200534923 九、發明說明： 【發明所屬之技術領域】 ，本發明係關於—種在有機過氧化物及經控制量氧存在下 製造含過氧化物官能度之聚烯烴之方法。 【先前技術】 a具有過氧化物官能度之反應性聚稀烴在此技藝中受到注 意’因為接附至聚烯烴主鏈之過氧化物官能基可用=引發 各種化學反應’如接枝聚合。美國專利5,817，加號揭示使 用由電子束照射法製備之反應性聚烯烴之接枝聚合。此法 包括照射粒狀聚丙烯材料於實質上惰性氛圍内、暴露經照 射丙烯聚合物材料至經控制氧及加熱聚合物材料至特定溫 度一段特定時間。所得聚合物可用於引發接枝聚合反應在 烯經聚合物與乙烯單體之間。 有機過氧化物亦可用於聚烯烴與乙烯單體之接枝聚合 内。美國專利4,990,558號揭示-種製造接枝聚合物之; 法接枝邛位係由用自由基聚合引發劑之有機過氧化物之 處理製成。由化學分解的結果於聚合物產生之自由基在聚 合物上形成活性接枝部位並引發乙烯單體在此等部位之接 j聚合。然而，如此產生之活性接枝部位具有極短半衰期 時間而含該活性接枝部位之中間體不會自反應系統分離。 已知有機過氧化物可引發乙烯般體之均聚合；因此，接枝 聚合對均聚合之比率相當低。此外，因為除了大量接枝聚 合或均聚合以外，有機過氧化物在反應系統内具有優異可 動性，所以其會引發不宜位置如反應器壁上之聚合而在聚 98345.doc 200534923 合期間導致反應器污損。 美國專利申請案序號10/305，8 16號揭示一種在經控制量 氧存在下藉有機過氧化物處理聚合物材料製備經氧化稀烴 聚合物材料之方法。因為氧化反應會放熱，所以一般熱壓 器型反應器無法有效地除熱，因而造成聚合物溫度增至其 軟化點並產生不宜聚合物團塊。 種製造細煙聚合物接枝共聚物 有在操作上互相連接之第一與第二反應區之反應冑置，揭 示於美國專利5,696,203號。接枝共聚物係藉混合烯煙聚合 物與可自由基聚合的單體於氣相過程中而保持自由基聚: 條件及實質上非氧化環境於反應區内製備。未曾指出反應 可在氧化環境内及在可自由基聚合的單體不存在下實施。〜 因此’需要製備含自由流動過氧化物烯煙聚合物， :引發接枝聚合及其他熟悉此技藝者已知之反應中呈有反 應性而不用昂責照射源。申請人頃發 、反 物可在有機過氧化物及經控制量氧存在於包含 小3物在不同流動模式下循環之第一盥 ^ ^ ^ ^ /、乐一互連反應區之 内1"備，而不會造成-般困難性如聚入物圖 塊、反應器污損等。 k 口物團 【發明内容】 於入人、* 取合物與有機 貝’、 3過氧化物烯烴聚合物自其排出 互連反應區之雙區式及廡、 之第一與筹 物之方法，其包括應㈣貫施之含過氧化物稀煙影 98345.doc 200534923 將烯烃小口物及有機過氧化物饋入雙區式反應器内，藉 此形成烯烴聚合物混合物，其包含： I.、力90.0至、、々99·9重量％，較佳為約95 〇至約99·8重量 % ’最佳為約98.0至約99·5重量〇/。稀烴聚合物材料； II·約0.1至約1〇.〇重量％，較佳為約〇·2至約5 〇重量％，最 佳為約G.5至約2.〇重量％有機過氧化物，· 其中成分1+11之總合等於100重量〇/〇 ; 八中烯k水合物混合物暴露至在溫度i少^但在聚合 物之|人化』以下’較佳在約8代至14代下大於&綱體積 /〇車乂佳為約0.1至6體積％，最佳為約〇·2至4體積％氧於氣 相中之經控制量氧，藉此產生含過氧化物稀烴聚合物； 八中又區式反應益包括第一互連反應區，聚合物混合物 透過，亥區在迅速流化條件下流動，離開該第一反應區並進 ^ 互連反應區，聚合物混合物透過該區以插塞流動模 、：重力移動’離開该第二反應區並再導入該第一反應區 内，因此成立稀烴聚合物在二個反應、區間之循環。 •裙據本^明之另一具體例，在自雙區式反應器排出前， ^過氧化物稀烴聚合物係在溫度為至少8〇。〇但在聚合物之 —’、、乂下於惰性氛圍内，以氧濃度為0.004體積％或以下 藉自反應器移除氧處理。 人據本^明之另一具體例，在自雙區式反應器排出後， =匕氧化物烯烴聚合物係在溫度為至少但在聚合物之 々^以下於惰性氛圍内，以氧濃度為〇 〇〇4體積％或以下 方；第一反應器内處理。 98345.doc 200534923 根據本發日+ u 含過氧彳㈣體例，在自雙區式反應器排出前， 化點以下夢可二㈣合物之軟 一袖 "永a乙烯單體進入雙區式反應器内而與至少 可聚合乙烯單體接觸。 人^據本發明之另—具體例’在自雙區式反應器排出後， 化點t化物烯垣聚合物係在溫度為至少5 G °c至聚合物之軟 觸。1下於第二反應器内與至少一個可聚合乙烯單體接 2於製造含過氧化物烯烴聚合物材料之烯烴聚合物材料 匕丙烯、乙烯及丁烯q聚合物材料。 當丙稀聚合物材料用作原料供製造含過氧化物烯入 物材料時，丙烯聚合物較佳選自： ° (a)具有等規指數大於約80% ,較佳約9〇%至約99乃％之 丙細之結晶均聚物； ()具有選自乙烯及C^CiG α _烯烴之烯烴的丙烯之結晶 無規共聚物，其中經聚合烯烴含量，當使用乙烯時， 其為約1-10重量❹/。，較佳為約！至約4重量％，當使用 C4-C1Ga-烯烴時，其為約！至約2〇重量％，較佳為約j 至約16重量％，共聚物具有等規指數大於約6〇%，較 佳至少約70% ; (c)具有丙烯及二個選自乙烯及GW8 α _烯烴之烯烴之 、、、σ曰a無規二t物，其中經聚合烯烴含量，當使用乙稀 時，其為約1至約5重量％，較佳為約2至約4重量0/〇， ί使用C4_C 1 〇 -烯煙時，其為約1至約2 〇重量％，較 98345.doc 200534923 k為約1至約16重詈％，此二取w 一 χκ物具有等規指數大於 約 85% ; ⑷ 〜種烯烴聚合物組合物，其包含· (〇約H)至約60重量％，較佳為約15至約55重量％具 有等規指數大於約8〇%，較佳為約90至約99.5%之 結晶丙稀均聚物，或具有單體之結晶共聚物，其 單體選自⑷丙浠及乙稀，⑼丙烯、乙稀及C4_C8 « -烯烴，及（c)丙烯及q-csa _烯烴，共聚物具有 經聚合丙烯含量為超過約85重量％，較佳為約9〇 至約99重量％，而等規指數大於約6〇%; (屮約3至約25重量％，較佳為約5至約2〇重量％乙烯 與丙烯或CU-Cw烯烴之共聚物，其係在周圍溫 度下不溶於二甲苯内；及 (川）約10至約85重量。/〇，較佳為約15至約65重量％單 體之彈性共聚物，其單體選自（a)丙烯及乙烯，（b) 乙烯、丙烯及CVC8 α _烯烴，及（c)乙烯及 α 烯烴，共聚物視需要含有約0.5至約1〇重量％ 經聚合二烯並含有低於70重量％，較佳為約1〇至 約60重量％，最佳為約12至約55重量％經聚合乙 烯’且在周圍溫度下可溶於二甲苯内並具有固有 黏度為約1.5至約6.0 dl/克；其中（ii)及（π〗）之全部 基於全部聚合物組合物為約5〇至約9〇重量％， (u)/(iii)之重量比為低於約〇·4，較佳為〇」至ο」， 組合物較佳由聚合在至少二個階段中製備；及 98345.doc 200534923 (e)其混合物。 