所用的聚合物混合物 最好含有10— 75重量%之®中所 含有10— 99重量%,最好含有 所提及的聚合物。 實施例,將本發明舉例說明之。 宜含有1 — 90重最% 提及的聚合 25— 90重 Μ Μ下,茲 〔實施例1 首先,依 共聚物。亦 〔1〕之容 器你被持缅 上述觸媒 .5羅I 0· 1 Bio I _ 0 . 5 η η ο 1 0 . 1 2 ·οιο 1 6 η η ο 1 物,因此•宜 %之(b)與(〇中 以下列若干儼 下述方式製備 即,在内容有 ft為250 的 攪拌*而且其 溶液中含有: 甲酵 _酸鈀 過氯酸辣 1*3-5 #11 - C 1 一種一氧化碳/十八烯一〔1〕 100 ·1四氳呋喃及40g十八烯一 颸热器中,等入簡媒溶液;壓热 內容物係簏罩於氮氣之氛圃中。 (二正丁基膦*)丙烷,4〕 (請先閱讀背面之注意事項再塡寫本頁) 經濟部中央標準局印製 然後,再將一氧化碳射入屋热器•在該一氧化碳之壓力 逹40b ar時,將該壓熱器之内容物加熱至5 0 t:。30小時以 後,»著將反應混合物冷卻_室溫及降懕而將聚合反應终 止。在將丙嗣添加於反®混合物中之後.將聚合物濾除· 並Μ丙酮將其沖洗,然後再予乾嫌。所獲得之產物為= 20300之40 g共聚物。 〔實腌例2〕
CL 甲 4(210x297公釐} Μ 經濟部中央標準局印製 五、創作説明(7 ) 對本寅施例中,侏採用輿實腌例1製備一氧化磺/十八 烯一〔1〕共聚物之步《大致相同的步驟,製備一氣化碳 /十四烯一 〔1〕/十八烯一 〔1〕之三聚物,惟與實施 例1間,有下列之不同點: (a)代替實施例1中之40 g:十八烯一 〔1〕 ’壓热器中含有 30s之十八烯一〔1〕,此外,復含有30g之十四烯一〔 1 ]; ❹代替實腌例1之50 υ,反應湩度採用35 υ ; (c)代替實施例1之30小時,反應時間係採用20小時。 所獲得之產物為Mw= 78000之41s三聚物。 〔實施例3〕 , 於本實腌例中,係採用與實施例~1製備一氧化碩/ +八 烯一〔1-〕共聚物之步驟大致相同的步骤·製備由—氧化 碳與每分子具有20— 24届碳原子之線型ot -烯烴 混合物 所構成的聚合物,惟與實施例1間,有下列之不同黏: ⑸代替實腌例1中之十八烯一 〔1〕,懕热器中含有40s 之每分子具有20 — 2 4個碳原子之線型ct—烯烴混合物; <b>代替S施例1之40bar · —氧化碳係W70bar之懕力射 入壓热器内; (〇代替寘施例1之3 0小時•反應時間係採用1 5小時。 所獲得之產物為fi«= 22700之38g聚合物。 〔實豳例4〕 於本霣施例中•係採用與寘豳例1製備一氧化碳/十八 烯一〔1〕共聚物之步驟大致相同的步驟,製衡—氧化碳 CL - 9 - (請先閲讀背面之注意事項再填寫本頁) 裝< 訂 線. 甲 4(210X297公釐} 經濟部中央標準局印製 五、創作説明(8 ) /十六烯一 〔1〕共聚物,惟與實施例1間,有下列之不 同黏: (a>代替賞施例1中之40g十八烯一 〔1〕,壓熱器中含有 38g之十六烯一〔1〕; (b>代替實施例1之40bar ,一氧化碳係以70bar之颸力射 入壓热器内; (α代替實施例1之30小時,反應時間係採用15小時。 所獲得之產物為iL= 35000之共聚物。 〔實施例5〕 於本實腌例中,涤採用與實施例1製備一氧化碳/十八 烯一 〔1〕共聚物之步驟大致相同的步驟,製備一氧化碳 十四烯一 〔1〕/十六烯一〔1_〕/十八烯一 〔1〕四 聚物•惟J與實施例1間•有下列之不同點: ⑻代替實腌例1中之40s十八烯一〔1〕 •壓熱器中含有 38s之奠耳比為1 : 2 : 1的正一C14 /正一Cie /正一 Cie α —烯烴混合物; (b)代替霣腌例1之40bar ,一氧化碳係K 70bar之壓力射 入®熱器内; (〇代替S施例1之30小時*反應時間涤採用15小時。 