A7 446 7 彳 7 ____B7__._ 五、發明說明（） II ( •裝---------訂- (請先閱讀背面之注意事項再填寫本頁) 本發明乃關於一種可用於生產超高分子量聚乙烯，尤 其纖維用超高分子量聚乙烯，之觸媒複合物，本發明之觸 媒複合物可於平常生產一般通用聚乙烯（Commodity PE)之 反應溫度下生產超高分子量聚乙烯，而達經濟效益。本發 明之觸媒複合物可控制聚乙懦之型態（morphology，爲粒徑 大小、粒徑分佈、形狀等之統稱）及分子量以符合凝膠紡絲 法(gel spinning)所需，製備高強度聚乙嫌纖維。 經濟部智慧財產局員工消費合作杜印製 眾所週知，在低壓法使用齊格勒（Ziegler)觸媒生產高 密度聚乙烯或線型低密度聚乙烯時，可藉著調整氫氣用量 (鏈移轉劑）及反應溫度來控制聚乙烯之分子量。在實際應 用上，爲便於操作，一般係在反應溫度變化不大下以調整 氫氣用量來控制聚乙烯之分子量，因此爲得高分子量聚乙 烯如吹膜級高密度聚乙烯，氫氣使用量極低，而一般如射 出級聚乙烯之較低分子量聚乙烯，則須使用較高量之聚乙 烯。然而，對於氣相法或淤漿法等聚乙烯製程，使用傳統 之齊格勒觸媒，如果不大幅降低反應溫度，即使完全不使 用氫氣以增高聚乙烯之分子量，亦很難生產超高分子量聚 乙烯。因此，傳統之超高分子量聚乙烯，皆使用—般之齊 格勒觸媒於淤漿法聚合製程中，在60 - 85°C之低反應溫度 下生產而得，相較於一般通用聚乙烯（Commodity PE)之反 應溫度低20 - 40°C。在較低之反應溫度下，不僅觸媒活性 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐) '~ 446 7 1 7 A7 ___B7__ 五、發明說明（） 差，亦影響單位時間内聚乙稀之產量（production rate)。因 此，本發明之觸媒，係針對該項缺點進行改良’可於生產 一般通用聚乙烯之反應溫度或更高之反應溫度下於淤漿 法、溶液法或氣相法中生產超高分子量聚乙烯’除不犧牲 ,聚乙烯之生產速率外，更具備高活性。本發明之觸媒，更 可在高的反應溫度下，藉著調整觸媒中成份的比例，來調 整所需之超高分子量聚乙烯的分子量。 本發明觸媒的另一項特點爲藉著所選用之無機載體 的型態（morphology)而可控制所生產超高分子量之型態。因 ，此，本發明觸媒所生產之超高分子量聚乙烯，具有高的堆 積密度（Bulk Density)、窄的粒徑分佈、可控制的粒徑大小， 本發明觸媒所生產的超高分子量聚乙烯，尤其適用於凝膠 紡絲法以生産高強度聚乙烯纖維。 因此，本發明之目的即爲提供一種可於高的反應溫度 下具備高活性而生產良好型態之超高分子量聚乙烯的觸媒 複合物。 本發明所稱之觸媒複合物係由下列各反應物反應製 備而得： 1)具有Mg(0 R')2化學式之鎂化合物（A) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公茇） (請先閱讀背面之注意事項再填寫本頁) t-----------參 經濟部智慧財產局員工消費合作社印製 .446 717 A7 ____B7_ 五、發明說明（） 2) 具有TiXm(0 R”)^m化學式之鈦化合物（B) 3) 具有CHXsCOOH化學式之醋酸鹵化物(C) ： --------^--- {請先閱讀背面之注意事項再填寫本頁) 4) 高表面積之無機載體（D) 5) 烷基鋁鹵化物（E) 其中尺'爲Ο - Cn之烷基，X爲鹵素原子，尺”爲C! - G。的 院基，m爲0至4之整數^ 觸媒之製備步驟係先將上述反應物（A)、 (B)及（C)於適 當溫度下熔融反應成澄淸液體狀後，再以惰性飽和碳氫化 合物稀釋，接著加入適量無機載體（D)，再於適當溫度下乾 燥、再稀釋後，於適當溫度下慢慢加入反應物（E)，最後以 前述稀釋溶劑洗滌數次後乾燥而得觸媒複合物。 經濟部智慧財產局員工消费合作社印製 本發明所稱之錶化合物，可爲單種鎂化合物或視需要 使用多種鎂化合物之混合，常見者爲二甲氧基鎂 (Mg(〇CH3)2)及二乙氧基鎂(Mg(OC晶)2)或兩者之混合物。 所稱之鈦化合物係作爲觸媒之主要活性成分，其中鈦化合 物中之IT較佳者爲-C6的烷基，X較佳者爲氯。這些鈦 化合物之實例如 TiCh、TiBn、Ti(OCH3)Br3、Ti(OC2H5)Ch、 Ti(OC%H9)Cl3、Ti(〇C6Hn)Brj、Ti(OCH3)2Br2、Ti(OC2H5)Cl3、 Ti(OC6Hn)2Bn、Ti(OCH3)3Br、Ti(OC2H5)3C1、Ti(〇C4H〇3Cl、 Ti(OC6Hn)3Br ' Ti(OCH3：l·、ΤΚΟΟΗφ、Ti(OC办)4、及 β 5 本紙張尺度遶用中國國家標準（CNS)A4規格（2〗0 X 297公釐） A7 44671 7 _B7___ 五、發明說明（）A7 446 7 彳 7 ____ B7 __._ V. Description of the Invention () II (• Equipment --------- Order- (Please read the precautions on the back before filling out this page) The present invention is about a product that can be used in production Ultra-high molecular weight polyethylene, especially ultra-high molecular weight polyethylene for fibers, catalyst composites, and the catalyst composites of the present invention can produce ultra-high molecular weight polyethylenes at the reaction temperature at which ordinary PE is generally produced The catalyst composite of the present invention can control the morphology (general name of particle size, particle size distribution, shape, etc.) and molecular weight of polyethylene to meet the gel spinning method. ) It is necessary to prepare high-strength polyethylene fibers. The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs and consumer printing is well known. When Ziegler