當乙烯聚合物材料用作原料供製 物材料時，乙稀聚合物材料較佳選自：乳化物細烴聚合 (&)乙細之均聚物； (b)乙卸與Q ·稀煙之血^目从 入 ι之無規共聚物’ α，烴選自具 D 烯烴含量為約1至約20重量％，較佳 重量0/<C3-C稀烴；及 ’、’、、力16 ⑷乙烯與二個C3-Cl°a_烯烴之無規三聚物，c3_c =具有經聚合α-稀烴含量為約1至約2。重量：:： 佳為1至約1 6重量％ ;及 (d)其混合物； 其中CVC1〇a_烯烴包括線性與分支稀烴，例如 烯、1_ 丁烯、異丁烯、卜戊婦、％甲基-!丁稀、!-已婦、 3广丁稀、ι庚烯、3_甲基]_己稀，及卜辛烯。 當乙烯聚合物為乙烯均聚物時，其通常具有密度為0 89 克/立方米或以上’當乙稀聚合物為具有Μ—·稀煙之乙 烯/、小物％ ’其通常具有密度為〇 9 i克/立方米或以上但低 於0別克/立方米。適當乙稀共聚物包括乙烯/丁婦]、乙—婦/ 己烯2、乙烯/辛烯·i及乙烯/4_甲基+戊烯。乙烯共聚物可 為阿後度乙烯共聚物或短鏈分支線性低密度乙烯共聚物 (LLDPE)，而乙烯均聚物可為高密度聚乙烯或低密 度聚乙稀（LDPE)。通常，LLDPEALDpE具有密度為〇9f〇 克/立方米或以上至低於〇·94克/立方米，HDPE及高密度乙 稀共&物具有密度大於0.940克/立方米，通常為0.95克/立方 98345.doc -10- 200534923200534923 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a method for producing a polyolefin containing peroxide functionality in the presence of an organic peroxide and a controlled amount of oxygen. [Prior art] a. Reactive polyhydrocarbons with peroxide functionality have received attention in this art 'because the peroxide functional groups attached to the polyolefin backbone are available = initiation of various chemical reactions' such as graft polymerization. U.S. Patent No. 5,817, Plus discloses graft polymerization using reactive polyolefins prepared by electron beam irradiation. This method involves irradiating the granular polypropylene material in a substantially inert atmosphere, exposing the irradiated propylene polymer material to controlled oxygen and heating the polymer material to a specific temperature for a specific period of time. The resulting polymer can be used to initiate a graft polymerization between an olefin polymer and an ethylene monomer. Organic peroxides can also be used in the graft polymerization of polyolefins and ethylene monomers. U.S. Patent No. 4,990,558 discloses a method for making a graft polymer; the method of grafting the nuclei is made by treating an organic peroxide with a radical polymerization initiator. As a result of chemical decomposition, free radicals generated by the polymer form active graft sites on the polymer and initiate the polymerization of ethylene monomers at these sites. However, the active graft site thus produced has an extremely short half-life time and the intermediate containing the active graft site is not separated from the reaction system. Organic peroxides are known to initiate homopolymerization of vinylenes; therefore, the ratio of graft polymerization to homopolymerization is relatively low. In addition, because in addition to a large number of graft polymerization or homopolymerization, the organic peroxide has excellent mobility in the reaction system, it will trigger polymerization at unfavorable locations such as the reactor wall and cause a reaction during polymerization 98345.doc 200534923 