[go: up one dir, main page]

TW574237B - Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith - Google Patents

Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith Download PDF

Info

Publication number
TW574237B
TW574237B TW90127567A TW90127567A TW574237B TW 574237 B TW574237 B TW 574237B TW 90127567 A TW90127567 A TW 90127567A TW 90127567 A TW90127567 A TW 90127567A TW 574237 B TW574237 B TW 574237B
Authority
TW
Taiwan
Prior art keywords
patent application
magnesium
scope
item
catalyst
Prior art date
Application number
TW90127567A
Other languages
Chinese (zh)
Inventor
Steven D Gray
Tim J Coffy
Original Assignee
Fina Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/687,688 external-priority patent/US6486274B1/en
Application filed by Fina Technology filed Critical Fina Technology
Application granted granted Critical
Publication of TW574237B publication Critical patent/TW574237B/en

Links

Landscapes

  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Description

574237 經濟部智慧財產局員工消費合作社印製 A7 _____B7 _五、發明説明（3 ) 但是，雖然在先前技藝中有這些發展，但是沒有任何 一個這些先前技藝文獻揭示或提出在1^(：14/了丨（〇1)4之混合 物中的R特性將提供具有改良型氫反應之觸媒，其可以提 供具有更窄的分子量分佈（“MWD”）。 因此，在本技藝中要求聚烯烴觸媒。 本技藝中另外要求製得聚烯烴觸媒之方法。 本技藝中甚至另外要求聚合烯烴類之方法。 本技藝中仍另外要求更窄的MWD之聚烯烴類。 本技藝中還另外要求具有改良型氫反應之觸媒。 本技藝中甚至仍另外要求提供製得具有窄分子量分佈 之聚合物的聚烯烴觸媒之方法，其中該方法包含使用 Ti(〇Pr)4及TiCl4之摻合物。、 本技藝甚至還另外要求製得更窄的MWD之聚烯烴類之 方法。 那些熟悉本技藝的人在檢視本說明書（包括其圖形及申 請專利範圍）時將會明白本技藝的這些及其它需求。 本發明的槪述 本發明的一個目的係提供聚烯烴觸媒。 本發明的另一個目的係提供製得聚烯烴觸媒之方法。 本發明的另一個目的係提供聚合烯烴類之方法。 本發明仍有的另一個目的係提供更窄的MWD之聚烯烴 本發明還有的另一個目的係提供具有改良型氫反應之 本紙張尺度適用中國國家標準（CNS &規格（210x297公釐）Ζ〇Ζ — (請先閱讀背面之注意事項再填寫本育) 訂 574237 A7 B7 五、發明説明（4 ) 觸媒。 本發明甚至仍有一個目的係提供製得具有窄分子量分 佈之聚合物的聚烯烴觸媒之方法，其中該方法包含使用 Ti(〇Pr)4及丁 iCh之摻合物。 本發明甚至還有一個目的係提供製得更窄的MWD之聚 烯烴類之方法。 本發明的一個具體實施例係提供以通常包含：a)以通式 Mg(OR")2之可溶性二烷醇鎂化合物與能夠以一個鹵素交換 一個烷醇鹽之鹵化劑接觸，以形成反應產物A，在此R"係 具有從1至20個碳原子之烴基或經取代之烴基；b)將反應產 物A與第一個鹵化/鈦酸化試劑接觸，以形成反應產物b ; 及c)將反應產物B與第二個鹵化/鈦酸化試劑接觸，以形成 觸媒組份之方法所生產之觸媒組份。第一個鹵化/鈦酸化試 劑係以ΤΚ〇Ρι·)4及TiCh之摻合物較佳。可溶性二烷醇鎂化 合物係包含通式MgRR’之烷基鎂化合物（其中R及V係1-10 個碳原子之烷基，並可以相同或不相同）與通式R"〇H之醇（ 其中醇係直鏈或支鏈醇及其中R’’係4-20個碳原子之烷基）的 反應之反應產物。 本發明的另一個具體實施例係提供觸媒。通常觸媒係 由本發明的觸媒組份與有機鋁預活化劑一起接觸所生產的 。觸媒通常由包含i)以通式Mg(〇R”l·-之二烷醇鎂化合物與 能夠以一個鹵素交換一個院醇鹽之鹵化劑接觸’以形成反 應產物A，在此R，，係具有從1至2 0個碳原子之烴基或經取代 之烴基；ii)將反應產物A與第一個鹵化/鈦酸化試劑接觸’ (請先閲讀背面之注意事項再填寫本頁) 、τ ii. 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -7 - 574237 經濟部智慧財產局員工消費合作社印製 A7 _ B7 _五、發明説明（5 ) 以形成反應產物B ;及iii)將反應產物B與第二個鹵化/欽 酸化試劑接觸之方法所生產的。第一個鹵化/鈦酸化試劑係 以Ti(〇P〇4及TiCU之摻合物較佳。本發明的觸媒具有改良 型氫反應，並有助於生產具有預期的分子量分佈之聚合物 〇 本發明甚至以另一個具體實施例提供以包含：a)以一或 多種α -烯烴單體在聚合條件下一起在觸媒的存在下接觸。 以使用觸媒聚合聚乙烯單體較佳，以生產聚乙烯聚合物。 觸媒通常由包含i)以通式Mg(OR)2之二烷醇鎂化合物與能夠 以一個鹵素交換一個烷醇鹽之鹵化劑接觸，以形成反應產 物A，在此R係具有從1至20個碳原子之烴基或經取代之烴 基；ii)將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 成反應產物B ;及iii)將反應產物B與第二個鹵化/鈦酸化 試劑接觸，以形成觸媒之方法所生產的。在至少其中一個 步驟b)及c)中，鹵化/鈦酸化試劑係以Ti(〇Pr)4/TiCl4較佳。 觸媒生產法尙可以包含以觸媒組份與有機鋁試劑接觸。 本發明仍以另一個具體實施例提供包含本發明的觸媒 及惰性擔體之觸媒系統。惰性單體係以鎂化合物較佳。 本發明還以另一個具體實施例提供用於形成觸媒組份 之方法。通常本方法包含：a)以通式Mg(〇R”）2之二烷醇鎂 化合物與能夠以一個鹵素交換一個烷醇鹽之鹵化劑接觸， 以形成反應產物A，在此R”係具有從1至20個碳原子之烴基 或經取代之烴基；ii)將反應產物A與第一個鹵化/鈦酸化試 劑接觸，以形成反應產物B ;及iii)將反應產物B與第二個 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -8 - —II—14丨丨丨-i------# (請先閱讀背面之注意事項存填寫本頁) 574237 A7 _ B7 五、發明説明（6 ) 鹵化/鈦酸化試劑接觸，以形成觸媒組份，或反應產物C。 在至少其中一個步驟b)及c)中，鹵化/鈦酸化試劑係以 Ti(〇Pr)4/TiCl4 較佳。 本發明甚至仍以另一個具體實施例提供用於形成觸媒 之方法，該方法包含以觸媒組份與有機鋁預活化試劑一起 接觸。 本發明甚至還以另一個具體實施例提供α -烯烴聚合法 。通常聚合法包含：a)以一或多種α -烯烴單體在聚合條件 下一起在觸媒的存在下接觸；及b)萃取聚烯烴聚合物。聚 合法有助於生產具有分子量分佈小於7之聚合物，以具有聚 乙烯較佳。 那些熟悉本技藝的人在檢視本說明書（包括其圖形及申 請專利範圍）時將會明白本技藝的這些及其它目的。_ 本發明的詳細說明 本發明的觸媒組份製法通常包括以二烷基金屬與醇形 成二烷醇金屬、鹵化二烷醇金屬、以二或多個步驟中的鹵 化/鈦酸化形成觸媒（以至少其中一個步驟利用Ti(OP〇4/TiCl4 之混合物）及接著以預活化劑（如有機鋁）處理觸媒，以形成 預活化之觸媒的步驟。 以本發明的方法提出之機制通常如下： 1. MRR，+ 2R"〇H -> M(〇R")2 ； 2. M(〇R，，）2 + C1AR，"X -> “A” ； 3·“Α” + TiCWTi(〇Pr)4 “B” ； 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9 - ——I-14—, (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 574237 A7 __ _B7_ 五、發明説明（7 ) 4·“Β” + TiCh — “C” ：及 5.“C” + TEAI —預活化之觸媒。 在上式中，Μ是任何適合的金屬，以IIA族金屬較佳 ’以Mg最佳。在上式中’ R、R’、R’’及R’"係各自獨立是 烴基或經取代之烴基部份，以R及IT具有從1至20個碳原子 ，以從1至10個碳原子較佳，以從2至6個碳原子更佳，並以 從2至4個碳原子甚至更佳。R”通常包含從3至20個碳原子， 通常包含從2-6個碳原子。二或多個R、R’、R"及R…之 任何組合可以相同或R基可以彼此不同。 在上式C1AIT'中，A係未還原之親氧基化合物，其能 夠以一個氯化物交換烷醇鹽，R"’係烴基或經取代之烴基及 X係A減1之價數。A之實例包括鈦、矽、鋁、碳、錫及鍺 ，以其中X是3之鈦及矽最佳。R…之實例包括甲基、乙基 、丙基、異丙基及具有2-6個碳原子之類似物。R"’通常是丙 基。 雖然不知道產物” A”的實際化合物，但是咸信其包括部 份氯化之金屬化合物，其的一個實例可以是ClMg(〇R")。 以第一個氯化/鈦酸化作用產生的反應產物” B”有可能是氯化 及部份氯化之金屬及鈦化合物之複合物，並例如有可能以 (MCh)y，·（TiCh(〇Pr)4_小’代表。以第二個氯化/鈦酸化作用 產生的觸媒組份”C”也有可能是氯化及部份氯化之金屬及鈦 化合物之複合物，但是，與υΒ”不同，並有可能以 (MCl2)y· (1^1^(〇？1‘)〇，）2，代表。吾人預期”0”之氯化程 度可能大於” B”之程度。該較大的氯化程度可能產生不同的 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -10- " ~ 1·~丨"♦11 (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 574237 A7 __ B7 _ 五、發明説明（8 ) 化合物不同的複合物。雖然該反應產物的說明提供在同時 最有可能的化學解釋，但是在申請專利範圍內說明的本發 明不受該理論上的機制所限制。 適用於本發明的二烷基金屬及所得二烷醇金屬包括任 何供本發明使用時將會得到適合的聚烯烴觸媒者。較佳的 二烷醇及二烷基金屬包括二烷醇及二烷基IIA族金屬。二 烷醇或二烷基金屬係以二烷醇或二烷基鎂更佳。 在本發明的實地應用中，二院基鎂[MgRR」可以是任何 二烷基鎂，在此R及R’係如以上的說明。R及R’可以相同 或不相同。適合的二烷基鎂的非限制性實例包括二乙基鎂 、二丙基鎂、二丁基鎂、丁乙基鎂等。以丁乙基鎂（BEM)係 較佳的二烷基鎂。 在本發明的實地應用中，二烷醇金屬係以通式 Mg(〇R”）2之鎂化合物較佳，在此R"係1至20個碳原子之烴 基或經取代之烴基。 二烷醇金屬以具有可溶性最佳及以未還原最佳。未還 原化合物具有形成MgCh之優點，取代以化合物的還原作用 所形成的不可溶之Ti + 3物種，如MgRR’，其傾向於形成具有 寬的粒子尺寸分佈之觸媒。此外，Mg(〇R”）2具有比MgRR’ 更低的反應性，並且以溫和的氯化劑之氯化作用，接著以 溫和的試劑同時的氯化/鈦酸化作用及第二個以較強的試劑 之氯化/鈦酸化作用係逐漸及依續較強的反應，其可以生成 更均勻的產物，即更好的觸媒粒子尺寸控制及分佈。 有用的二烷醇金屬較佳的物種的非限制性實例包括丁 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐） -11 - — I.-I — (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 574237 經濟部智慧財產局員工消費合作社印製 A7 __B7_五、發明説明（9 ) 醇鎂、戊醇鎂、己醇鎂、二（2-乙己醇基）鎂及任何適合於製 造可溶性系統之烷醇鹽。最佳的烷醇金屬物種是二（2-乙己 醇基）鎂。 可以烷基鎂化合物（MgRm(如丁乙基鎂（BEM))與醇 (ROH)(如2-乙己醇）反應可以生產作爲非限芾丨J性實例之二烷 醇鎂，如二（2-乙己醇基）鎂。 MgRR, + 2R,5OH — Mg(〇R”）2 + RH + ITH 在BEM之情況中，RH及R’H分別是丁烷及乙基。反 應發生在室溫下及以反應物形成溶液。 在本發明的實地應用中，可以利用任何得到預期的二 烷醇金屬之醇。可以任何通式R"OH之醇作爲醇的非限制 性實例，在此R"係4-20個碳原子之烷基。雖然咸信可以利 用幾乎任何醇，但是最好利用高碳支鏈醇。醇可以是直鏈 或支鏈醇。醇的非限制性實例包括丁醇、異丁醇、2-乙基-1-己醇等。較佳的醇是2-乙基-卜己醇。通常所利用的醇將 具有至少3個碳原子，以至少4個較佳，以至少5個更佳及以 至少6個最佳。 加入泥漿中的醇量通常係以約0.5當量至約4當量爲範圍 (該當量係相對於整個鎂或金屬化合物），以約1至約3當量爲 範圍較佳。 烷基金屬化合物具有高締結性，由於缺乏電子之鍵結 ^以其生成在溶液中非常黏的局分子量物種。以加入院基 鋁（如三乙基鋁）可以降低該高黏度，以其瓦解在各個烷基金 屬分子之間的締結作用。較佳的烷基鋁對金屬之比例是 本G張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- I n I I - n n I I I I I_ I T I I__I. (請先閱讀背面之注意事項再填寫本X) 574237 經濟部智慧財產局員工消費合作社印製 A7 ___B7 _五、發明説明（10 ) 0.001··1至 1··1，以 0.01:1至 〇·1:1更佳，並以 0.03:1 至 0.05:1最 佳。此外，可以使用電子給予體進一步降低烷基金屬之黏 度，如醚，例如，二異戊醚（DIAE)。較佳的電子給予體對 金屬之比例是0:1至1 0:1，並以0.1:1至1:1更佳。 在使烷醇金屬鹵化的鹵化步驟中有用的試劑包括任何 供本發明使用時將會得到適合的聚烯烴之鹵化劑。鹵化步 驟係以氯化步驟較佳，並且較佳的鹵化劑是氯化物。 氯化物鹵化劑（“氯化劑”）係以只將烷醇鎂以部份氯化之 單氯化物較佳，較佳的氯化劑具有通式 C1AR"\·或 C1AOR"、，在此A係未還原之親氧基化合物，其能夠以一 個氯化物交換烷醇鹽，R…係烷基及X係A減1之價數。A 之實例包括欽、砂、錦、碳、錫及鍺’以其中X是3之欽及 矽最佳。R…之實例是甲基、乙基、丙基、異丙基及具有2-6 個碳原子之類似物。在本發明有效的氯化劑之實例是 ClTUCVPrh及 ClSi(Me)3。 通常在惰性氣體下的烴溶劑中進行烷醇金屬化合物之 鹵化。適合的溶劑的非限制性實例包括甲苯、庚烷、己烷 、辛烷及類似物。較佳的溶劑是己烷。 通常在約0。(：至約1 〇〇 °C爲範圍之溫度下及以約〇 · 5小時 至約24小時爲範圍之反應時間進行鹵化步驟。以在約20 °c 至約90°C爲範圍之溫度下及以約1小時至約4小時爲範圍之 反應時間進行鹵化步驟較佳° 一旦進行鹵化步驟及將烷醇金屬鹵化時’則將可溶性 鹵化物產物” A”進行一或多次鹵化/鈦酸化處理，至少其中一 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）_ 13 - (請先閲讀背面之注意事項再填寫本頁) 574237 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（11 ) 次必須利用TiClWTUCVPrh之混合物。第一個鹵化/鈦酸化步 驟以利用TiCh/TUCT.Prh之混合物較佳。 通常鹵化/鈦酸化試劑係全部4個是相同的取代基及以其 是鹵或物或具有2至10個碳原子之烷醇鹽或酚鹽之取代基經 四取代之鈦化合物，如TiCh或Ti(Of…）4。鹵化/鈦酸鹽試 劑係以氯化/鈦酸化試劑較佳。 較佳的氯化/鈦酸化試劑可以是單一化合物或化合物之 組合物。本發明的方法係在第一個氯化/鈦酸化步驟之後提 供活性觸媒；但是，以每次使用不同的化合物或化合物組 合物進行兩次氯化/鈦酸化作用較佳，並在每個依續的氯化/ 鈦酸化處理使用更強的氯化/鈦酸化試劑。 第一個氯化/鈦酸化試劑係以溫和的鈦酸化試劑較佳， 以鹵化鈦與有機鈦酸鹽之摻合物較佳。咸信以鹵化鈦與有 機鈦酸鹽之摻合物反應會形成烷氧基鹵化鈦Ti(〇R)aXb，在 此OR及X分別是在烷醇鹽及鹵化物中，a + b是鈦之價數， 其以4爲代表，並且a及b可以是分數，例如，a = 2.5及 b= 1.5 〇 第一個氯化/鈦酸化試劑係以TiCl4與Ti(〇iP〇3之摻合物 或以TiCl4與Ti(0iPr)4之摻合物更佳。至少其中一個氯化/鈦 酸化步驟必須利用TiCh與Ti(0iP〇4之摻合物，並最好以第 一個氯化/鈦酸化試劑是TiCl4與Ti(0iPr)4之摻合物。 或 TiCl4/Ti(〇Bu)4，或 TiClWTi(〇iPr)4，TiCU 對或 Ti(〇Bu)4或Ti(〇iP〇4之比例係從0.5:1至6:1爲範圍，以i:i至 4:1更佳及從2:1至3:1最佳。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-14 - (請先閲讀背面之注意事項再填寫本頁) 574237 經濟部智慧財產局員工消費合作社印製 A7 B7_五、發明説明（12) 通常在烴溶劑中進行第一個鹵化/錄酸化步驟。適合的 烴溶劑的非限制性實例包括庚烷、己烷、甲苯、辛烷及類 似物。產物”A”可溶於烴溶劑中。 將固體產物” B”在室溫下沉澱，接著將鹵化/鈦試劑加入 可溶性產物”A”中。 所使用的鹵化/鈦試劑量必須充份自溶液沉澱固體產物 。通常所使用的鹵化/鈦試劑量以鈦對金屬之比例爲基礎計 通常以約0.5至約5爲範圍，以約1至約4爲範圍較佳，並以約 1.5至約2.5爲範圍最佳。 接著以任何回收技術回收在該第一個鈦酸化步驟中沉 澱的固體產物”B”，並接著以烴溶劑淸洗。 適合作爲第二個鹵化/鈦酸化試劑使用的化合物包括那 些適合作爲第一個鹵化/鈦酸化試劑使用的化合物，除了第 二個試劑是較強的試劑之外（較佳）。第二個鹵化/鈦酸化試 劑較強，並以鹵化鈦較佳，以四氯化鈦[TiCh]更佳。 通常將固體產物”B”在烴溶劑中泥漿化，以進行第二個 鹵化/鈦酸化步驟，以生產反應產物或觸媒組份”C”。可以利 用適合於第一個鹵化/鈦酸化步驟所陳列之烴溶劑。通常所 使用的四氯化鈦量通常以約〇. 1至約5當量爲範圍，以約0.1 5 至約4當量爲範圍較佳，以約0.175至約2.5爲範圍最佳。 可將觸媒組份”C”與有機鋁共觸媒組份（“預活化劑”）組 合，以形成適合於烯烴類聚合之預活化之觸媒。與含觸媒 組份”C”之過渡金屬一起使用的共觸媒典型係la、Ila及Ilia 金屬之有機金屬化合物，如烷基鋁、烷基氫化鋁、烷基鋰 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -15 - (請先閲讀背面之注意事項再填寫本頁) 574237 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明説明（13) 鋁、烷基鋅、烷基鎂及類似物。 預活化劑係以有機鋁化合物較佳，以式airs之烷基鋁 更佳，在此RM系具有1-8個碳原子之烷基或鹵化物。較佳的 有機鋁預活化劑包括三烷基鋁，例如，三甲基鋁（TMA)、三 乙基鋁（TEA1)及三異丁基鋁（TiBAl)。最佳的預活化劑是 TEA1。A1對鈦之比例係以從0.1:1至2:1爲範圍，並以0.25:1 至1.2·· 1較佳。接著將觸媒回收及以烴溶劑淸洗。 可視需要將電子給予體與鹵化劑、第一個溫和的鹵化/ 鈦酸化試劑或第二個較強的鹵化/鈦酸化試劑一起加入。以 在第二個鹵化/鈦酸化步驟中使用電子給予體最佳。已熟知 在烯烴製備作用中使用的電子給予體，並可在本發明利用 任何將提供適合的觸媒之適合的電子給予體。 也是已知的路易士鹼之電子給予體係氧、氮、磷或硫 之有機化合物，其可以給予觸媒電子對。 電子給予體可以是有利於選自脂肪族或芳族羧酸及其 烷基酯、脂肪族或環系醚、酮、乙烯酯、丙烯基衍生物（特 別是丙烯酸烷基酯或甲基丙烯酸烷基酯）及甲矽烷之間的單 官能或多官能化合物。適合的電子給予體較佳的實例是酞 酸二正丁酯。適合的電子給予體更佳的實例是通式 RSi(〇R’）v之烷基甲矽烷基烷醇鹽，例如，甲基甲矽烷基三 乙醇鹽[MeSi(〇Et3)]，在此R及R’係具有1-5個碳原子之烷 基，並可以相同或不相同。 本發明的觸媒系統之擔體應該是與任何熟知的齊格爾-納塔型觸媒之組份不具化學反應之惰性固體。擔體係以鎂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) -16 - (請先閲讀背面之注意事項再填寫本頁) 574237 A7 __ B7 五、發明説明（14 ) 化合物較佳。可用於提供作爲觸媒組份之擔體的鎂化合物 之實例是鹵化鎂、二院氧基鎂、鹵化院氧基鍾及鎮之羧酸 鹽。較佳的鎂化合物是氯化鎂（MgCh)。 可視需要將齊格爾-納塔型觸媒預聚合。通常以少量的 早體與已與共觸媒接觸之後的觸媒接觸可以完成預聚合法 。在美國專利第5，106,804號、第5，153，158號及第5,594,07 1 號說明預聚合法，將其倂入本文以供參考。 可在任何已知用於任何型.式的α -烯烴類的均聚合或共 聚合之方法中使用觸媒。例如，本發明的觸媒可以有助於 催化乙烯、丙烯、丁烯、戊烯、己烯、4-甲基戊烯及其它 具有至少2個碳原子之α -烯烴類，並也有助於催化其混合 物。利用本發明的觸媒聚合乙烯，以生產聚乙烯。 本發明的觸媒活性至少部份係依據聚合法及條件而定 。通常觸媒具有至少6,000公克ΡΕ/公克觸媒之活性，並且 活性也可以大於100,000公克ΡΕ/公克觸媒。 此外，以本發明的所得觸媒提供具有極佳的鬆散形態 學之聚合物。因此，以本發明的觸媒供給具有均勻的尺寸 分佈之大聚合物粒子，其中小及極細的粒子（小於約1 25微米 )只出現在低濃度中。以包括具有高粉末鬆密度之大及可輕 易轉移之粉末的本發明觸媒易符合聚合生產法。 聚合法可以是整體相、泥漿相或氣相。最好在泥獎相 聚合作用中使用以上合成的觸媒。聚合條件（例如，溫度及 壓力）係依據所利用的設備型式與所進行的聚合法型式而定 ，並是本技藝已知的條件。通常溫度將以約50-200°C爲範圍 ^氏張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐）TyfZ -- (請先閲讀背面之注意事項再填寫本頁)574237 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7 _V. Description of Invention (3) However, although there have been these developments in prior art, none of these prior art documents have disclosed or proposed in The characteristics of R in the mixture of (〇1) 4 will provide a catalyst with an improved hydrogen reaction, which can provide a narrower molecular weight distribution ("MWD"). Therefore, polyolefin catalysts are required in this technology In this technology, a method for preparing a polyolefin catalyst is additionally required. In this technology, a method for polymerizing olefins is additionally required. In this technology, a narrower MWD polyolefin is also required. In this technology, an improvement is also required. Catalysts for hydrogen-type reactions. In the art, it is even further required to provide a method for preparing a polyolefin catalyst having a polymer having a narrow molecular weight distribution, wherein the method includes using a blend of Ti (〇Pr) 4 and TiCl4. 2. This technique even requires another method to make narrower MWD polyolefins. Those who are familiar with this technique are reviewing this specification (including its graphics and patent applications). These and other needs of the art will be understood when the present invention is described. One object of the present invention is to provide a polyolefin catalyst. Another object of the present invention is to provide a method for producing a polyolefin catalyst. The present invention Another object of the present invention is to provide a method for polymerizing olefins. Another object of the present invention is to provide a narrower MWD polyolefin. Another object of the present invention is to provide a paper with an improved hydrogen reaction. This paper is applicable to China. National Standards (CNS & Specifications (210x297 mm) Z〇Z — (Please read the notes on the back before filling in this education) Revision 574237 A7 B7 V. Description of the invention (4) Catalyst. The invention even has a purpose The present invention provides a method for preparing a polyolefin catalyst having a polymer having a narrow molecular weight distribution, wherein the method includes using a blend of Ti (〇Pr) 4 and butyl iCh. There is even another object of the present invention to provide a method for preparing a polymer having a narrow molecular weight distribution. Narrow polyolefin method of MWD. A specific embodiment of the present invention is to provide a magnesium dialkoxide compound generally containing: a) a general formula Mg (OR ") 2 and a halogen Exchanging contact of a halogenating agent of an alkoxide to form a reaction product A, where R " is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms; b) the reaction product A and the first halide / titanium Contacting the acidifying agent to form a reaction product b; and c) contacting the reaction product B with a second halogenating / titanating agent to form a catalyst component produced by a method of forming a catalyst component. The first halogenated / titanated reagent is preferably a blend of TKOP ·) 4 and TiCh. Soluble magnesium dialkanol compounds are magnesium alkyl compounds of the general formula MgRR '(wherein R and V are alkyl groups of 1-10 carbon atoms, and may be the same or different) and alcohols of the general formula R " 〇H ( Among them, the alcohol is a linear or branched chain alcohol and the reaction product of R ″ is an alkyl group of 4-20 carbon atoms). Another embodiment of the present invention provides a catalyst. The catalyst is usually produced by contacting the catalyst component of the present invention with an organoaluminum preactivator. The catalyst is usually contacted by a magnesium alkoxide compound comprising i) with the general formula Mg (OR) and a halogenating agent capable of exchanging a halogen alkoxide with a halogen to form a reaction product A, where R ,, A hydrocarbon group or substituted hydrocarbon group having from 1 to 20 carbon atoms; ii) contacting the reaction product A with the first halogenation / titanation reagent '(please read the precautions on the back before filling this page), τ ii. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is printed to the Chinese National Standard (CNS) A4 specification (210X297 mm) -7-574237 Printed by the Consumers’ Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 _ V. Invention Explanation (5) to form reaction product B; and iii) produced by the method of contacting reaction product B with a second halogenating / cinnifying agent. The first halogenating / titanating agent is made of Ti (〇PO4 and The blend of TiCU is better. The catalyst of the present invention has an improved hydrogen reaction and helps to produce a polymer with an expected molecular weight distribution. The present invention is even provided in another embodiment to include: a) a Or more α-olefin monomers under polymerization conditions The catalyst is then contacted together in the presence of a catalyst. It is preferred to use a catalyst to polymerize a polyethylene monomer to produce a polyethylene polymer. The catalyst is usually composed of a magnesium dialkoxide compound containing i) in the general formula Mg (OR) 2. Contact with a halogenating agent capable of exchanging an alkoxide with one halogen to form a reaction product A, where R is a hydrocarbon group or substituted hydrocarbon group having 1 to 20 carbon atoms; ii) reacting the reaction product A with the first Produced by a method of contacting a halogenated / titanated reagent to form a reaction product B; and iii) contacting the reaction product B with a second halogenated / titanated reagent to form a catalyst. At least one of steps b) and In c), the halogenation / titanation reagent is preferably Ti (〇Pr) 4 / TiCl4. The catalyst production method may include contacting a catalyst component with an organoaluminum reagent. The present invention is still provided in another specific embodiment. A catalyst system comprising the catalyst of the present invention and an inert support. The inert single system is preferably a magnesium compound. The present invention also provides a method for forming a catalyst component in another specific embodiment. Generally, the method includes: a) Magnesium dialkoxide with the general formula Mg (〇R ") 2 And a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product A, where R "is a hydrocarbon group or substituted hydrocarbon group having from 1 to 20 carbon atoms; ii) reacting the reaction product A with The first halogenation / titanation reagent is contacted to form a reaction product B; and iii) the reaction product B is applied to a second paper size of the Chinese National Standard (CNS) A4 specification (210X297 mm) -8-—II— 14 丨 丨 丨 -i ------ # (Please read the notes on the back and fill in this page first) 574237 A7 _ B7 V. Description of the invention (6) The halogenated / titanated reagent is contacted to form the catalyst component , Or reaction product C. In at least one of steps b) and c), the halogenation / titanation reagent is preferably Ti (〇Pr) 4 / TiCl4. The invention even provides, in another embodiment, a method for forming a catalyst, the method comprising contacting a catalyst component with an organoaluminum preactivation reagent. The present invention even provides an α-olefin polymerization method in another specific embodiment. Common polymerization methods include: a) contacting one or more alpha-olefin monomers together in the presence of a catalyst under polymerization conditions; and b) extracting the polyolefin polymer. The polymerization method facilitates the production of polymers having a molecular weight distribution of less than 7, preferably polyethylene. Those skilled in the art will understand these and other purposes of this technique when reviewing this specification, including its graphics and patentable scope. _ Detailed description of the present invention The method for preparing the catalyst component of the present invention generally includes forming a dialkyl alcohol metal with an alcohol and a dialkyl alcohol halide, and forming a catalyst by halogenation / titanation in two or more steps. (Using at least one of the steps Ti (OP04 / TiCl4 mixture) and then treating the catalyst with a preactivator (such as organoaluminum) to form a preactivated catalyst. Mechanism proposed by the method of the present invention It is usually as follows: 1. MRR, + 2R " 〇H-> M (〇R ")2; 2. M (〇R ,,) 2 + C1AR, " X->"A"; 3. "Α ”+ TiCWTi (〇Pr) 4“ B ”; This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) -9-——I-14—, (Please read the precautions on the back before filling in this Page), 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574237 A7 __ _B7_ V. Description of the Invention (7) 4 · “Β” + TiCh — “C”: and 5. “C” + TEAI — Touch of Preactivation In the above formula, M is any suitable metal, preferably a group IIA metal, and most preferably Mg. In the above formula, 'R, R', R 'And R' " are each independently a hydrocarbyl or substituted hydrocarbyl moiety, with R and IT having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, and from 2 to 6 carbons Atoms are better, and even better from 2 to 4 carbon atoms. R "usually contains from 3 to 20 carbon atoms, usually from 2 to 6 carbon atoms. Two or more R, R ', R " And any combination of R ... may be the same or R groups may be different from each other. In the above formula C1AIT ', A is an unreduced oxyphilic compound, which can exchange an alkoxide with a chloride, and R " Substituted hydrocarbyl and X are the valence of A minus 1. Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, with titanium and silicon where X is 3 being the best. Examples of R ... include methyl, ethyl Propyl, propyl, isopropyl, and the like having 2 to 6 carbon atoms. R " is usually propyl. Although the actual compound of the product "A" is unknown, it is believed to include partially chlorinated metals A compound, an example of which may be ClMg (〇R "). The reaction product "B" produced by the first chlorination / titanation may be chlorine Compounds of metallized and partially chlorinated metals and titanium compounds, and may be represented, for example, by (MCh) y, · (TiCh (〇Pr) 4_ 小 '. Produced by the second chlorination / titanation The catalyst component "C" may also be a complex of chlorinated and partially chlorinated metals and titanium compounds, but it is different from υΒ "and may be (MCl2) y · (1 ^ 1 ^ (〇? 1 ’) 〇,) 2, representative. We expect that the degree of chlorination of "0" may be greater than that of "B". The greater degree of chlorination may produce different paper sizes. Applicable to China National Standard (CNS) A4 specifications (210X297 mm) -10- " ~ 1 · ~ 丨 " ♦ 11 (Please read the precautions on the back first (Fill in this page again) Order 574237 A7 __ B7 _ printed by the Intellectual Property Bureau's Consumer Cooperatives of the Ministry of Economic Affairs 5. Description of the invention (8) Compounds with different compounds. Although the description of the reaction product provides the most likely chemical explanation at the same time, the invention described within the scope of the patent application is not limited by this theoretical mechanism. The dialkyl metal and the resulting dialkanol metal suitable for use in the present invention include anyone who will obtain a suitable polyolefin catalyst when used in the present invention. Preferred dialkanols and dialkyl metals include dialkanols and dialkyl Group IIA metals. The dialkanol or dialkyl metal is more preferably a dialkanol or a dialkyl magnesium. In the field application of the present invention, Eryuanji magnesium [MgRR "may be any dialkyl magnesium, and R and R 'are as described above. R and R 'may be the same or different. Non-limiting examples of suitable dialkyl magnesium include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butyl ethyl magnesium, and the like. Butyl magnesium (BEM) is the preferred dialkyl magnesium. In the field application of the present invention, the metal dialkanol is preferably a magnesium compound having the general formula Mg (〇R ") 2, where R " is a hydrocarbon group of 1 to 20 carbon atoms or a substituted hydrocarbon group. Alcohol metal is best to have solubility and best to be unreduced. Unreduced compounds have the advantage of forming MgCh, instead of insoluble Ti + 3 species, such as MgRR ', formed by the reduction of compounds, which tend to form Catalyst for particle size distribution. In addition, Mg (〇R ") 2 has lower reactivity than MgRR ', and is chlorinated by a mild chlorinating agent, followed by simultaneous chlorination / titanium with a mild reagent. Acidification and the second chlorination / titanation reaction with a stronger reagent are gradually and successively stronger reactions, which can generate more uniform products, that is, better control and distribution of catalyst particle size. Non-limiting examples of useful species of metal dialkanols include butyl paper sizes applicable. National National Standard (CNS) A4 (210X297 mm) -11-— I.-I — (Please read the back first Please note this page, please fill in this page) Order printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574237 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7_ V. Invention Description , Bis (2-ethylhexanol) magnesium and any alkanolate suitable for the manufacture of soluble systems. The best metal alkanol species is bis (2-ethylhexyl) magnesium. Alkyl magnesium compounds (MgRm (such as butyl ethyl magnesium (BEM)) and alcohols (ROH) (such as 2-ethylhexanol) can be reacted to produce non-limiting examples of magnesium dialkoxides such as di (2-ethylhexyl) Alcohol) magnesium. MgRR, + 2R, 5OH — Mg (〇R ”) 2 + RH + ITH In the case of BEM, RH and R'H are butane and ethyl, respectively. The reaction takes place at room temperature and below The reactants form a solution. In the field application of the present invention, any alcohol that gives the desired metal dialkanol can be utilized. Any alcohol of the general formula R " OH can be used as a non-limiting example of an alcohol, where R " is 4- An alkyl group of 20 carbon atoms. Although almost any alcohol can be used, it is best to use a high-carbon branched alcohol. The alcohol can be a linear or branched alcohol. Non-limiting examples of alcohols include butanol, isobutanol , 2-ethyl-1-hexanol, etc. The preferred alcohol is 2-ethyl-hexanol. Usually the alcohol used will have at least 3 carbon atoms, preferably at least 4 and at least 5 More preferably and at least 6. The amount of alcohol added to the mud is usually in the range of about 0.5 equivalent to about 4 equivalent (the equivalent is relative to the entire magnesium or metal Compound), preferably in the range of about 1 to about 3 equivalents. Alkyl metal compounds have high association properties, due to the lack of electron bonding ^, they generate local molecular species that are very viscous in solution. (Such as triethylaluminum) can reduce the high viscosity and disintegrate the connection between the alkyl metal molecules. The preferred ratio of alkylaluminum to metal is that this national standard (CNS) A4 specifications (210X297 mm) -12- I n II-nn IIII I_ ITI I__I. (Please read the notes on the back before filling in this X) 574237 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 ___B7 _V. Invention Explanation (10) 0.001 ·· 1 to 1 ·· 1, more preferably 0.01: 1 to 〇 · 1: 1, and most preferably 0.03: 1 to 0.05: 1. In addition, an electron donor can be used to further reduce the alkyl group. Metal viscosity, such as ether, for example, diisoamyl ether (DIAE). The preferred electron donor to metal ratio is 0: 1 to 1 0: 1, and more preferably 0.1: 1 to 1: 1. Reagents useful in the halogenation step for halogenating metal alkanols include any A suitable halogenating agent for polyolefins will be obtained. The halogenation step is preferably a chlorination step, and the preferred halogenating agent is a chloride. The chloride halogenating agent ("chlorinating agent") is based on only magnesium alkoxide. Part of chlorinated monochloride is preferred, and the preferred chlorinating agent has the general formula C1AR " \ or C1AOR ", where A is an unreduced oxyphilic compound, which can exchange an alkoxide with one chloride , R ... is an alkyl group and X is the valence of A minus 1. Examples of A include Chin, Sand, Brocade, Carbon, Tin, and Germanium ', where X is 3 and Chin and Silicon are the best. Examples of R ... are methyl, ethyl, propyl, isopropyl and the like having 2-6 carbon atoms. Examples of chlorinating agents effective in the present invention are ClTUCVPrh and ClSi (Me) 3. The halogenation of the metal alkanol compound is usually carried out in a hydrocarbon solvent under an inert gas. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane, and the like. The preferred solvent is hexane. Usually around 0. (: The halogenation step is performed at a temperature ranging from about 100 ° C and a reaction time ranging from about 0.5 hours to about 24 hours. At a temperature ranging from about 20 ° c to about 90 ° C It is preferred to perform the halogenation step with a reaction time ranging from about 1 hour to about 4 hours. Once the halogenation step is performed and the alkanol metal is halogenated, the soluble halide product "A" is subjected to one or more halogenation / titanation Processing, at least one of the paper sizes is in accordance with Chinese National Standards (CNS) A4 specifications (210X297 mm) _ 13-(Please read the precautions on the back before filling this page) 574237 Printed by A7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs B7 V. Explanation of the invention (11) The mixture of TiClWTUCVPrh must be used for the first time. The first halogenation / titanation step is better to use the mixture of TiCh / TUCT.Prh. Usually all 4 of the halogenation / titanation reagent system are the same substituent And a titanium compound with a tetra-substituted substituent such as a halogen or a substance or an alkoxide or phenate having 2 to 10 carbon atoms, such as TiCh or Ti (Of ...) 4. The halogenation / titanate reagent is based on Chlorination / titanation reagent The preferred chlorination / titanation agent can be a single compound or a combination of compounds. The method of the present invention provides an active catalyst after the first chlorination / titanation step; however, each time a different It is better to perform the chlorination / titanation twice for the compound or compound composition, and use a stronger chlorination / titanation agent in each successive chlorination / titanation treatment. The first chlorination / titanation agent A mild titanating agent is preferred, and a blend of titanium halide and an organic titanate is preferred. It is believed that the reaction of a blend of titanium halide and an organic titanate will form an alkoxy titanium halide Ti (〇 R) aXb, where OR and X are in the alkoxide and halide respectively, a + b is the valence of titanium, which is represented by 4, and a and b can be fractions, for example, a = 2.5 and b = 1.5 〇 The first chlorination / titanation reagent is more preferably a blend of TiCl4 and Ti (〇iP〇3 or a blend of TiCl4 and Ti (0iPr) 4. At least one of the chlorination / titanation The step must use a blend of TiCh and Ti (0iP〇4, and preferably the first chlorination / titanation reagent is TiCl4 and Ti (0iP r) 4. Or the ratio of TiCl4 / Ti (〇Bu) 4, or TiClWTi (〇iPr) 4, the ratio of TiCU to Ti (〇Bu) 4 or Ti (〇iP〇4) is from 0.5: 1 to 6: 1 as the range, i: i to 4: 1 is better, and 2: 1 to 3: 1 is the best. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -14-(Please (Please read the notes on the back before filling this page) 574237 Printed by A7 B7_7, Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (12) The first halogenation / acidification step is usually performed in a hydrocarbon solvent. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane, and the like. The product "A" is soluble in a hydrocarbon solvent. The solid product "B" was precipitated at room temperature, and then the halogenated / titanium reagent was added to the soluble product "A". The amount of halogenated / titanium reagent used must be sufficient to precipitate a solid product from the solution. The amount of halogenation / titanium reagent usually used is based on the ratio of titanium to metal, usually in the range of about 0.5 to about 5, preferably in the range of about 1 to about 4, and most preferably in the range of about 1.5 to about 2.5. . The solid product "B" precipitated in this first titanation step is then recovered by any recovery technique and then washed with a hydrocarbon solvent. Compounds suitable for use as the second halogenation / titanation reagent include those suitable for use as the first halogenation / titanation reagent, except that the second reagent is a stronger reagent (preferred). The second halogenated / titanated reagent is stronger, with titanium halide being preferred, and titanium tetrachloride [TiCh] being more preferred. The solid product "B" is usually slurried in a hydrocarbon solvent to perform a second halogenation / titanation step to produce a reaction product or catalyst component "C". Hydrocarbon solvents suitable for use in the first halogenation / titanation step can be utilized. The amount of titanium tetrachloride usually used is usually in the range of about 0.1 to about 5 equivalents, preferably in the range of about 0.1 5 to about 4 equivalents, and most preferably in the range of about 0.175 to about 2.5. The catalyst component "C" can be combined with an organoaluminum co-catalyst component ("pre-activator") to form a pre-activated catalyst suitable for olefin polymerization. Co-catalysts used with transition metals containing catalyst component "C" are typically organometallic compounds of la, Ila, and Ilia metals, such as alkyl aluminum, alkyl aluminum hydride, and lithium alkyl. Standard (CNS) A4 specification (210X297 mm) -15-(Please read the precautions on the back before filling out this page) 574237 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) Aluminium, alkanes Zinc, alkyl magnesium and the like. The preactivator is preferably an organoaluminum compound, more preferably an alkylaluminum of formula airs. Here RM is an alkyl or halide having 1 to 8 carbon atoms. Preferred organoaluminum preactivators include trialkylaluminums, such as trimethylaluminum (TMA), triethylaluminum (TEA1), and triisobutylaluminum (TiBAl). The best pre-activator is TEA1. The ratio of A1 to titanium ranges from 0.1: 1 to 2: 1, and preferably from 0.25: 1 to 1.2 · 1. The catalyst is then recovered and washed with a hydrocarbon solvent. If desired, the electron donor is added with the halogenating agent, the first mild halogenating / titanating agent or the second stronger halogenating / titanating agent. It is best to use an electron donor in the second halogenation / titanation step. Electron donors for use in the preparation of olefins are well known and any suitable electron donor that will provide a suitable catalyst can be utilized in the present invention. Also known as Lewis bases are electron donating systems to organic compounds of oxygen, nitrogen, phosphorus or sulfur, which can donate catalyst electron pairs. The electron donor may be favorably selected from aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, propenyl derivatives (especially alkyl acrylates or alkyl methacrylates) Mono- or polyfunctional compounds between silyl esters) and silane. A preferred example of a suitable electron donor is di-n-butyl phthalate. A more preferred example of a suitable electron donor is an alkylsilylalkanoate of the general formula RSi (〇R ′) v, for example, methylsilyltriethanol salt [MeSi (〇Et3)], where R And R 'is an alkyl group having 1-5 carbon atoms, and may be the same or different. The carrier of the catalyst system of the present invention should be an inert solid that does not chemically react with the components of any well-known Ziegel-Natta catalyst. The system is based on the magnesium paper standard applicable to the Chinese National Standard (CNS) A4 specifications (210X297 mm) -16-(Please read the precautions on the back before filling this page) 574237 A7 __ B7 V. Description of the invention (14) good. Examples of magnesium compounds which can be used to provide a support for the catalyst component are magnesium halides, dioxomagnesium, halogenated oxocarbons, and carboxylates of the town. The preferred magnesium compound is magnesium chloride (MgCh). If necessary, the Ziegel-Natta type catalyst is pre-polymerized. Prepolymerization can usually be accomplished by contacting the catalyst with a small amount of early body after it has been contacted with the cocatalyst. Prepolymerization methods are described in U.S. Patent Nos. 5,106,804, 5,153,158, and 5,594,07 1, which are incorporated herein by reference. The catalyst can be used in any method known for the homopolymerization or copolymerization of any type of α-olefin. For example, the catalyst of the present invention can help catalyze ethylene, propylene, butene, pentene, hexene, 4-methylpentene, and other α-olefins having at least 2 carbon atoms, and also help catalyze Its mixture. The catalyst of the present invention is used to polymerize ethylene to produce polyethylene. The catalyst activity of the present invention is at least partly determined by the polymerization method and conditions. The catalyst usually has an activity of at least 6,000 grams of PE / g catalyst, and the activity can also be greater than 100,000 grams of PE / g catalyst. In addition, the obtained catalyst of the present invention provides a polymer having an excellent loose morphology. Therefore, the catalyst of the present invention is used to supply large polymer particles with a uniform size distribution, in which small and extremely fine particles (less than about 125 microns) appear only in low concentrations. The catalyst of the present invention including a large and easily transferable powder having a high powder bulk density easily conforms to the polymerization production method. The polymerization method may be a monolithic phase, a slurry phase, or a gas phase. It is best to use the catalysts synthesized above for mud-phase polymerization. Polymerization conditions (for example, temperature and pressure) are determined according to the type of equipment used and the type of polymerization method being performed, and are conditions known in the art. Usually the temperature will be in the range of about 50-200 ° C. ^ 'S scale is applicable to China National Standard (CNS) A4 specification (210X 297 mm) TyfZ-(Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 574237 A7 __—_ B7___ 五、發明説明（15) 及壓力係以約10-800磅/平方英吋爲範圍。 可將烯烴單體引入在反應條件下是液體之非反，應性熱 轉移試劑之稀釋液中的聚合反應區中。這種稀釋液之實例 疋己丨兀及異丁丨兀。弟一^個6K -傭煙可以0.01-20莫耳％存在於 乙烯與另一種α -烯烴（例如，丁燦或己烯）之共聚合作用中 ，以0.02-10莫耳％較佳。 關於聚合法，其最好可以包括在觸媒合成中的內電子 給予體及外電子給予體或立體選擇性控制劑（SCA)，以活化 在聚合時的觸媒。可在氯化或氯化/鈦酸化步驟期間的觸媒 形成作用中使用內電子給予體。適合作爲製備熟知的經支 撐之齊格爾-納塔型觸媒組份之內電子給予體之化合物包括 醚類、二醚類、酮類、內酯類、具有N、P及/或S原子之 電子給予體及特殊的醚種類。以酞酸之酯類（如酞酸二異丁 酯、二辛酯、二苯酯及苯甲丁酯）、戊二酸之酯類（如戊二酸 二異丁酯及二乙酯）、特戊酸烷基及芳基酯、馬來酸烷基、 h丨兀基及方基酯、碳酸;)：完基及芳基酯（如碳酸二異丁酯、乙 苯酯及二苯酯）與丁二酸酯類（如丁二酸單及二乙酯）。 可在根據本發明的觸媒製備作用中利用的外給予體包 括有基甲矽烷化合物，如通式SiRm(〇R’）4.m之烷氧基甲矽烷 ’在此R係選自由烷基、環烷基、芳基及乙烯基所構成的 群組’其中R可與R’相同；當m是0、1或2時，則R’基可 以相同或不相同，及在m是2或3時，則R基可以相同或不 相同。 本發明的內給予體係選自由下式之甲矽烷化合物： 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） :18 - ~ 1——i衊！ (請先閲讀背面之注意事項再填寫本頁) 、11 經濟部智慧財產局員工消費合作社印製 574237 A7 B7 五、發明説明（π )Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 1T 574237 A7 ____ B7___ V. Description of Invention (15) and pressure are in the range of about 10-800 psi. The olefin monomer can be introduced into the polymerization reaction zone in a diluent of the reactive thermal transfer reagent which is liquid under the reaction conditions. Examples of such a diluent are self-contained and isoformed. A 6K-mercury may be present in the copolymerization of ethylene with another α-olefin (e.g., butan or hexene) at a rate of 0.01-20 mole%, preferably 0.02-10 mole%. As for the polymerization method, it may preferably include an internal electron donor and an external electron donor or a stereoselective control agent (SCA) in the catalyst synthesis to activate the catalyst during polymerization. An internal electron donor can be used in the catalyst formation during the chlorination or chlorination / titanation step. Compounds suitable as internal electron donors for the preparation of well-known supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, having N, P and / or S atoms Electron donors and special ether types. The esters of phthalic acid (such as diisobutyl phthalate, dioctyl ester, diphenyl ester, and butyl butyl ester), the esters of glutaric acid (such as diisobutyl glutarate and diethyl ester), Alkyl and aryl esters of pivalic acid, alkyls of maleic acid, alkyl and squaryl esters, carbonic acid;): Endyl and aryl esters (such as diisobutyl carbonate, ethylphenyl ester, and diphenyl ester ) And succinates (such as succinate mono and diethyl ester). External donors that can be used in the catalyst preparation according to the present invention include a silyl compound, such as an alkoxysilane of the general formula SiRm (〇R ′) 4.m where R is selected from the group consisting of alkyl , Cycloalkyl, aryl and vinyl group 'where R can be the same as R'; when m is 0, 1 or 2, then the R 'groups can be the same or different, and when m is 2 or When 3, the R groups may be the same or different. The internal administration system of the present invention is selected from the silane compounds of the following formula: The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm): 18-~ 1——i 蔑! (Please read the notes on the back before filling out this page) 、 11 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574237 A7 B7 V. Description of the invention (π)