catalyst is used in the low-pressure method to produce high-density polyethylene or linear low-density polyethylene, The molecular weight of polyethylene can be controlled by adjusting the amount of hydrogen (chain transfer agent) and the reaction temperature. In practical applications, for ease of operation, it is generally to adjust the amount of hydrogen when the reaction temperature does not change much. For the molecular weight of polyethylene, in order to obtain high molecular weight polyethylene such as blown film grade high density polyethylene, the amount of hydrogen used is very low, and generally lower molecular weight polyethylene such as injection grade polyethylene must use a higher amount of polymer. However, for polyethylene processes such as the gas phase process or slurry process, traditional Ziegler catalysts are used. If the reaction temperature is not significantly reduced, even if hydrogen is not used at all to increase the molecular weight of polyethylene, it is difficult to produce ultra-thin polyethylene. High molecular weight polyethylene. Therefore, traditional ultra high molecular weight polyethylenes are produced using a general Ziegler catalyst in a slurry polymerization process at a low reaction temperature of 60-85 ° C, compared to The reaction temperature in general PE is 20-40 ° C lower. At a lower reaction temperature, not only the catalyst activity 3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ) '~ 446 7 1 7 A7 ___B7__ 5. The description of the invention () Poor, it also affects the production rate of polyethylene per unit time. Therefore, the catalyst of the present invention is to improve the shortcoming of this defect' may The reaction temperature for producing general-purpose polyethylene or higher reaction temperature is to produce ultra-high molecular weight polyethylene in the slurry method, solution method or gas phase method. In addition to sacrificing the production rate of polyethylene, it has high activity. The catalyst of the present invention can adjust the molecular weight of the ultra-high molecular weight polyethylene required by adjusting the proportion of the components in the catalyst at a high reaction temperature. Another feature of the catalyst of the present invention is by The morphology of the selected inorganic carrier can control the type of ultra-high molecular weight produced. Therefore, the ultra-high molecular weight polyethylene produced by the catalyst of the present invention has a high bulk density (Bulk Density), With a narrow particle size distribution and a controllable particle size, the ultra-high molecular weight polyethylene produced by the catalyst of the present invention is particularly suitable for gel spinning to produce high-strength polyethylene fibers. Therefore, an object of the present invention is to provide a catalyst composite which can have a high activity at a high reaction temperature and produce a good type of ultra-high molecular weight