Device is dirty. U.S. Patent Application Serial No. 10/305, 8-16 discloses a method for preparing an oxidized dilute hydrocarbon polymer material by treating a polymer material with an organic peroxide in the presence of a controlled amount of oxygen. Because the oxidation reaction is exothermic, the general autoclave type reactor cannot effectively remove heat, which causes the polymer temperature to increase to its softening point and produces unsuitable polymer agglomerates. This type of fine smoke polymer graft copolymer has a reaction set of first and second reaction zones which are operatively connected to each other and is disclosed in U.S. Patent No. 5,696,203. Graft copolymers are prepared by mixing ene-fume polymer and free-radically polymerizable monomers in a gas phase process to maintain free-radical polymerization: conditions and a substantially non-oxidizing environment are prepared in the reaction zone. It has not been stated that the reaction can be carried out in an oxidizing environment and in the absence of free-radically polymerizable monomers. ~ Therefore, it is necessary to prepare a free-flowing peroxide-containing nicotinic polymer that is reactive in initiating graft polymerization and other reactions known to those skilled in the art without the need to blame a source of radiation. Applicants have found that organic peroxides and controlled amounts of oxygen exist in the first bath containing small three substances circulating in different flow modes ^ ^ ^ ^, Leyi Interconnected Reaction Zone 1 " Without causing-like difficulties such as conglomerates, reactor fouling, etc. K-mouth complex [Content of the invention] Yu Renren, * Extraction and organic shellfish ', 3-peroxide olefin polymer discharged from the interconnected reaction zone of the two-zone type, and the first method and method It includes a thin smoke shadow containing peroxides that should be applied consistently 98345.doc 200534923 Feeding olefinic mouthpieces and organic peroxides into a two-zone reactor, thereby forming an olefin polymer mixture, including: I. The force is from 90.0 to 99.99% by weight, preferably from about 95.0 to about 99.8% by weight, and most preferably from about 98.0 to about 99.5% by weight. Dilute hydrocarbon polymer material; II. About 0.1 to about 10.0% by weight, preferably about 0.2 to about 50% by weight, most preferably about G.5 to about 2.0% by weight organic peroxide Material, where the sum of ingredients 1 + 11 is equal to 100 weight 0 / 〇; the octaeneene k hydrate mixture is exposed to a temperature i less than ^ but below the polymer | humanization "preferably in about 8 generations to 14th generation is greater than & gang volume / 0 car is better about 0.1 to 6 vol%, most preferably about 0.2 to 4 vol% controlled amount of oxygen in the gas