OROR

R1~~Si--R I 4 〇r3 其中R 1及R4兩者係包括附著至矽之一級、二級或三級 之院基或環院基，R1及R4是相同的或不相同的；R2及R3係 烷基或芳基。R1可以是甲基、.異丙基、環戊基、環己基或 特丁基；R2及R3可以是甲基、乙基、丙基或丁基，並且沒 有必要相同；及R4也可以是甲基、異丙基、環戊基、環己 基或特丁基。特殊的外給予體是環己基曱基二甲氧基甲矽 烷（CMDS)、二異丙基二甲氧基甲矽烷（DIDS)、環己基異丙 基二甲氧基甲矽烷（CIDS)、二環戊基二甲氧基甲矽烷（CpDS) 或二特丁基二甲氧基甲矽烷（DTDS)。 使用上述的觸媒所生產之聚乙烯將具有小於約7.0之 MWD，以小於約6.0較佳，以小於約5.5更佳及以小於約5.0 甚至更佳。 以提供以下的實例作爲已槪括說明的本發明的特殊具 體實施例’並證明其實地應用和優點。當然提供以例證方 式之實例’並不是企圖以其依照任何方式限制說明書的範 圍或申請專利範圍。 實例 只提供以下已的實例例證本發明特定的具體實施例， 本紙張尺度適用中國國家標準（CNS ) Μ規格（21〇><297公釐） 1——一—衊！ (請先閲讀背面之注意事項再填寫本頁)R1 ~~ Si--RI 4 〇r3 Among them, R 1 and R 4 both include the first, second, or third level courtyard or ring courtyard attached to silicon. R1 and R4 are the same or different; R2 And R3 is an alkyl group or an aryl group. R1 may be methyl, isopropyl, cyclopentyl, cyclohexyl, or tert-butyl; R2 and R3 may be methyl, ethyl, propyl, or butyl, and need not be the same; and R4 may also be methyl Base, isopropyl, cyclopentyl, cyclohexyl or tert-butyl. Special external donors are cyclohexylfluorenyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyldimethoxysilane (CIDS), Cyclopentyldimethoxysilane (CpDS) or di-tert-butyldimethoxysilane (DTDS). The polyethylene produced using the above catalysts will have an MWD of less than about 7.0, preferably less than about 6.0, more preferably less than about 5.5, and even less than about 5.0 or even better. The following example is provided as a specific embodiment of the present invention, which has been described in detail, and proves its practical application and advantages. Of course, providing an example by way of illustration 'is not an attempt to limit the scope of the specification or the scope of patent application in any way. Examples Only the following specific examples are provided to illustrate specific specific embodiments of the present invention. This paper size applies the Chinese National Standard (CNS) M specification (21〇 < 297 mm). (Please read the notes on the back before filling this page)

-、1T 經濟部智慧財產局員工消費合作社印製 574237 A7 _B7 五、發明説明（17 ) 並不意味以其限制申請專利的範圍。 (請先閲讀背面之注意事項再填寫本頁) 觸媒製備作用 本實例係提供形態學受控制之聚乙烯觸媒之例證，其 容許以觸媒生產更窄的分子量分佈（MWD)聚合物。可以利 用以窄的觸媒特性能使樹脂適合於注模應用。 觸媒製備作用 以下係合成形態學受控制之觸媒的合成策略。在表1中 提供關於以該觸媒在標準的批組反應器條件下得到的聚合 物MWD之突出的數據。可自該數據發現以切變反應（SR5) 及多分散度値（Mw/Mn)估計聚合物的MWD非常窄。 觸媒之製造如下： 步驟1 ·-、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 574237 A7 _B7 V. The invention description (17) does not mean to limit the scope of patent application. (Please read the notes on the back before filling this page.) Catalyst Preparation This example provides an example of a morphology-controlled polyethylene catalyst that allows the production of a narrower molecular weight distribution (MWD) polymer with the catalyst. The narrow catalyst properties can be used to make the resin suitable for injection molding applications. Catalyst Preparation The following is a synthesis strategy of synthetic morphology-controlled catalysts. Table 1 provides outstanding data on the polymer MWD obtained with this catalyst under standard batch reactor conditions. From this data, it can be found that the MWD of the polymer estimated from the shear response (SR5) and polydispersity 値 (Mw / Mn) is very narrow. The catalyst is manufactured as follows: Step 1 ·

BuEtMg/DIAE/TEAI (1··0·6:0·03) + 2-乙基己醇（2.09)，以 提供可溶性中間物Α。 經濟部智慧財產局員工消費合作社印製 步驟2. 中間物 + 1.0 CITi(〇Pi-)3，以提供可溶性中間物B。 步驟3 · 中間物B + Ti(〇Pr)4/TiCh (2.0丄0)，以提供固體預觸 媒。 本紙張尺度適用中.國國家標準（CNS ) A4規格（210X297公釐）-20- ^ 574237 Α7 Β7 五、發明説明（18 ) 步驟4. 預觸媒 + TiCU (0.25) + TEA1，以提供最終觸媒。 聚合作用 乙烯聚合作用所使用之反應器（加壓釜工程）具有4公升 容量，並配備四個具有兩個對立的傾斜混合推進器之混合 擋板。將乙烯及氫經由Teledyne-Hastings Raydist質量流速 控制器引入反應容器中，同時以裝載在拱頂的返壓調節器 維持固定的反應內壓。使用連接至B a r b e r - C ο 1 e m a η控制器 之K a m m e ι·閥以蒸氣及冷水維持（在反應器套中的）反應溫度 。使用己烷作爲稀釋液。 實驗變數: I —— 11 —— 11 —- I — — I ϋ n 丁 (請先閲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 溫度 80°C 反應時間 60分鐘 壓力 125磅/平方英吋 觸媒 0.2毫升泥漿（約10毫克觸媒） 共觸媒 TEAL@0.25毫莫耳/公升 流速 H2/C2@0.25 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）-21 - 574237 A7 B7 五、發明説明（19 ) 表1 ·形態學受控制之觸媒的M WD數據 觸媒 ppt.試劑 ΜΙ5 HLMI SR5 Mw/Mn) (公合/分鐘） (公合/分鐘） 標準 TiCh (〇Bu)4 1.86 19.5 10.4 5.4 改良型 TiCh (〇Ρι·)4 9.07 85.2 9.4 4.9 雖然已詳細說明本發明例證的具體實施例，但是應該 暸解的是那些熟悉本技藝的人將會明白及可輕易進行不違 背本發明精神及範圍的各種其它改良作用。因此，不想以 本文所附的申請專利範圍限制在本文陳述的實例及說明， 但是寧可將申請專利範圍解釋成包含所有歸屬於本發明的 專利創新事物之特性，包括所有可能由那些熟悉本技藝的 人以屬於本發明的同等物處理的特性。 —---------— (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CMS ) A4規格（210X 297公釐）-22 -BuEtMg / DIAE / TEAI (1 ·· 0 · 6: 0 · 03) + 2-ethylhexanol (2.09) to provide a soluble intermediate A. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Step 2. Intermediate + 1.0 CITi (〇Pi-) 3 to provide soluble intermediate B. Step 3 · Intermediate B + Ti (〇Pr) 4 / TiCh (2.0 丄 0) to provide a solid pre-catalyst. This paper size is applicable. National National Standard (CNS) A4 specification (210X297 mm) -20- ^ 574237 A7 B7 V. Description of the invention (18) Step 4. Pre-catalyst + TiCU (0.25) + TEA1 to provide the final catalyst. Polymerization The reactor used in the polymerization of ethylene (the autoclave project) has a capacity of 4 liters and is equipped with four mixing baffles with two opposing inclined mixing thrusters. Ethylene and hydrogen were introduced into the reaction vessel via the Teledyne-Hastings Raydist mass flow controller, while maintaining a fixed internal reaction pressure with a back pressure regulator mounted on the vault. The reaction temperature (in the reactor jacket) was maintained with steam and cold water using a Kamme valve connected to the Baarbe-r -C ο 1 ema a controller. Hexane was used as the diluent. Experimental variables: I —— 11 —— 11 —- I — — I ϋ n Ding (Please read the precautions on the back before filling out this page) Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economics Printing temperature 80 ° C Response time 60 minutes Pressure: 125 psi / 0.2 inch catalyst 0.2ml slurry (about 10mg catalyst) Total catalyst TEAL@0.25mmol/L flow rate H2/C2@0.25 This paper size applies to China National Standard (CNS) A4 specification (210X297 (Mm) -21-574237 A7 B7 V. Description of invention (19) Table 1 · M WD data of morphologically controlled catalyst Catalyst ppt. Reagent ΜΙ5 HLMI SR5 Mw / Mn) (Combined / minute) (Common) (Per minute) Standard TiCh (〇Bu) 4 1.86 19.5 10.4 5.4 Improved TiCh (〇Ρι ·) 4 9.07 85.2 9.4 4.9 Although specific examples of the present invention have been described in detail, it should be understood that those skilled in the art One will appreciate and can easily perform various other improvements without departing from the spirit and scope of the invention. Therefore, I do not want to limit the scope of the patent application attached to the examples and descriptions stated here, but rather to interpret the scope of the patent application to include all the characteristics of the patented innovations belonging to the present invention, including all those that may be familiar with the technology. The property of being treated by an equivalent belonging to the present invention. —---------— (Please read the notes on the back before filling out this page) Order printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CMS) A4 specification (210X 297 Mm) -22-

Claims (1)