polyethylene. The catalyst complex referred to in the present invention is prepared by reacting the following reactants: 1) a magnesium compound with a chemical formula of Mg (0 R ') 2 (A) The paper size is applicable to the Chinese National Standard (CNS) A4 specification ( 210 X 297 public money) (Please read the notes on the back before filling out this page) t ------------- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 446 717 A7 ____B7_ V. Invention Explanation () 2) Titanium compound (B) with the chemical formula of TiXm (0 R ”) ^ m 3) Acetic acid halide (C) with the chemical formula of CHXsCOOH: -------- ^ --- {Please read first Note on the back page, please fill in this page again) 4) High surface area inorganic support (D) 5) Aluminium alkyl halide (E) where the rule 'is an alkyl group of 0-Cn, X is a halogen atom, and rule "is C! -G. The base of the catalyst, m is an integer from 0 to 4 ^ The preparation steps of the catalyst are first to melt the above reactants (A), (B) and (C) to a clear liquid at a suitable temperature, and then inert. Saturated hydrocarbons are diluted, then an appropriate amount of inorganic carrier (D) is added, dried at a suitable temperature, and then diluted, the reactant (E) is slowly added at a suitable temperature, and finally washed with the aforementioned dilution solvent several times and dried to Get the catalyst complex. The consumer compound of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the compound mentioned in the present invention, which can be a single magnesium compound or a mixture of multiple magnesium compounds if necessary. The common one is dimethoxymagnesium (Mg (〇CH3) 2) And diethoxymagnesium (Mg (OC crystal) 2) or a mixture of both. The so-called titanium compound is used as the main active ingredient of the catalyst. Among the titanium compounds, IT is preferably -C6 alkyl group, and X is preferably chlorine. Examples of these titanium compounds are TiCh, TiBn, Ti (OCH3) Br3, Ti (OC2H5) Ch, Ti (OC% H9) Cl3, Ti (〇C6Hn) Brj, Ti (OCH3) 2Br2, Ti (OC2H5) Cl3, Ti (OC6Hn) 2Bn, Ti (OCH3) 3Br, Ti (OC2H5) 3C1, Ti (〇C4H〇3Cl, Ti (OC6Hn) 3Br 'Ti (OCH3: l, TKKOΗφ, Ti (OC Office) 4, and β 5 copies Paper dimensions are in accordance with Chinese National Standard (CNS) A4 specifications (2〗 0 X 297 mm) A7 44671 7 _B7___ 5. Description of the invention ()
Ti(OC6H]3；U、等，也可_使用上述物質之混合物，較佳者爲 四烷氧基鈦，尤其爲Ti(0(M^：u。所稱之醋酸鹵化合物係 作爲鎂化合物之熔融劑，其實例如CHFaCOOH、 CHChCOOH、CHBnC〇〇H、及 CHIsCOOH 等’最隹者爲 CHChCOOH。其中鎂化合物、鈦化合物及醋酸鹵化合物係 在鈍性氣體保護下於室溫同時加入反應器中再慢慢升溫至 30 - 80t的反應溫度漸漸熔融反應，而得澄淸液體。其中 鎂化合物對鈦化合物用量之莫耳比在3 - 20之間，視所需 超高分子量聚乙烯的分子量而定，較高的鎂/鈦比，可得較 高之分子量。醋酸鹵化合物對鎂化合物的莫耳比在0.6-3 之間，較佳爲0.8 - 1.5之間。其莫耳比太低，則無法熔融 鎂化合物，太高則影響烷基鹵化物對鈦及鎂化合物之活化 而影響最終觸媒之活性。 所稱之高表面積無機載體可依所欲控制之觸媒顆粒大 小來選擇適用之載體種類，而其比表面積200 πί/g以上， 孔隙體積在〇.5cc/g以上爲宜。比表面積以250 - 400 iri/g ’ 孔隙體積以0.7 - 2.0cc/g者較佳。而其平均粒徑以10 -ΙΟΟμιη較佳，用於生產凝膠紡絲法所需之超高分子量聚乙 烯，則以10 - 50μπι較佳。在使用前須經處理以減低表面 上之羥（ΟΗ)基數目，一般多在200 - 800°C，以乾燥氮氣吹 滌操作2 - 16小時。該高表面積無機載體用量，則須能夠 完全將反應物（A)、（B)及（C)完全含浸於其孔隙中。 