phase, thereby generating peroxide-containing Dilute hydrocarbon polymer; The eight-zone zone-type reaction benefit includes a first interconnected reaction zone, where the polymer mixture penetrates, and the zone flows under rapid fluidization conditions, leaving the first reaction zone and entering the interconnected reaction zone. The polymer The mixture passes through the zone to plug the flow pattern: gravity moves' out of the second reaction zone and re-introduces into the first reaction zone, so a cycle of dilute hydrocarbon polymer in two reactions and intervals is established. • According to another specific example of the present invention, before being discharged from the dual-zone reactor, the peroxide dilute hydrocarbon polymer is at least 80 ° C. 〇 However, the polymer was removed from the reactor by treating it with an oxygen concentration of 0.004% by volume or less under an inert atmosphere. According to another specific example of the present invention, after being discharged from the two-zone reactor, the olefin oxide olefin polymer is at a temperature of at least but below the temperature of the polymer in an inert atmosphere, with an oxygen concentration of 0. 0.004% by volume or less; treatment in the first reactor. 98345.doc 200534923 According to the present day + u peroxygen-containing carcass system, before being discharged from the dual-zone reactor, the soft one-sleeve of the Meng Ke two admixture below the chemical point " yong a vinyl monomer enters the dual zone The reactor is in contact with at least a polymerizable ethylene monomer. According to another specific example of the present invention, after being discharged from the two-zone reactor, the polymer having a melting point of t-alkylene is at a temperature of at least 5 G ° C to the soft touch of the polymer. It is connected with at least one polymerizable ethylene monomer in the second reactor in one step. It is used in the production of olefin polymer materials containing peroxide olefin polymer materials, such as propylene, ethylene, and butene q polymer materials. When the acrylic polymer material is used as a raw material for the production of the peroxide-containing polyolefin material, the propylene polymer is preferably selected from: (a) having an isotactic index greater than about 80%, preferably about 90% to about 99 is a fine crystalline homopolymer; () a crystalline random copolymer of propylene having an olefin selected from the group consisting of ethylene and C ^ CiG α-olefins, wherein the content of the polymerized olefin, when ethylene is used, is about 1-10 weight ❹ /. , Preferably about! To about 4% by weight, when C4-C1Ga-olefin is used, it is about! To about 20% by weight, preferably about j to about 16% by weight, the copolymer has an isotactic index greater than about 