574237- 公告本 A8 B8 C8 D8 修正替換本 年8月>9曰 六、申請專利範圍1 附件4: 第90 1 275 67號專利申請案 修正後無劃線之中文申請專利範圍替換本 (請先閱讀背面之注意事項再填寫本頁) 民國9 2年8月27日修正 1. 一種由包含以下步驟所生產之觸媒組份： 以通式Mg(〇R’’）2之可溶性二烷醇鎂化合物與能夠以一 個鹵素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物A ，在此R”係具有從1至20個碳原子之烴基或經取代之烴基 > 將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形成 反應產物B ;及 將反應產物B與第二個鹵化/鈦酸化試劑接觸，以形成 觸媒組份， 其中第一個鹵化/鈦酸化試劑係TUOPOWTMCh之摻合物 〇 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項之觸媒組份，其中可溶性二烷 醇鎂化合物係包含通式MgRR’之烷基鎂化合物（其中R及R’ 係1-1 0個碳原子之烷基，並可以相同或不相同）與通式 R’’〇H之醇（其中醇係直鏈或支鏈醇及其中R"係4-20個碳原 子之烷基）的反應之反應產物。 3. 如申請專利範圍第2項之觸媒組份，其中可溶性鎂化 合物是二（2-乙基己醇基）鎂。 4. 如申請專利範圍第2項之觸媒組份，其中烷基鎂化合 物是二乙基鎂、二丙基鎂、二丁基鎂或丁乙基鎂。 5. 如申請專利範圍第2項之觸媒組份，其中醇是乙醇、 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 574237 A8 B8 C8 D8 六、申請專利範圍2 丙醇、異丙醇、丁醇、異丁醇或2-乙己醇。 6.如申請專利範圍第2項之觸媒組份，其中反應尙包含 烷基鋁。 7·如申請專利範圍第6項之觸媒組份，其中烷基鋁是三 乙基鋁。 8. 如申請專利範圍第1項之觸媒組份，其中第一個氯化/ 欽酸化試劑係Ti(OPr)4/TiCl^ TiCU對Ti(OPi.)4之比例係以 0.5:1至6:1爲範圍之摻合物。 9. 如申請專利範圍第1項之觸媒組份，其中反應尙包含 電子給予體。 10·如申請專利範圍第9項之觸媒組份，其中電子給予體 對鎂之比例係以0:1至1 〇:丨爲範圍。 11 ·如申請專利範圍第1 〇項之觸媒組份，其中電子給予 體是一種醚。 12·如申請專利範圍第1項之觸媒組份，其中鹵化劑具有 通式C1AR’’\，其中A係未還原之親氧基化合物，R’，，x係具 有從2至6個碳原子之烴基部份及x係A減1之價數。 13·-種由包含以下步驟之方法所生產之觸媒： a)以觸媒組份與有機鋁預活化劑接觸，其中觸媒組份係 由包含： i) 以通式Mg(OR")2之二烷醇鎂化合物與能夠以一個鹵 素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物A，在 此R"係具有從1至20個碳原子之烴基或經取代之烴基； ii) 將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 574237 A8 B8 C8 D8 穴、申請專利乾圍3 成反應產物B ;及 (請先閲讀背面之注意事項再填寫本頁) iii)將反應產物B與第二個鹵化/鈦酸化試劑接觸，以形 成觸媒組份之方法所生產的，其中第一個鹵化/鈦酸化試劑 係Ti(〇P〇4/TiCl4之摻合物。 14. 如申請專利範圍第13項之觸媒，其中可溶性二烷醇 鎂化合物係包含通式MgRR’之烷基鎂化合物（其中R及R’係 1-10個碳原子之烷基，並可以相同或不相同）與通式R’’〇H 之醇（其中醇係直鏈或支鏈醇及其中R"係4-20個碳原子之烷 基）的反應之反應產物。 * 15. 如申請專利範圍第14項之觸媒，其中可溶性鎂化合 物是二（2-乙基己醇基）鎂。 16. 如申請專利範圍第14項之觸媒，其中烷基鎂化合物 是二乙基鎂、二丙基鎂、二丁基鎂或丁乙基鎂。 17. 如申請專利範圍第14項之觸媒，其中醇是乙醇、丙. 醇、異丙醇、丁醇、異丁醇或2-乙己醇。 18. 如申請專利範圍第14項之觸媒，其中反應尙包含烷 基鋁。 經濟部智慧財產局員工消費合作社印製 19·如申請專利範圍第18項之觸媒，其中烷基鋁是三乙 基鋁。 20.如申請專利範圍第13項之觸媒組份，其中第一個氯 化/鈦酸化試劑係Ti(〇P〇WTiCl4以TiCh對Τι(〇Ρι·)4之比例係 以0.5 :1至6:1爲範圍之摻合物。 21·如申請專利範圍第14項之觸媒，其中反應尙包含電 子給予體。 本紙張尺度適用中國國家榡準（CNS ) Μ規格（21〇><297公釐） 574237 ABCD 六、申請專利範圍4 22·如申請專利範圍第21項之觸媒，其中電子給予體對 鎂之比例係以0:1至1 0:1爲範圍。 (請先閲讀背面之注意事項再填寫本頁) 23·如申請專利範圍第22項之觸媒，其中電子給予體是 一種醚。 24·如申請專利範圍第13項之觸媒，其中鹵化劑具有通 式C1AR"、，其中A係未還原之親氧基化合物，R"’x係具有 從2至6個碳原子之烴基部份及X係A減1之價數。 25.如申請專利範圍第13項之觸媒，其中第二個氯化/鈦 酸化試劑是鹵化鈦。 26·如申請專利範圍第25項之觸媒，其中第二個氯化/鈦 酸化試劑是四氯化鈦及其中鈦對鎂之範圍係〇: 1至2:1。 27. 如申請專利範圍第13項之觸媒，其中有機鋁預活化 劑係通式A1Ra32烷基鋁，在此RA係具有1-8個碳原子之烷 基或鹵化物，RA是相同或不相同的，並且至少一個RA是院. 基。 28. 如申請專利範圍第25項之觸媒，其中有機鋁預活化 劑是三烷基鋁。 經濟部智慧財產局員工消費合作社印製 29. 如申請專利範圍第1 3項之觸媒，其中鋁對鈦之比例 係以從0.1:1至2:1爲範圍。 30. 如申請專利範圍第13項之觸媒，其中觸媒具有符合 聚合生產法之鬆散形態學，將提供具有大於7.0之分子量分 佈之聚乙烯，將具有至少6,000公克PE/公克觸媒之活性， 並將提供具有少量粒子小於1 25微米之均勻的粒子尺寸分佈 本紙張尺度適用中國國家榡準（CMS ) A4規格（210 X 297公釐） -4 - 574237 A8 B8 C8 ___ D8 六、申請專利範圍5 3 1 · —種由包含以下步驟之方法所生產之聚合物： (請先閲讀背面之注意事項再填寫本頁) a)以一或多種α -烯烴單體在聚合條件下一起在觸媒的 存在下接觸，其中觸媒係由包含： υ以通式Mg(〇R’，）2之二烷醇鎂化合物與能夠以一個鹵 素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物A，在 此R’’係具有從1至20個碳原子之烴基或經取代之烴基； ii) 將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 成反應產物B ;及 iii) 將反應產物B與第二個鹵化/欽酸化試劑接觸，·以形 成觸媒組份之方法所生產的，其中第一個鹵化/鈦酸化試劑 係Ti(〇P〇4/TiCl4之摻合物。 3 2.如申請專利範圍第3 1項之聚合物，其中觸媒係由尙 包含： iv) 以觸媒組份與有機鋁試劑接觸之方法所生產的。 33·如申請專利範圍第31項之聚合物，其中單體是乙烯 單體。 經濟部智慧財產局員工消費合作社印製 3 4 ·如申請專利範圍第3 1項之聚合物，其中聚合物是聚 乙烯。 35·如申請專利範圍第3 1項之聚合物，其中可溶性二烷 醇鎂化合物係包含通式MgRR’之烷基鎂化合物（其中R及 R’係1 -1 0個碳原子之烷基，並可以相同或不相同）與通式 R"〇H之醇（其中醇係直鏈或支鏈醇及其中R’’係4-20個碳原 子之烷基）的反應之反應產物。 36.如申請專利範圍第35項之聚合物，其中可溶性鎂化 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 574237 A8 B8 C8 D8 六、申請專利範圍6 合物是二（2-乙基己醇基）鎂。 (請先閲讀背面之注意事項再填寫本頁) 3 7 ·如申請專利範圍第3 5項之聚合物，其中院基鎂化合 物是二乙基鎂、二丙基鎂、二丁基鎂或丁乙基鎂。 3 8.如申請專利範圍第3 5項之聚合物，其中醇是乙醇、 丙醇、異丙醇、丁醇、異丁醇或2 -乙己醇。 39.如申請專利範圍第35項之聚合物，其中反應尙包含 院基I呂。 4 0 ·如申請專利範圍第3 9項之聚合物，其中烷基鋁是三 乙基鋁。 41. 如申請專利範圍第31項之聚合物，其中第一個氯化/ 鈦酸化試劑係Ti(〇Pr)WTiCl4以丁1(：14對Ti(〇P〇4之比例係·以 0.5 :1至6 :1爲範圍之摻合物。 42. 如申請專利範圍第35項之聚合物，其中反應尙包含 電子給予體。 43. 如申請專利範圍第42項之聚合物，其中電子給予體 對鎂之比例係以0:1至10:1爲範圍。 經濟部智慧財產局員工消費合作社印製 44. 如申請專利範圍第43項之聚合物，其中電子給予體 是一種醚。 45. 如申請專利範圍第31項之聚合物，其中鹵化劑具有 通式C1AR’"X，其中A係未還原之親氧基化物，R’'係具有 從2至6個碳原子之烴基部份及X係A減1之價數。 4 6.如申請專利範圍第31項之聚合物，其中第二個氯化/ 鈦酸化試劑是鹵化鈦。 47.如申請專利範圍第46項之聚合物’其中第二個氯化/ ^紙張尺度適用中國國家標準（CNS ) A4規格(2川X 297公釐） 574237 A8 B8 C8 D8 六、申請專利範圍7 鈦酸化試劑是四氯化鈦及其中鈦對鎂之範圍係0:1至2:1。 48.如申請專利範圍第32項之聚合物，其中有機鋁預活 化劑係通式A1RA3之烷基鋁，在此RA係具有1-8個碳原子之 烷基或鹵化物，RA是相同或不相同的’並且至少一個以是 烷基。 4 9.如申旨靑專利範圍第46項之聚合物，其中有機鋁預活 化劑是三烷基鋁。 5 0.如申請專利範圍第47項之聚合物，其中鋁對鈦之比 例係以從0.1:1至2:1爲範圍。_ 51.—種形成觸媒組份之/方^>該方法包含： a) 以通式Mg (OR’’）2之可溶性二烷醇鎂化合物與能夠以 一個鹵素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物 A，在此R"係具有從1至20個碳原子之烴基或經取代之烴基 b) 將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 成反應產物B ;及 c) 將反應產物B與第二個鹵化/鈦酸化試劑接觸，以形 成觸媒組份， 其中第一個鹵化/鈦酸化試劑係Ti(OPr)4/TiCl4之摻合物 〇 5 2.如申請專利範圍第5 1項之Γ方法，其中可溶性二烷醇 鎂化合物係包含通式MgRR’之烷基鎂化合物'(其中R及R’係 1-10個碳原子之烷基，並可以相同或不相同）與通式R"〇H 之醇（其中醇係直鏈或支鏈醇及其中R’’係4-20個碳原子之烷 本紙張尺度適用中國國家標準（CNS ) A4規格（2】0X297公釐） (請先閲讀背面之注意事項再填寫本頁) 、1T 經濟部智慧財產局員工消費合作社印製 574237 A8 B8 C8 D8 六、申請專利範圍8 基）的反應之反應產物。 (請先閲讀背面之注意事項再填寫本頁) 53.如申請專利範圍第52項之方法，其中可溶性鎂化合 物是二（2-乙基己醇基）鎂。 一 5 4.如申請專利範圍第52項之^方法，其中烷基鎂化合物 是二乙基鎂、二丙基鎂、二丁基鎂或丁乙基鎂。 55·如申請專利範圍第52項之^方法，其中醇是乙醇、丙 醇、異丙醇、丁醇、異丁醇或2 -乙己醇。 56.如申請專利範圍第52項之方法，其中反應尙包含烷 基鋁。 57·如申請專利範圍第56項之方法，其中烷基鋁是三乙 基IS。 5 8.如申請專利範圍第51項之方法，其中第一個氯化/鈦 酸化試劑係Ti(〇Pr)4/TiCl4以TiCl4對Ti(〇Pr)4之比例係以 0.5:1至6:1爲範圍之摻合物。 59. 如申請專利範圍第51項之方法，其中第二個氯化/鈦 酸化試劑是鹵化鈦。 60. 如申請專利範圍第59項之方法，其中第二個氯化/鈦 酸化試劑是四氯化鈦及其中鈦對鎂之範圍係0:1至2 :1。 經濟部智慧財產局員工消費合作社印製 61. —種製得觸媒之方法，該方法包含： a)以觸媒組份與有機鋁預活化劑接觸，其中觸媒組份係 由包含： i)以通式Mg(〇R")2之二烷醇鎂化合物與能夠以一個鹵 素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物A，在 此R"係具有從1至20個碳原子之烴基或經取代之烴基； 本紙張尺度適用中國國家標準（CNS ) A4規格（21ϋΧ297公釐) ~ _ 574237 A8 B8 C8 D8 穴、申請專利範圍9 ii) 將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 成反應產物B ;及 iii) 將反應產物B與第二個鹵化/鈦酸化試劑接觸 之方法所生產的，其中第一個鹵化/鈦酸化試劑係 Ti(〇Pr)4/TiCl4之摻合物。 62.如申請專利範圍第61項之方法，其中第一個氯化/欽 酸化試劑係Ti(〇P〇4/TiCl4以TiC]4對Τι(〇Ρι·)4之比例係以 0.5 :1至6:1爲範圍之摻合物。 63. 如申請專利範圍第62項之方法，其中 TrCL·對 ΤΚΟΡιψ之比例係2:1。 64. 如申請專利範圍第61項之方法，其中可溶性二院醇 鎂化合物係包含通式MgRR’之烷基鎂化合物（其中R及R’係 1-10個碳原子之烷基，並可以相同或不相同）與通式R’’〇H 之醇（其中醇係直鏈或支鏈醇及其中R"係4-20個碳原子之院. 基）的反應之反應產物。 65. 如申請專利範圍第61項之方法，其中可溶性鎂化合 物是二（2-乙基己醇基）鎂。 66. 如申請專利範圍第6 1項之方法，其中烷基鎂化合物 是二乙基鎂、二丙基鎂、二丁基鎂或丁乙基鎂。 67. 如申請專利範圍第6 1項之方法，其中醇是乙醇、丙 醇、異丙醇、丁醇、異丁醇或2-乙己醇。 .68.如申請專利範圍第61項之方法，其中反應尙包含烷 基鋁。 69.如申請專利範圍第68項之方法，其中烷基鋁是三乙 ^紙張尺度適用中國國家樣準（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁) 、^Τ 經濟部智慧財產局員工消費合作社印製 574237 Α8 Β8 C8 D8 々、申請專利範圍10 基鋁。 70·如申請專利範圍第61項之方法，其中反應尙包含電 子給予體。 7 1.如申請專利範圍第70項之方法，其中電子給予體對 鎂之比例係以0:1至1 0:1爲範圍。 72·如申請專利範圍第71項之方法，其中電子給予體是 一種醚。 7 3 ·如申請專利範圍第6 1項之方法，其中鹵化劑具有通 式C1AR"’X，其中A係未還原之親氧基化合物，R’’，x係具有 從2至6個碳原子之烴基部份。 74.如申請專利範圍第61項之方法，其中鹵化劑係 TiCl/TUOipi·)〗之摻合物。 7 5 ·如申請專利範圍第6 1項之方法，其中第二個氯化/欽 酸化試劑是鹵化鈦。 7 6·如申請專利範圍第6 1項之方法，其中第二個氯化/鈦 酸化試劑是四氯化鈦及其中鈦對鎂之範圍係〇: 1至2 :1。 7 7 ·如申請專利範圍第6 1項之方法，其中有機鋁預活化 劑是烷基鋁。 7 8 ·如申請專利範圍第61項之方法，其中電子給予體 存在於任何其中一個步驟a)、i)、i i)或H i)中，及其中電子 給予體對金屬之比例係以0:1至10:1爲範圍。 7 9. —種使α -烯烴聚合之方法，其包含： a)以一或多種α -烯烴單體在聚合條件下一起在觸媒的 存在下接觸，其中觸媒係由包含： 本紙張尺度適用中國國家標準（CNS ) Α4規格（21〇:<297公釐） (請先閲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 574237 A8 B8 C8 D8 六、申請專利範圍11 i)以通式Mg(OR")2之二烷醇鎂化合物與能夠以一個鹵 素交換一個烷醇鹽之鹵化劑接觸，以形成反應產物A，在 此R"係具有從1至20個碳原子之烴基或經取代之烴基； i i)將反應產物A與第一個鹵化/鈦酸化試劑接觸，以形 成反應產物B ;及 iii) 將反應產物B與第二個鹵化/欽酸化試劑接觸，以形 成反應產物C之方法所生產的，其中第一個鹵化/鈦酸化試 劑係Ti(〇P〇4/TiCl4之摻合物。 80. 如申請專利範圍第79項之方法，其尙包含： b)萃取聚烯烴聚合物。 81. 如申請專利範圍第80項之方法，其中聚合物具有'小 於7.0之分子量分佈。 8 2·如申請專利範圍第80項之方法，其中聚合物是聚乙 烯。 83·如申請專利範圍第79項之方法，其中觸媒係由尙包 含： iv) 以反應產物C與有機鋁試劑接觸之方法所生產的。 84.如申請專利範圍第79項之方法，其中第一個氯化/鈦 酸化試劑係Ti(OP〇WTiCl4以丁1(：14對Ti(〇P〇4之比例係以 0.5:1至6:1爲範圍之摻合物。 85.如申請專利範圍第84項之方法.，其中 TiCl4對 ΤΚ〇Ρι·)4之比例係2:1。 86·如申請專利範圍第79項之方法，其中步驟ϋ之鹵化 劑具有通式C]AR’’\，其中Α係未還原之親氧基化物，R’’’x 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) 、π. 經濟部智慧財產局員工消費合作社印製 574237 B8 C8 D8 六、申請專利範圍12 係具有從2至6個碳原子之烴基部份。 87·如申請專利範圍第86項之方法，其中鹵化劑是 ClTi(〇iPr)3。 88·如申請專利範圍第86項之方法，其中第二個氯化/鈦 酸化試劑是鹵化鈦。 89.如申請專利範圍第88項之方法，其中第二個氯化/鈦 酸化試劑是四氯化鈦及其中鈦對鎂之範圍係〇: 1至2 :1。 90·如申請專利範圍第79項之方法，其中有機鋁試劑是 三乙基鋁。 9 1.如申請專利範圍第79項之方法，其中電子給予體 存在於任何其中一個步驟1)-i v)中，及其中電子給予體對金 屬之比例係以0:1至10:1爲範圍。 (請先聞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 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -12-574237- Announcement A8 B8 C8 D8 Amendment and Replacement in August of this year > 9th, 6th, Patent Application Scope 1 Annex 4: No. 90 1 275 67 Chinese Patent Application Scope Replacement (Unlined) Please read the precautions on the reverse side before filling out this page) Amended on August 27, 1992 1. A catalyst component produced by the following steps: Soluble dioxane with the general formula Mg (〇R '') 2 The magnesium alkoxide compound is contacted with a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product A, where R "is a hydrocarbon group or substituted hydrocarbon group having from 1 to 20 carbon atoms > the reaction product A Contact with the first halogenation / titanation reagent to form a reaction product B; and contact the reaction product B with a second halogenation / titanation reagent to form a catalyst component, wherein the first halogenation / titanation reagent system is TUOPOWTMCh Blends 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. If the catalyst component of the first patent application scope, the soluble magnesium dialkoxide compound contains an alkyl magnesium compound of the general formula MgRR '( Where R and R 'is an alkyl group of 1 to 10 carbon atoms, and may be the same or different) and an alcohol of the general formula R''OH (wherein the alcohol is a linear or branched alcohol and R " is 4-20 The reaction product of the reaction of the alkyl group of carbon atom) 3. The catalyst component of item 2 in the scope of the patent application, wherein the soluble magnesium compound is bis (2-ethylhexanol) magnesium. 4. The scope of the patent application The catalyst component of item 2, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butyl ethyl magnesium. 5. If the catalyst component of item 2 of the patent application scope, wherein the alcohol It is ethanol. This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 574237 A8 B8 C8 D8 6. Application scope of patent 2 Propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol. 6. The catalyst component according to item 2 of the patent application, wherein the reaction 尙 includes an aluminum alkyl. 7. The catalyst component according to item 6 of the patent application, wherein the aluminum alkyl is triethyl aluminum. 