6 ----------------^----------^ (請先閱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） 446717 A7 B7 經濟邨智慧財產局員工消費合作社印製 五、發明說明（） 本發明所稱之烷棊鋁鹵化物，係作爲觸媒主要之活化 劑。所稱之烷基鋁鹵化物爲具有A1 RjX^-p之化學式者， 其中以及X與前述者相同，p爲1至3之整數。其實例如 A1(C2H5)2C1、Al(C2H5)2Br、Al(i-C4H小C1、ΑΙΟΟΗφΒι·、 Al(C6Hn)2Cl、Al(C6H13)2Br、A1(C2H5)C12、Al(C2H5)Bn、 Al(i-C4H〇Cl2、Al(i-C4H9)Br2、Al(C6Hn)Ch 及 Al(C6H〗3)Br2 等，或其混合物，其中以AUC2H〇2Cl及AUC2H5)Ch較佳， ，又以A1(C2H5)C12爲最佳。其加入方式係在鈍性氣體保護 下，逐滴加入前述反應物中，操作溫度爲0 - 70°C，以30 -50t爲較佳，其用量爲使鋁與鎂之莫耳比爲2 - 12，以3 -6之間較佳。 本發明之觸媒可用於各種常用之低壓烯烴聚合之烯烴 ，反應製程生產超高分子量聚乙烯，例如溶液法、淤漿法及 氣相法。該聚合反應之壓力通常在lOOkg/cm2以下，以10 -50kg/cm2之間較佳。本發明之觸媒可於高於100°C之反應溫 度下生產超高分子量聚乙烯。聚合反應系統中除使用本發 明之觸媒，仍添加齊格勒觸媒常用之有機鋁化合物，如三 乙基鋁、三異丁基鋁等作爲助觸媒。 本發明所謂之分子量之測定係根據ASTM D1601方 法，依下述步驟測定計算而得 7 本紙張尺度適用中國國家標準（CNS)A4規格（21〇χ 297公釐） —：------- ------..—訂.---------1^· (請先閱讀背面之注意事項再填寫本頁) A7 4 46 71 7 五、發明說明（） (1) 首先將〇.〇25g之樣品，溶於25ml之Decalin中， 再置入矽油中加熱到150°C並溶解4hr。 (2) 取溶液l〇ml加入黏度計中’置入135°C的恆溫矽 油浴下測定。 (3) 測試開始，吸取黏度管內的試液上升，升到上儲存 部後，停止吸取，試液以自由落體落下。 (4) 當試液到達黏度管上刻度線時’計時器開始計時’ 直到試液到達下刻度線時，計時器按下（stop)，紀 錄所需時間。 (5) 取每一濃度測定誤差爲0.5秒以內之五個値予以平 均。 (6) 測得一濃度値之後，加入l〇ml decalin (145°C )並予 以攪拌，逐一測試五個濃度。 (7) 由每一濃度所測得溶液自黏度計中毛細管中流下 所需的時間，經計算及作圖之後可得IV値。 (8) 將IV値帶入公式【7?】=67^10“（Mw广7可計算 出重量平均分子量[ref]。 ref : Journal of Applied Polymer Science, Vol.36.567-582 (1988) 下列實施例係爲了方便說明本發明之施行步驟，但本 發明並不侷限於下列之任一或所有實施例。 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） . -裝---------訂----------.^- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局貧工消費合作社印製 經濟部智慧財產局員工消費合作社印Μ 446 7 17 A7 ____B7 _____ 五、發明說明（） 實施例1 - (A) 製備觸媒 在附有夾套及迴流裝置之5升玻璃容器中’加 入1莫耳的Mg(〇C2H5)2、0.1莫耳的Ti(〇CMi〇4、及1.25 莫耳的CHChCOOH，在60 °C下反應2小時’俟 Mg(〇C2H5)2已熔融後，加入正己烷1.5升稀釋後’加入 350克氧化矽載體（比表面積220 πί/g’孔隙體積1.3cc/g 平均粒徑15μιη，經600°C、4小時氮氣吹滌預處理）， 於65T：、氮氣吹漉下乾燥。再以1.5生之正己烷稀釋 後，再於40°C逐滴加入500毫升的EADC(二氯化乙基 鋁），再予以熟化1小時後，以每次1.5升之烷洗滌觸 媒3次後，乾燥即得觸媒複合物。 (B) 聚合反應 聚合反應於每小時具有可達25公斤生產速率之 氣相流體化床中進行，觸媒進料維持約2克/小時’觸 媒之平均滯留時間爲3.5小時，助觸媒爲三乙基鋁’其 進料速度爲10毫升/小時，反應溫度維持在l〇5°C，反 應壓力爲20kg/cm2，乙烯濃度爲35%，其餘爲氮氣’ 結果聚乙烯分子量爲1，590,000(凝膠紡絲法適用之分 子量在110-200萬間）、堆積密度爲0.5348/〇1^、平均 粒徑199μιη，觸媒活性爲2.05 X 106克聚乙烯/克鈦。所 得聚乙烯本國專利第235978號凝膠紡絲所得之聚乙烯 —----------- ------>—訂----------,^- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS>A4規格（210 X 297公爱〉 綠濟部智慧財產局員工消費合作社印製 446 7 1 7 A7 _____B7__ 五、發明說明（） 纖維強度達SOg/dei?以上。 比較官施例i 如實施例1，但觸媒使用取自美國永備公司用於其 Unipol製程製造線型低密度聚乙烯之商業化觸媒 UCAT - A3030(其觸媒製法如其美國專利第4,302,565 號所述）並改變反應溫度，其結果如下 應溫度 (°〇 分子量 堆稽密度 fe/cm5) 平均粒徑 (μηι) 觸媒活件 fsPE/sTi) 60 2.13X106 0.433 655 6.2xl04 70 1.49X106 0.412 743 1.4xl05 80 7.91x10s 0.394 866 2.8xl05 90 3.82xl05 0.372 998 5.3xl05 100 1.56xl05 0.354 1100 9.8xl05 由上表可看出，該傳統觸媒欲得100萬以上之超高 子量聚乙烯，反應溫度須低至70°c或以下，因此觸媒 活性大幅降低，亦將影響聚乙烯之生產速度。 實施例2〜5 同實施例1，僅改變其中ΤΚΟΟΗΟ,之莫耳數，其 結果如下： 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） . '---------訂---------I (請先閱讀背面之注意事項再填寫本頁) 4 46 7 A7 B7 經濟部智慧財產局貝工消费合作社印製 五、發明說明（） 尬 例輞 Ti(OCMI9) “草 Με/Τ: 分子景 堆稽密度 平均粒撺 (\xm) 觸媒活性 (ePE/eTi) 2 0.2 5 4.6χ105 0.562 165 9.8x10' 3 0.125 8 9.8Χ105 0.554 183 1.65xl0e 4 0.083 12 3.42x10' 0.519 216 2.27xl06 5 0.067 15 5.98x10s 0.512 232 3.32xl06 1 0.1 10 1.59xl06 0.534 .199 2.05xl06 由上表可看出， 調整觸媒 Mg/Ti比例，可達調整聚 乙烯分子量之目的。 