所獲得之產物為22000之42 g四聚物。 〔實施例6〕 於本*施例中,係將下列聚合物作為添加物予K測試, 將其添加於兩種原油(A與B)及兩種瓦斯油(C與D) 中,以降低此等油類之PP。 CL - 10 - Μ (請先閱讀背面之注意事項再填寫本頁) 裝- 線_ 甲 4(210 x 297公釐) Μ 經濟部中央標準局印製 五、創作説明(9) 添加物1 :依★施例1所製備之共聚物。 添加物2 :依貫腌例2所製備之三聚物。 添加物3 :依實腌例3所製備之聚合物。 添加物4:甲基丙烯酸正十二烷酯/甲基丙烯酸正十八烷 酯/ 2—乙烯基吡啶三聚物,^為66000 。 添加物5:丙烯酸正十八烷酯/丙烯酸正廿烷酯/丙烯酸 正廿二烷酯三聚物· 1^«為220000。 添加物6 :由4 一乙烯基吡啶與烷基部份含有18 — 22«碳 原子之丙烯酸正烷酯類混合物所構成的聚合物· 1為 135000 〇 添加物7 :由烷基部份含有12—15俚碳原子之丙烯酸正烷 ,酯類混合物所構成之聚合物,iL為-160000。 添加物8-:由丙烯酸甲醣與烷基部份含有12— 15俚《原子 之丙烯酸正垸酯類混合物所形成之聚合物· 1為224000。 將上述各種聚合物,M50重量%固體溶於甲苯所得之溶 液的形態,導入各種油類之中。霣驗之结果係示於下列之 表I中;表中,PP係在預熱至上述溫度(50艺或90=)後 測定•此外,若可行的話•在50t:才將上述量之聚合物溶 液添加於油類中*於聚合物溶液係以聚合物溶液/ kg鐽 烷烴油之方式表示。所有添加物之混合物,添加物之重量 比均為1 : 1 ,惟測試5中之混合物的重量比為1 : 2。 又.PP偽依檷準法ASTM D97测得》 CL - 11 _ 甲 4< 210 X 297公釐) (請先閱讀背面之注意事項再塡寫本頁) 裝- #- -線· 2l5i〇6 Λ 6 B6 五、發明説明(10 ) 表I傾點 經濟部中央標準局3工消費合作社印製 測試 No 烴油 添加物 Nos 溶液 ng/kg 預熱 PP 它 *1 A 50 30 2 A 1+6 2000 50 21 3 A 1+6 4000 50 15 4 A 1+6 6000 50 12 n5 A 1+6 6000 50 12 *6 A - - 90 30 7 A 3+6 400 90 21 8 A 3+6 600 90 18 9 A 3+6 1000 90 12 10 A 3+6 2000 90 12 *11 B . - — - 90 27 12 B 3+5 400 90 3 IS- B 3+5 600 90 0 14 B 3+5 800 90 0 ★15 C - - 50 -12 16 r 2 + 7 200 50 -21 *17 C 1 100 50 -15 ^18 C 1 2000 50 -18 *19 C 1 4000 50 -18 *20 C 4 100 50 -15 *21 c 4 2000 50 -21 *22 c 4 4000 50 -21 23 - c 1+4 ' 100 50 -21 24 c 1+A 2000 50 -33 25 c 1+4 4000 50 -36 *26 D - - 50 -18 *27 D 1 200 50 -21 *28 D 8 200 50 -24 29 D 1+8 200 50 -27 CL -12- (請先閲讀背面之注意事項再填寫本頁) 裝· 訂- 線- 本紙》JUtii用中《«家«準(CNS)甲4規格(210x297公龙) 經濟部中央標準局印製 五、創作説明(11) χ =非本發明•僅供比較用 # =添加物1 :添加物6之重量比=1 : 2 上述供测試PP之十六種含有聚合物混合物之烴油姐合物 ,偽本發明之姐合物。