8. For example, the catalyst component of the first scope of the patent application, in which the first chlorination / acetic acid reagent is Ti (OPr) 4 / TiCl ^ TiCU vs. Ti (O The ratio of Pi.) 4 is a blend in the range of 0.5: 1 to 6: 1. 9. For example, the catalyst component of the scope of patent application item 1, wherein the reaction plutonium contains an electron donor. 10 · If a patent is applied for The catalyst component of the scope item 9, wherein the ratio of the electron donor to the magnesium is in the range of 0: 1 to 10:11. 11 · As the catalyst component of the scope of the patent application item 10, wherein the electron donor The body is an ether. 12. The catalyst component of item 1 in the scope of the patent application, wherein the halogenating agent has the general formula C1AR '' \, where A is an unreduced oxyphilic compound, R ′, and x are The hydrocarbyl moiety of 2 to 6 carbon atoms and x is the valence of A minus 1. 13 · -A catalyst produced by a method comprising the following steps: a) contacting a catalyst component with an organoaluminum preactivator, wherein the catalyst component is composed of: i) the general formula Mg (OR ") 2 The magnesium bisalkoxide compound is contacted with a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product A, where R " is a hydrocarbyl group or a substituted hydrocarbyl group having from 1 to 20 carbon atoms; ii ) Contact the reaction product A with the first halogenation / titanation reagent and apply the Chinese National Standard (CNS) A4 specification (210 X 297 mm) to the paper size (please read the precautions on the back before filling this page) Order 574237 A8 B8 C8 D8 points printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, apply for patents to dry reaction products B; and (please read the precautions on the back before filling this page) iii) It is produced by the method of contacting two halogenating / titanating reagents to form a catalyst component. Among them, the first halogenating / titanating reagent is a blend of Ti (〇PO4 / TiCl4. 14. Such as the scope of patent application Catalyst according to item 13, wherein soluble two A magnesium alkoxide compound is an alkyl magnesium compound of the general formula MgRR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms, and may be the same or different) and an alcohol of the general formula R "OH Among them, the alcohol is a reaction product of a linear or branched alcohol and an R " alkyl group of 4-20 carbon atoms). * 15. For example, the catalyst in item 14 of the patent application scope, in which the soluble magnesium compound is two (2-ethylhexyl alcohol) magnesium. 16. The catalyst according to item 14 of the application, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 17. For example, the catalyst in item 14 of the patent application, where the alcohol is ethanol, propyl alcohol, isopropanol, butanol, isobutanol, or 2-ethylhexanol. 18. In the case of the catalyst in item 14 of the patent application, where The reaction 尙 contains aluminum alkyl. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 19 · If the catalyst for the scope of patent application No. 18, the aluminum alkyl is triethyl aluminum. Catalyst component, of which the first chlorination / titanation reagent is Ti (〇PO〇TiCl4, TiCh vs. Ti (〇Ρι ·) 4 The ratio is a blend in the range of 0.5: 1 to 6: 1. 21. For example, the catalyst in the scope of patent application No. 14 in which the reaction plutonium contains an electron donor. This paper standard applies to China National Standards (CNS) Μ specification (21〇 > < 297 mm) 574237 ABCD VI. Patent application scope 4 22 · If the catalyst of patent application scope item 21, the ratio of electron donor to magnesium is from 0: 1 to 1 0 : 1 is the range. (Please read the precautions on the back before filling out this page.) 23. If the catalyst in the scope of patent application No. 22, the electron donor is an ether. 24. The catalyst according to item 13 of the scope of patent application, wherein the halogenating agent has the general formula C1AR ", wherein A is an unreduced oxyphilic compound, and R " 'x is a hydrocarbon base having 2 to 6 carbon atoms Parts and X are the price of A minus 1. 25. The catalyst of claim 13 in which the second chlorinating / titanating agent is a titanium halide. 26. The catalyst according to item 25 of the patent application scope, in which the second chlorinating / titanating agent is titanium tetrachloride and the range of titanium to magnesium in the range of 0: 1 to 2: 1. 27. For example, the catalyst in item 13 of the scope of patent application, in which the organoaluminum preactivator is an alkyl aluminum of the general formula A1Ra32, where RA is an alkyl or halide having 1-8 carbon atoms, and RA is the same or not. The same, and at least one RA is home. 28. The catalyst in the scope of patent application No. 25, wherein the organoaluminum preactivator is trialkylaluminum. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 29. For the catalyst in item 13 of the scope of patent application, the ratio of aluminum to titanium ranges from 0.1: 1 to 2: 1. 30. If the catalyst in item 13 of the patent application scope, wherein the catalyst has a loose morphology conforming to the polymerization production method, will provide polyethylene with a molecular weight distribution greater than 7.0, and will have at least 6,000 grams of PE / gram of catalyst activity , And will provide a uniform particle size distribution with a small number of particles smaller than 125 microns. This paper size is applicable to China National Standard (CMS) A4 (210 X 297 mm) -4-574237 A8 B8 C8 ___ D8 6. Apply for a patent Scope 5 3 1 · — A polymer produced by a method that includes the following steps: (Please read the notes on the back before filling this page) a) One or more α-olefin monomers are contacted together under polymerization conditions. The catalyst is contacted in the presence of a catalyst, wherein the catalyst is formed by contacting: a magnesium alkoxide compound having the general formula Mg (〇R ′,) 2 and a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product. A, where R '' is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms; ii) contacting reaction product A with the first halogenating / titanating reagent to form reaction product B; and iii) will The reaction product B is contacted with a second halogenating / cinnifying agent, and is produced by a method of forming a catalyst component, wherein the first halogenating / titanating agent is a blend of Ti (〇PO4 / TiCl4). 3 2. The polymer according to item 31 of the scope of patent application, wherein the catalyst is made of: iv) produced by a method in which the catalyst component is contacted with an organoaluminum reagent. 33. The polymer according to item 31 of the application, wherein the monomer is an ethylene monomer. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 4 · If the polymer in the scope of patent application No. 31, the polymer is polyethylene. 35. The polymer according to item 31 of the scope of the patent application, wherein the soluble magnesium dialkoxide compound is an alkyl magnesium compound of the general formula MgRR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms, It may be the same or different) from the reaction product of an alcohol of the general formula R " OH (wherein the alcohol is a straight or branched chain alcohol and R "is an alkyl group of 4-20 carbon atoms). 36. If the polymer in the scope of patent application No. 35, the size of soluble magnesium paper is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) 574237 A8 B8 C8 D8 (2-ethylhexanol) magnesium. (Please read the notes on the back before filling out this page) 3 7 · If the polymer in the scope of patent application No. 35, the hospital-based magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium or butyl ethyl magnesium. 38. The polymer according to item 35 of the application, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol. 39. The polymer according to item 35 of the patent application, wherein the reaction hydrazone comprises a radical I. 40. The polymer according to item 39 of the application, wherein the aluminum alkyl is triethylaluminum. 41. For example, the polymer according to item 31 of the scope of patent application, in which the first chlorination / titanation reagent is Ti (〇Pr) WTiCl4 with a ratio of butadione: 14 to Ti (〇P〇4 · 0.5: 0.5: 1 to 6: 1 is the blend of the range. 42. For example, the polymer of the scope of the patent application No. 35, wherein the reaction 尙 includes an electron donor. 43. For the polymer of the scope of the patent application No. 42, wherein the electron donor is The ratio to magnesium is in the range of 0: 1 to 10: 1. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 44. For example, the polymer in the scope of patent application No. 43 in which the electron donor is an ether. 45. Such as The polymer of claim 31, wherein the halogenating agent has the general formula C1AR '" X, where A is an unreduced oxyphilic compound, and R' 'is a hydrocarbon-based moiety having 2 to 6 carbon atoms and X is the price of A minus 1. 4 6. If the polymer in the scope of patent application No. 31, the second chlorination / titanation reagent is titanium halide. 47. If the polymer in scope of patent application No. 46 ' The second chlorinated / ^ paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 Sichuan X 297 mm) 574237 A 8 B8 C8 D8 6. Scope of patent application 7 The titanating reagent is titanium tetrachloride and the range of titanium to magnesium in the range of 0: 1 to 2: 1. 48. For example, the polymer in item 32 of the scope of patent application, of which organic aluminum The preactivator is an aluminum alkyl of the general formula A1RA3, where RA is an alkyl or halide having 1 to 8 carbon atoms, RA is the same or different and at least one is an alkyl. 4 9. Such as The polymer in item 46 of the patent application, wherein the organoaluminum preactivator is trialkyl aluminum. 