實施例6〜:Π 同實施例1，但改變其中聚合反應溫度，其結果如 下 實施例號反應，溫度CC) 分子量 觸媒活件（gPE/gTi) 6 60 3.54x10® 1.36x10 7 70 3,40xl06 1.42x10 8 80 3.28χ106 1.48x10 9 85 2.78χ106 1.52x10 10 90 2.26χ106 1.84x10' 11 95 1.96Χ106 1.87x10: 1 105 1.47Χ106 2.05x10' 11 本紙張尺度適用中國囤家標準（CNS)A4規格（210 X 297公笼） ------------* 裝-------1 訂---------f ^ (請先閱讀背面之注意事項再填寫本頁) 44671 A7 B7 五、發明說明（） 由上表可看出，.本發明之觸媒亦可藉調整聚合反應 溫度，以達控制超高分子量聚乙烯之分子量之目的。 反應溫度愈低，分子量愈高，但觸媒活性亦愈差。 實施例12 同實施例i，但以Ti(0-iC3H小取代Ti(OCMi〇4，結 果聚乙烯分子量爲1，120,000、堆積密度爲0.562g/cm3， 平均密徑172μιη，觸媒活性爲7.2 xlOsgP_E/g‘Ti。 (請先閱讀背面之注意事項再填寫本頁) 裝---------訂·--------^! 經濟部智慧財產局貝工消費合作杜印製 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐）Ti (OC6H] 3; U, etc. can also be used as a mixture of the above substances, preferably titanium tetraalkoxide, especially Ti (0 (M ^: u. The so-called acetic acid halogen compound is used as a magnesium compound The melting agent is actually CHChCOOH, such as CHFaCOOH, CHChCOOH, CHBnCOOH, and CHIsCOOH. Among them, the magnesium compound, titanium compound and halogen acetate are added to the reactor at the same time under the protection of a passive gas. Then slowly raise the temperature to 30-80t, and the reaction temperature gradually melts to obtain a clear liquid. The molar ratio of the magnesium compound to the titanium compound is between 3 and 20, depending on the molecular weight of the ultra-high molecular weight polyethylene required. The higher the magnesium / titanium ratio, the higher the molecular weight. The molar ratio of the acetic acid halogen compound to the magnesium compound is between 0.6-3, preferably between 0.8 and 1.5. Its molar ratio is too low. It is impossible to melt the magnesium compound, and too high will affect the activation of the titanium and magnesium compounds by the alkyl halide and affect the activity of the final catalyst. The so-called high surface area inorganic carrier can be selected according to the size of the catalyst particles to be controlled. Carrier type, and its ratio The area is more than 200 πί / g, and the pore volume is more than 0.5 cc / g. The specific surface area is 250-400 iri / g ', and the pore volume is 0.7-2.0 cc / g. The average particle size is 10- ΙΟΟμιη is preferred. For the production of ultra-high molecular weight polyethylene required for the gel spinning method, 10-50μπι is preferred. Before use, it must be treated to reduce the number of hydroxyl (ΟΗ) groups on the surface, which is generally more than 200. -800 ° C, dry nitrogen blowing operation for 2-16 hours. The amount of this high surface area inorganic support must be able to completely impregnate the reactants (A), (B) and (C) in its pores. 