使用前述銳明部份©>中之聚合物與 (b)中之聚合物所姐成的混合物時,所造成之協同作用,係 可由使用添加物1 (測試17 — 19>或添加物4 (测試20 — 22)之實驗结果,與使用添加物1及4之1 : 1混合物( 测試23— 25)之實驗结果的比較*獲得充份之瞭解。比較 針對瓦斯油D實施之_試26— 29的结果可發現,此一協同 作用也會顯著地呈現。 ,〔實腌例7〕 一 於此實-Ife例中•偽將下列聚合物作為添加物予Μ测試· 將其添加於瓦斯油(Ε)中·Μ降低該瓦斯油之CFPP。 添加物9:依霣施例4所製備之共聚物。 添加物10:依霄梅例5所製侮之共聚物。 添加物11:乙烯與醏酸乙烯酯之共聚物,可由商業行為Μ 溶液狀_得,商檷名為PARAMIN ECA 5920 ° 添加物12:乙烯與醣酸乙烯歯之共聚物,可由商業行 溶液狀購得,商檷名為PARAMIN PARAFL0V 214。 添加物13:乙烯與酗酸乙烯酯之共聚物,可由商業行為以 溶液狀購得•商檷名為PARAMIN ECA 8182。 添加物9與10,係K50重量%固《溶於甲笨所得之溶液 CL - 13 - (請先閱讀背面之注意事項再塡寫本頁) -装· 訂_ 線. 甲 4(210X 297公釐) 五、創作説明(12) 的形態,添加於瓦斯油中。添加物11— 13,係Μ其商樂溶 液之形態,添加於瓦斯油中。實驗之结果你示於下列之表 I中;表中,CFPP係在預熱50Τ後測定,此外,若可行的 話•在501C才將上述量之聚合物溶液添加於瓦斯油中,該 聚合物溶液係Mug聚合物溶液/ kg瓦斯油之方式表示。所 有添加物之混合物*添加物之重量比約為1 : 1。又, CFPP係依檷準法IP 309测得。 表ϋ冷過濾姐塞點 (請先閱讀背面之注意事項再塡寫本頁) 經濟部中央橾準局印製 测試 ,Νο 添加物 Nos 溶液 rag / k g ~ CFPP t: *30 - - - -6 *31 9 40 -9 *32 12 40 -12 33 9+12 40 -19 *34 9 75 -12 ★35 12 75 -14 *36 12 300 -19 37 9+12 .75 -20 *38 11 40 -12 *39 11- 75 -16 *40 11 .300 -21 41 9+11 75 -24 *42 13 40 -15 43 9+13 40 -20 44 10+12 75 -19 *45 10 75 -13 *46 13 75 -16 Φ7 10+13 75 -19 CL -14- 線· 甲 4(210X 297公釐} i 五 、創作説明(l3) X =非本發明,僅供比較用 上述 •係本 (C>中之 可由潮 試31, 試姐之 敘述 1-5 ,可瞭 ,由一氣 此係呈 烴的單 所產生 供洒試CFPP之 發明之姐合物 聚合物所姐成 試31— 33,測 42及43,測試 相互比較结果 用於實施例6 ,並非落於本 解此等聚合物 化碳產生,另 交-替之狀態。 «混合物所製 之單元•係相 六種含有聚合物混合 °使用前述說明部份 的混合物時,所造成 試34 · 35及37,測試 35 · 44及45,或是測 •獲得深入之瞭解。 及7中之添加物的製 發明之範匾之内。輅 係呈埭型之鍵狀•其 物之烴油姐合物 中之聚合物與 之協同作用,係 34 , 39及 41 * Μ 試45— 47等各测 儋«程之實施例 著13C-KMR分析 中•一種單元係 一種箪元係由-烯烴產生,彼 更多Cio-a —嫌 此外·由含有兩種或 得之聚合物中•由各種(^ 對他者呈無規之次序狀態 烯烴 閱 讀 背. 