60%, preferably at least about 70%; (c) having propylene and two selected from ethylene and GW8 α_olefin, olefin, σ, σ, a random di-t, wherein the content of the polymerized olefin, when using ethylene, is from about 1 to about 5% by weight, preferably from about 2 to about 4% by weight. / 〇, when using C4_C 1 0-ene smoke, it is about 1 to about 20% by weight, compared to 98345.doc 200534923 k is about 1 to about 16% by weight, the second taking w-χκ has an isotactic The index is greater than about 85%; 〜 ~ an olefin polymer composition comprising: (0 to about H) to about 60% by weight, preferably about 15 to about 55% by weight has an isotactic index greater than about 80%, more than It is preferably about 90 to about 99.5% of a crystalline acrylic homopolymer, or a crystalline copolymer having a monomer selected from the group consisting of propylene and ethylene, propylene, ethylene and C4_C8 «-olefins, and ( c) propylene and q-csa olefin, the copolymer has a polymerized propylene content of more than about 85% by weight, preferably about 90 to about 99% by weight, and an isotactic index greater than about 60%; (屮 about 3 Up to about 25 % By weight, preferably about 5 to about 20% by weight of a copolymer of ethylene with propylene or CU-Cw olefin, which is insoluble in xylene at ambient temperature; and (Sichuan) about 10 to about 85 weight. 〇, preferably about 15 to about 65% by weight of an elastomeric copolymer of monomers selected from (a) propylene and ethylene, (b) ethylene, propylene, and CVC8 α-olefins, and (c) ethylene and α Olefins, copolymers, if desired, contain from about 0.5 to about 10% by weight of polymerized diene and contain less than 70% by weight, preferably from about 10 to about 60% by weight, and most preferably from about 12 to about 55% by weight Polymerized ethylene 'and soluble in xylene at ambient temperature and having an inherent viscosity of about 1.5 to about 6.0 dl / g; wherein (ii) and (π) are all about 50 to about 50 based on the total polymer composition About 90% by weight, (u) / (iii) weight ratio is less than about 0.4, preferably 0 ″ to ο ″, the composition is preferably prepared by polymerization in at least two stages; and 98345. doc 200534923 (e) mixtures thereof. When the ethylene polymer material is used as the raw material supply material, the ethylene polymer material is preferably selected from the group consisting of: emulsion fine hydrocarbon polymer &Amp; B homopolymer of B fine; (b) B random discharge and Q · dilute smoke ^ random random copolymer 'α, hydrocarbon is selected from D with olefin content of about 1 to about 20 % By weight, preferably 0 / < C3-C dilute hydrocarbons; and ',' ,, force 16 ⑷ random copolymer of ethylene and two C3-Cl ° a_ olefins, c3_c = with polymerized α- The dilute hydrocarbon content is from about 1 to about 2. Weight: :: preferably from 1 to about 16% by weight; and (d) a mixture thereof; wherein the CVC10a-olefin includes linear and branched dilute hydrocarbons, such as olefins, 1-butene , Isobutylene, buprofen,% methyl-! Butan,! -Coated, 3 butyl butan, ιheptene, 3_methyl] _hexane, and bucinene. When the ethylene polymer is an ethylene homopolymer, it usually has a density of 0 89 g / m3 or more. 