6- --------------- ^ ---------- ^ (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 446717 A7 B7 Printed by the Consumers ’Cooperative of the Economic Village Intellectual Property Bureau V. Description of the invention () As the main activator of the catalyst, the alkyl aluminum halide is said to have the chemical formula of A1 RjX ^ -p, where X and the foregoing The same, p is an integer from 1 to 3. In fact, for example, A1 (C2H5) 2C1, Al (C2H5) 2Br, Al (i-C4H small C1, ΑΙΟΟΗφΒι, Al (C6Hn) 2Cl, Al (C6H13) 2Br, A1 ( C2H5) C12, Al (C2H5) Bn, Al (i-C4H〇Cl2, Al (i-C4H9) Br2, Al (C6Hn) Ch, Al (C6H〗 3) Br2, etc., or a mixture thereof, in which AUC2H〇2Cl And AUC2H5) Ch is better, and A1 (C2H5) C12 is the best. It is added under the protection of a blunt gas, and is added dropwise to the aforementioned reactants. The operating temperature is 0-70 ° C, preferably 30-50t, and the amount is such that the molar ratio of aluminum to magnesium is 2- 12, preferably between 3 and 6. The catalyst of the present invention can be used for various commonly used low-pressure olefin polymerization olefins, and the reaction process produces ultra-high molecular weight polyethylene, such as a solution method, a slurry method, and a gas phase method. The pressure of the polymerization reaction is usually below 100 kg / cm2, preferably between 10 and 50 kg / cm2. The catalyst of the present invention can produce ultra-high molecular weight polyethylene at a reaction temperature higher than 100 ° C. In addition to using the catalyst of the present invention in the polymerization reaction system, organoaluminum compounds commonly used in Ziegler catalysts, such as triethylaluminum and triisobutylaluminum, are added as auxiliary catalysts. The so-called molecular weight measurement of the present invention is based on the method of ASTM D1601, and is measured and calculated according to the following steps. 7 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇χ 297 mm). -------..— Order .--------- 1 ^ (Please read the notes on the back before filling this page) A7 4 46 71 7 V. Description of the invention () (1 ) First, 0.25 g of the sample was dissolved in 25 ml of Decalin, and then placed in silicone oil and heated to 150 ° C and dissolved for 4 hr. (2) Take 10 ml of the solution and add it to the viscometer 'and place in a constant temperature silicone oil bath at 135 ° C for measurement. (3) At the beginning of the test, the test solution in the suction viscosity tube rises and rises to the upper storage part, then stops the suction, and the test solution falls as a free fall. (4) When the test solution reaches the upper scale line of the viscosity tube, the 'timer starts timing'. When the test solution reaches the lower scale line, the timer is pressed (stop) to record the time required. (5) Take five radon of each concentration within 0.5 seconds and average them. (6) After measuring a concentration of ml, 10 ml of decalin (145 ° C) was added and stirred, and five concentrations were tested one by one. (7) The time required for the solution measured at each concentration to flow down from the capillary in the viscometer can be calculated and plotted to obtain IV 値. (8) Take IV 値 into the formula [7?] = 67 ^ 10 "(Mw Can 7 can calculate the weight average molecular weight [ref]. Ref: Journal of Applied Polymer Science, Vol. 36.567-582 (1988) The following implementation The examples are for the convenience of explaining the implementation steps of the present invention, but the present invention is not limited to any or all of the following embodiments. 