面 之 注 意 事 項 再 填 寫 本 頁 裝 ΤΓ 線 經濟部中央標準局印製 甲 4(210X297公釐) 5 hi· hi· Η L._______. 第八〇 — 〇七〇-八號專利申請栗 中文補充說明書(八+二年三月) 以下列聚合物作為添加物,進行測試: 添加物14: ίΰ為7100之一氧化碳/卜十二碳烯共聚物’ 添加物15 : ΪΓ„為93600之一氧化碳/1-十四烯共聚物’ 添加物16 : ί:為8600之一氧化碳/卜十六烯共聚物,及 添加物17 : ίΰ·為110,000之乙烯與乙酸乙烯酯聚合物。 Κ貢例1之方式製得添加物14-16之共聚物,但Μ通宜α -烯烴取代 1-十八烯。添加物17之聚合物係市售可得者。 於測試中使用下列鍵烷烴性烴油: 油F :流動點為-27的煤油, 油G :流動點為-36T:的低硫、低芳番汽油(low-sulphur lovr-aromat i c gas oil), 油H :流動點為-4610的低硫、低芳香汽油, 油J :流動點為ου之脫蠼輕機油。 烴油與添加物之混合方法、及測試方法,實質上均如實例6所描述 。含重量比1:1之二棰不同聚合物的添加物混合物係Κ每公斤油 300毫克聚合物的重量加入*於5¾下進行預熱。所得结果如下所系 EN\0157.g 4丨 ----------------- 表m —流動點 測試編號 油 添加物編號 流動點(C ) 48* F — -27 49 F 14 + 17 -39 50Λ G — -36 51 G 15 + 17 -57 52* Η 一 -46 53 Η 15 + 17 -66 54* J 一 0 55 J 16 + 17 -6 比較用,非依據本發明。 ENX0157.g -2-

Claims (1)

  1. 號專利肀請業 到範g修正本CVHMl _ iE 82. B 六、中妹森』丨15[11 ‘ * % 2. A7 B7 C7 D7 公告本 種烴油組合物,其特戡為該烴油姐合物含有流動黏為 -60t:至401C之鍵烷烴性烴油,以及作為添加物之: <a) 一種多種線型聚合物,此聚合物係由一氧化碳及一 或多種ot -烯烴類所構成,該烯烴類每分子係含有 12-24涠碳原子(C12*cx —烯烴)所構成;於該聚 合物中•其一端係起始自一氧化碳,另一皤則起始 .自烯烴類,該聚合物係具一般式- C0-A-之重覆單元 ,其中A係源自該烯烴之單元,及選自下列(b>、<〇 之一種或多種聚合物: (b) 由一種或多種烯烴性不跑和化合物所構成之聚合物 *該化合物至少部份由丙烯酸烷酯類或甲基丙烯酸 烷酯類所構成,此等酯類之烷基部份係含12- 18個 碳原子(C12*ct -烷酯),該聚合物含一般式 -CD-CH2-之單體單元,其中B表具12-18倨碳原子 I C0-0B 之烷基且D為氳或甲基•及 (〇 由乙烯與丙酸乙酯或乙酸乙酯所構成的聚合物, 其中於⑻.⑮及(〇中所提友之》合物係具1〇3 - ι〇β之重 量平均分子量(1ΓΓ)且其於姐合物.中之量為每公斤烴油 0.1 -10,000»g該聚合物混合物·該聚合物混合物係含 1-90%重之(¾中所述聚合物與1〇 - 99%重之(b>及<〇中所 述聚合物。 根據申讅專利範匾第1項之烴油姐合物,其特微為該聚 f 4 (210X297 二、餐) (請先閩讀背面之注意事項再瑱珥本页) 一 Α7 Β7 C7 D7 AW 六、申請專利範面 合物係具ίο4 - ι〇β之重量平均分子量(G)。 3. 