50. The polymer in item 47 of the application, wherein the ratio of aluminum to titanium is from 0.1: 1 The range is up to 2: 1. _ 51.—A catalyst-forming component / method ^ > The method includes: a) a soluble magnesium dialkoxide compound of the general formula Mg (OR '') 2 and Halogen exchange of an alkoxide with a halogenating agent is contacted to form reaction product A, where R " is a hydrocarbyl or substituted hydrocarbyl group having from 1 to 20 carbon atoms b) the reaction product A and the first halide / titanium Contacting an acidifying agent to form reaction product B; and c) contacting reaction product B with a second halogenating / titanating agent to form Media component, where the first halogenation / titanation reagent is a blend of Ti (OPr) 4 / TiCl4. 05. The Γ method according to item 51 of the patent application scope, wherein the soluble magnesium dialkoxide compound comprises An alkyl magnesium compound of the general formula MgRR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms and may be the same or different) and an alcohol of the general formula R " OH (wherein the alcohol is a linear or Branched-chain alcohols and R "in them are alkane of 4-20 carbon atoms. The paper size is applicable to Chinese National Standard (CNS) A4 specification (2) 0X297 mm. (Please read the precautions on the back before filling this page). 1T Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 574237 A8 B8 C8 D8 VI. Application for patent scope 8) The reaction product of the reaction. (Please read the precautions on the back before filling this page) 53. For the method of claim 52, the soluble magnesium compound is bis (2-ethylhexanol) magnesium. 1-4. The method according to item 52 of the application, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butyl ethyl magnesium. 55. The method of claim 52, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol. 56. The method of claim 52, wherein the reaction hydrazone comprises an aluminum alkyl. 57. The method according to claim 56 in which the aluminum alkyl is triethyl IS. 5 8. The method of claim 51, wherein the first chlorination / titanation reagent is Ti (〇Pr) 4 / TiCl4 with a ratio of TiCl4 to Ti (〇Pr) 4 ranging from 0.5: 1 to 6 : 1 is a blend in the range. 59. The method of claim 51, wherein the second chlorinating / titanating agent is a titanium halide. 60. The method of claim 59, wherein the second chlorinating / titanating agent is titanium tetrachloride and the range of titanium to magnesium is from 0: 1 to 2: 1. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 61. A method for preparing a catalyst, the method includes: a) contacting a catalyst component with an organoaluminum preactivator, wherein the catalyst component is composed of: i ) Contact a magnesium alkoxide compound of the general formula Mg (〇R ") 2 with a halogenating agent capable of exchanging an alkoxide with one halogen to form a reaction product A, where R " has from 1 to 20 carbons Atomic hydrocarbon group or substituted hydrocarbon group; This paper size applies Chinese National Standard (CNS) A4 specification (21ϋ × 297 mm) ~ _ 574237 A8 B8 C8 D8 cavity, application patent scope 9 ii) Reaction product A with the first halogenation / Titanating reagent to form reaction product B; and iii) produced by a method of contacting reaction product B with a second halogenating / titanating reagent, wherein the first halogenating / titanating reagent is Ti (〇Pr) 4 / TiCl4 blend. 62. The method according to item 61 of the patent application scope, wherein the first chlorination / cinnification reagent is Ti (〇PO4 / TiCl4 TiC) 4 to Ti (〇Ρι ·) 4 ratio is 0.5: 1 To 6: 1 is the blend of the range. 63. For the method of applying for the scope of the patent No. 62, the ratio of TrCL · to TKIPOP is 2: 1. 64. For the method of applying for the scope of the patent No. 61, where the soluble two The magnesium alkoxide compound is an alkyl magnesium compound of the general formula MgRR '(wherein R and R' are alkyl groups of 1 to 10 carbon atoms, and may be the same or different) and an alcohol of the general formula R''OH Wherein the alcohol is a linear or branched chain alcohol and the reaction product of R " is a group of 4-20 carbon atoms. 65. For example, the method of the scope of patent application No. 61, wherein the soluble magnesium compound is two ( 2-Ethylhexyl) magnesium. 66. The method according to item 61 of the application, wherein the alkyl magnesium compound is diethyl magnesium, dipropyl magnesium, dibutyl magnesium, or butyl ethyl magnesium. 67. Such as The method of claim 61 in the scope of patent application, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol, or 2-ethylhexanol. Please apply for the method in the scope of patent No. 61, wherein the reaction 尙 includes an aluminum alkyl. 69. For the method in the scope of the patent application No. 68, wherein the aluminum alkyl is triethyl ^ paper size applicable to China National Standard (CNS) A4 specifications ( 210X 297 mm) (Please read the notes on the back before filling out this page), ^ Τ Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 574237 Α8 Β8 C8 D8 々, patent application scope 10 base aluminum. 70. If applying for a patent The method of the scope item 61, wherein the reaction 尙 includes an electron donor. 7 1. The method of the scope of the patent application, item 70, wherein the ratio of the electron donor to the magnesium ranges from 0: 1 to 10: 1. 72 · Method according to item 71 of the patent application, wherein the electron donor is an ether. 7 3 · Method according to item 61 of the patent application, wherein the halogenating agent has the general formula C1AR " 'X, where A is an unreduced Oxyphilic compound, R ", x is a hydrocarbyl moiety having 2 to 6 carbon atoms. 74. The method according to item 61 of the patent application, wherein the halogenating agent is a blend of TiCl / TUOipi ·)] . 7 5 · The method according to item 61 of the patent application scope, wherein the second chlorination / acetic acid reagent is a titanium halide. 76. The method according to item 61 of the patent application range, wherein the second chlorinating / titanating agent is titanium tetrachloride and the range of titanium to magnesium in the range of 0: 1 to 2: 1. 7 7 · The method according to item 61 of the patent application scope, wherein the organoaluminum preactivator is an aluminum alkyl. 7 8 · The method according to item 61 of the patent application, wherein the electron donor is present in any of steps a), i), ii) or H i), and the electron donor to metal ratio therein is 0: 1 to 10: 1 is the range. 7 9. A method for polymerizing an α-olefin, comprising: a) contacting one or more α-olefin monomers together in the presence of a catalyst under polymerization conditions, wherein the catalyst is composed of: Applicable to China National Standard (CNS) Α4 specification (21〇: < 297 mm) (Please read the notes on the back before filling out this page) * 1Τ Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives 574237 A8 B8 C8 D8 Six 11 、 Application patent scope 11 i) The magnesium alkoxide compound of the general formula Mg (OR ") 2 is contacted with a halogenating agent capable of exchanging an alkoxide with a halogen to form a reaction product A. Here, R " A hydrocarbon group of 1 to 20 carbon atoms or a substituted hydrocarbon group; ii) contacting the reaction product A with a first halogenation / titanation reagent to form a reaction product B; and iii) contacting the reaction product B with a second halogenation / It is produced by the method of contacting the acetic acid reagent to form the reaction product C, where the first halogenation / titanation reagent is a blend of Ti (〇PO4 / TiCl4. 80. The method of the 79th scope of the application for patent Which includes: b) extracting polyolefin polymer Thereof. 81. The method of claim 80, wherein the polymer has a molecular weight distribution of 'less than 7.0. 8 2. The method of claim 80, wherein the polymer is polyethylene. 83. The method of claim 79, wherein the catalyst is produced by a method comprising: iv) contacting the reaction product C with an organoaluminum reagent. 84. The method according to item 79 of the patent application scope, wherein the first chlorination / titanation reagent is Ti (OP〇WTiCl4 with butyl 1 (: 14 to Ti (〇P〇4 ratio 0.5: 1 to 6) : 1 is the blend in the range. 85. The method according to item 84 of the patent application, wherein the ratio of TiCl4 to TKOP ·) 4 is 2: 1. 86. If the method in item 79 of the patent application, The halogenating agent in step 具有 has the general formula C] AR '' \, where A is an unreduced alkoxylate, R '' 'x This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) ( (Please read the notes on the back before filling this page), π. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed 574237 B8 C8 D8 6. Application for patent scope 12 is a hydrocarbon-based part with 2 to 6 carbon atoms. 87 · The method according to the scope of application of the patent item 86, wherein the halogenating agent is ClTi (〇iPr) 3. 88. The method according to the scope of the patent application, wherein the second chlorination / titanation agent is titanium halide. 89. For example, the method of claim 88, wherein the second chlorination / titanation reagent is titanium tetrachloride and its The range of titanium to magnesium is 0: 1 to 2: 1. 90. The method of claim 79 in the patent application, wherein the organoaluminum reagent is triethylaluminum. 9 1. The method of claim 79 in the patent application, wherein The electron donor is present in any one of steps 1) -iv), and the ratio of the electron donor to the metal is in the range of 0: 1 to 10: 1. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -12-
TW90127567A 2000-10-13 2001-11-06 Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith TW574237B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US09/687,688 US6486274B1 (en) 1997-01-28 2000-10-13 Hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith

Publications (1)

Publication Number Publication Date
TW574237B true TW574237B (en) 2004-02-01

Family

ID=32736637

Family Applications (1)

Application Number Title Priority Date Filing Date
TW90127567A TW574237B (en) 2000-10-13 2001-11-06 Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith

Country Status (1)

Country Link
TW (1) TW574237B (en)

Similar Documents

Publication Publication Date Title
US6486274B1 (en) Hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith
US6734134B1 (en) Ziegler-natta catalyst for tuning MWD of polyolefin, method of making, method of using, and polyolefins made therewith
US6930071B2 (en) Ziegler-natta catalyst for polyolefins
US6174971B1 (en) Ziegler-natta catalysts for olefin polymerization
US6864207B2 (en) Ziegler-Natta catalyst for polyolefins
US6693058B1 (en) Ziegler-natta catalyst for narrow to broad MWD of polyoefins, method of making, method of using, and polyolefins made therewith
JPS607642B2 (en) Catalyst for production of polyalphaolefin
JP4976129B2 (en) Ziegler-Natta catalyst for polyolefin
TW574237B (en) Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making, method of using, and polyolefins made therewith
US8063159B2 (en) Process for controlling morphology of Ziegler-Natta catalysts
JP4001477B2 (en) Ziegler-Natta catalyst for adjusting MWD of polyolefin, production method, method of use, and polyolefin produced using the same
TW575591B (en) Ziegler-natta catalyst for narrow to broad MWD of polyolefins, method of making, method of using, and polyolefins made therewith
TW585876B (en) Ziegler-Natta catalyst for tuning MWD of polyolefin, method of making, method of using, and polyolefins made therewith
EP1306391B1 (en) Ziegler-Natta catalyst for tuning MWD of polyolefin, method of making, method of using and polyolefins made therewith
JP2003155305A (en) Hydrogen response ziegler-natta catalyst improved to narrow mwd of polyolefin, method for producing the same, use thereof and polyolefin produced by using the catalyst
KR100851032B1 (en) Improved hydrogen response ziegler-natta catalyst for narrowing mwd of polyolefin, method of making, method of using, and polyolefins made therewith
EP1306394B1 (en) Ziegler-Natta catalyst for narrow to broad MWD of polyolefins, method of making, method of using, and polyolefins made therewith
JP2003147012A (en) Ziegler-natta catalyst for producing polyolefin having narrow mwd to broad mwd, method for producing the same, method for using the same and polyolefin produced by using the same
EP1308465A1 (en) Improved hydrogen response Ziegler-Natta catalyst for narrowing MWD of polyolefin, method of making it, polymerisation process using it, and polyolefins made therewith
KR100997132B1 (en) Ziegler-natta catalyst for tuning mwd of polyolefin, method of making, method of using, and polyolefins made therewith
JPS643210B2 (en)
KR20030044351A (en) Ziegler-natta catalyst for tuning mwd of polyolefin, method of making, method of using, amd polyolefins made therewith
BR0105223B1 (en) a process for the manufacture of a catalyst component, for the manufacture of a catalyst and for the polymerization of alpha olefin.
CN1418894A (en) Polyolefine catalyst, its making method, using method, and polymer made from said catalyst
KR20100082330A (en) Ziegler-natta catalyst for tuning mwd of polyolefin, method of making, method of using, and polyolefins made therewith

Legal Events

Date Code Title Description
GD4A Issue of patent certificate for granted invention patent
MM4A Annulment or lapse of patent due to non-payment of fees