8 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). --------- Order ----------. ^-(Please read the notes on the back before filling out this page) The Intellectual Property Bureau of the Ministry of Economic Affairs prints the wisdom of the Ministry of Economy Property Bureau employee consumer cooperative printing M 446 7 17 A7 ____B7 _____ V. Description of the invention () Example 1-(A) Preparation of catalyst In a 5 liter glass container with a jacket and a reflow device, add 1 mole of Mg (〇C2H5) 2, 0.1 mol of Ti (〇CMi〇4, and 1.25 mol of CHChCOOH, and reacted at 60 ° C for 2 hours. After 俟 Mg (〇C2H5) 2 has been melted, add 1.5 liters of n-hexane to dilute After adding 350 grams of silicon oxide support (specific surface area 220 πί / g), pore volume 1.3cc / g, average particle size 15μιη, and pretreatment by nitrogen blowing at 600 ° C for 4 hours. Dry) at 65T: under a nitrogen purge. After diluting with 1.5 liters of n-hexane, 500 ml of EADC (ethyl aluminum dichloride) was added dropwise at 40 ° C, and then aged for 1 hour. After washing the catalyst 3 times with 1.5 liters of alkane each time, the catalyst composite is dried to obtain the catalyst compound. (B) Polymerization Polymerization is carried out in a gas-phase fluidized bed with a production rate of up to 25 kg per hour. The media feed was maintained at about 2 g / h. The average retention time of the catalyst was 3.5 hours and the auxiliary catalyst was triethylaluminum. The feed rate was 10 ml / h. The reaction temperature was maintained at 105 ° C. The pressure is 20kg / cm2, the ethylene concentration is 35%, and the rest is nitrogen. As a result, the molecular weight of polyethylene is 1,590,000 (the molecular weight applicable to the gel spinning method is between 1.1 million and 2 million), and the bulk density is 0.5348 / 〇1 ^, The average particle diameter is 199μιη, and the catalytic activity is 2.05 X 106 g polyethylene / g titanium. The polyethylene obtained by gel spinning of the national patent No. 235978 —----------- --- --- > —Order ----------, ^-(Please read the precautions on the back before filling this page) This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 Kimiyoshi> Green Economic Affairs Intellectual Property Office employees consumer cooperatives printed 446 7 1 7 A7 _____B7__ V. invention is described in () fiber strength of SOg / dei above?. Comparative Example I is the same as in Example 1, but the catalyst used is the commercial catalyst UCAT-A3030, which was obtained from Yongbei Company for its Unipol process to produce linear low-density polyethylene (the catalyst manufacturing