根據申請專利範圍第1或2項之烴油姐合物,其特微為該 烴油組合物涤含⑻中所述的聚合物’該聚合物係由一氧 化碳與一或多種C12*ct —烯烴所構成,具有超過’104 之此一聚合物係可藉著在較高之溫度及臛力,以及 在含有超過90體積%之中性溶液的稀釋劑之存在下,使 單級與觸媒姐成物接觸而製成;此觸媒姐成物中含有族 VI金靨及二配位基瞵,具有) 2R之通式*式中 • R1及R2係代表相同或不同之經選擇性極性取代的脂族 氳化二價碳基,R係在橋接兩個磷原子處至少含有兩届 碳原子之二價有檐橋連基。 4. 根據申謫專利範圍第1或2項之烴油組合物,其特微為該 烴油狙合物係含(b)中所述的聚合物,該聚合物係選自: 甲基丙烯酸正十二烷醏/甲基丙烯酸正十八烷醏/2— 乙烯基吡啶三聚物*丙烯酸正十八烷醅/丙烯酸正廿焼 酯/丙烯酸正廿二烷酯三聚物•由4 一乙烯基吡啶與焼 基部份含有18—22俚碳原子之丙烯酸正烷酯類混合物所 形成之聚合物,由烷基部份具有12— 15個碳原子之丙嫌 酸正烷酯類混合物所形成乏聚奋.'物,以及由丙烯酸甲酶 與烷基部份含有12—15儷碳原字之丙烯酸正烷酯類混合 物所形成之聚合物。 5. 根據申讅專利断圔第1或2項之烴油组合物*其特微為該 烴油姐合物僅含有(a)中所述聚合物之一種,以及(b)輿⑵ 中所述聚合物之一種。 f 4(210X 297 二Ί :,........^.....................ί ................St..............................ίτ..............................##.- (請先閱讀背面之注意事項再洗寫本一β) 蜓濟邶中央搮準局印装 2 _ D7 六、申請專利範® 6. 根據申請專利範園第1或*2項之烴油姐合物,其特激為 該烴油組合物係含有相對每公斤之煙油用最為1-1,000 鼍克之聚合物混合物。 7. 根據申請專利範画第1或2項之烴油組合物,其特徴為該 所用之聚合物混合物係含有10- 75重量%之(¾中所述的 聚合物。 (請先聞讀背面之注意事項再*寫本页) 經濟部中央標準扃印繁 為* it..............................ίτ..............................Sf ίΡ4(210Χ 297^¥) 2
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EP0479353A1 (en) 1992-04-08
BR9104056A (pt) 1992-06-02
US5246608A (en) 1993-09-21
KR920006484A (ko) 1992-04-27
DE69102750D1 (de) 1994-08-11
JPH04261123A (ja) 1992-09-17
KR0176252B1 (ko) 1999-04-01
CA2052008C (en) 2001-12-04
AU645607B2 (en) 1994-01-20
CN1032371C (zh) 1996-07-24
EP0479353B1 (en) 1994-07-06
ES2055958T3 (es) 1994-09-01
CA2052008A1 (en) 1992-03-26
CN1060106A (zh) 1992-04-08
DE69102750T2 (de) 1994-12-01
RU2027741C1 (ru) 1995-01-27
AU8469891A (en) 1992-04-02
JP3064058B2 (ja) 2000-07-12

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