method is as in its US Patent No. 4,302,565 (Described above) and change the reaction temperature, the results are as follows: (° 〇 molecular weight stack density fe / cm5) average particle size (μηι) catalyst activity fsPE / sTi) 60 2.13X106 0.433 655 6.2xl04 70 1.49X106 0.412 743 1.4xl05 80 7.91x10s 0.394 866 2.8xl05 90 3.82xl05 0.372 998 5.3xl05 100 1.56xl05 0.354 1100 9.8xl05 As can be seen from the table above, the traditional catalyst wants to obtain ultra-high-quantity polyethylene of more than 1 million, and the reaction temperature must be as low as 70 ° c or below, so the catalyst activity is greatly reduced, which will also affect the production speed of polyethylene. Examples 2 to 5 are the same as in Example 1, except that the number of moles of TKKOΗ is changed, and the results are as follows: 10 This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm). '---- ----- Order --------- I (Please read the notes on the back before filling out this page) 4 46 7 A7 B7 Printed by the Shellfish Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ) Example Ti (OCMI9) "Grass Mε / Τ: Molecular Kernel Density Average Particle Size (\ xm) Catalyst Activity (ePE / eTi) 2 0.2 5 4.6χ105 0.562 165 9.8x10 '3 0.125 8 9.8χ105 0.554 183 1.65xl0e 4 0.083 12 3.42x10 '0.519 216 2.27xl06 5 0.067 15 5.98x10s 0.512 232 3.32xl06 1 0.1 10 1.59xl06 0.534 .199 2.05xl06 As can be seen from the table above, adjusting the catalyst Mg / Ti ratio can reach adjustment The purpose of the molecular weight of polyethylene. Example 6 ~: Π Same as in Example 1, except that the polymerization reaction temperature was changed. The results are shown in Example No. Reaction, temperature CC) Molecular weight catalyst activity (gPE / gTi) 6 60 3.54x10® 1.36x10 7 70 3,40xl06 1.42x10 8 80 3.28χ106 1.48x10 9 85 2.78χ106 1.52x10 10 90 2.26χ106 1.84x10 '11 95 1.96 × 106 1.87x10: 1 105 1.47 × 106 2.05x10' 11 This paper size is applicable to China Store Standard (CNS) A4 (210 X 297 male cage) ------------ * Pack ------- 1 Order --------- f ^ (Please read the notes on the back before filling this page) 44671 A7 B7 V. Description of the invention () As can be seen from the above table. The catalyst of the present invention can also adjust the polymerization reaction temperature to control the molecular weight of ultra-high molecular weight polyethylene. The lower the reaction temperature, the higher the molecular weight, but the worse the catalyst activity. Example 12 Same as Example i However, with Ti (0-iC3H small substitution of Ti (OCMi〇4), the polyethylene molecular weight was 1,120,000, the bulk density was 0.562g / cm3, the average diameter was 172μιη, and the catalyst activity was 7.2 x lOsgP_E / g'Ti. ( Please read the precautions on the back before filling this page) Loading --------- Order · -------- ^! 12 paper sizes printed by the Shellfisher Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economy Applicable to China National Standard (CNS) A4 (210 x 297 mm)