'When the ethylene polymer is ethylene with M— · smoke, the small%. It usually has a density of 0. 9 i / m3 or more but less than 0 bu / m3. Suitable ethylene copolymers include ethylene / butylene, ethylene-butylene / hexene 2, ethylene / octene · i, and ethylene / 4-methyl + pentene. The ethylene copolymer may be an ethylene copolymer or a short-chain branched linear low density ethylene copolymer (LLDPE), and the ethylene homopolymer may be a high density polyethylene or a low density polyethylene (LDPE). In general, LLDPEALDpE has a density of 0.95 g / m3 or more to less than 0.94 g / m3. HDPE and high-density ethylene copolymers have a density greater than 0.940 g / m3, usually 0.95 g / m3. Cubic 98345.doc -10- 200534923
::二物材料適有*度為。·89至。·97克/立方米之乙烯 及hDPE。 於實施本發明。乙烯聚合物較佳為LLD，PE 合物材二時，物材料用作原料供製造含過氧化物烯烴聚 丁烯-1聚合物材料較佳選自· ⑷丁稀]之均聚物； . 'I烯·：乙烯、丙歸或C5_C 一烴之共聚物或三聚 二:用單體含量範圍為約1至―;及 適當聚丁烯-1均或丑臂 ^(MFR)A^〇 ! 一 可為荨規或間規並具有熔物流 )為約0·1至15〇 dg/分鐘，較 η 為約0·5至75。 叙彳土為約〇·3至1〇〇，最佳 此等丁烯-1聚合物材料' 1 已知。適者咬 /、製備方法及其特性為此技藝 週田艰丁烯-1聚合物 之齊格勒-納塔（Ziegie卜使用具有丁稀_1 述，„戈由烯 a) 1媒獲得，如WO 99/45043所 4由丁席-1之金屬茂平人 π 1揭干铋/、， 士 Α σ焱侍，如WO 02/10281 1所述， -揭不物併入本文供參考。 丁烯-1聚合物材料較佳 气丙株θ 3有取多約Η莫耳％共聚合乙烯 4内烯。更佳的是，丁 曰後用μ条H色 Λ 3物材料為一種均聚物，在7 爰用廣角X射線剛定之結晶度為至少約更 佳為約45%至約70%，最私炎 取仏為約55¾至約6〇%。 本發明之方法可以連讀赤 ^ . 、2刀批方式實施。在連續或分批” 方式中，烯烴聚合物材料另士 、 牡迚刀子 51 ^ ^ ^ ^ ^ 為過氧化物饋入雙區式反應 杰内，較佳在有機過氧仆 之進料速率為每分鐘每100份 98345.doc 200534923 (PPh)浠《合物材料約u至㈣份錢過氧化物，最 約0.2至約2 Pph/分鐘’藉此形成稀烴聚合物混合物。二: 反應之有機過氧化物之全部量為約(M至約10重量％，复中 聚合物材料與有機過氧化物之總合為1〇〇重量％。氧在雔 、 孖在，辰度大於0.004體積％，較佳為低於 15%，更佳為低於8%，最佳為約1〇至約5體積 目 中。’在溫度高於饥但在聚合物之軟化點以下，較佳 80C至約140C或軟化點’無論多低，藉此形成含化 婦煙聚合物。在第-與第二反應區内之反應溫度^ 不同。 ,U及 根據分批方式，含過氧化物烯烴聚合物視需要 溫度為至少，C但在聚合物之軟化點以下於具有氧濃声為 〇:〇4體積%或以下之惰性氛圍内藉自反應器除氧處理二 滅任何反隸自纟基，並自有機料化物移除降解副; 物。。或二含過氧化崎聚合物視需要在溫度為至= 50 C至♦合物之軟化點以下，藉單體饋入雙區式反應 與至少一個可聚合乙烯單體接觸。 根據連續方式，含過氧化物烯烴聚合物係 ㈣出並視需要在溫度為至少約，c但在聚合物之= 二I:有=度為。A。4體積MM之惰性氛圍内處 理以‘滅任何反應性自由基’並自第二反應 r物移除降解副產物。或者，含過氧化物歸烴聚= 個可聚合乙烯單體於第 兩要在溫度為至少約5(rc至聚合物之軟化，： 應器内接觸 98345.doc 200534923 *第反應B。可為雙區式反應益、熱壓器或其他熟悉此技 藝者已知之反應n 1二反應器較佳為雙區式反應器。 雙區式反應器為-種具有二個互連反應區之反應器，盆 包括： 第互連反應區，聚合物混合物透過該區在迅速流化條 件下流動，離開該第一反應區並進入第二互連反應區，聚 合物混合物透過該區以插塞流動模式藉重力移動，離開該 第二反應區並再導入該第一反應區内，因此成立稀煙聚合 物在二個反應區間之循環。 ^確而σ，水合物顆粒在迅速流化條件下流過該反應區 之第-區’透過管連接器離開該第—反應區進入氣/固分離 構件如旋風分離H内，其可自氣體材料分離㈣顆粒而顆 粒離開氣/固分離構件並進人該反應區之第二區，其透過該 區以插塞机動核式藉重力移動，藉另一管連接器離開該第 二反錢並再導人該第—反應區内，因此成立聚合物在二 個反應區間之循環。導入反應器之氣體流動具有足夠高流 速以在速率為約每分鐘約G 5至1G個循環，較佳為每分鐘約 1至4個循環來循環聚合物顆粒。 反應器設計及其操作條件揭示於美國專利5,696,2〇3號， 其併入本文供參考。 為了在反應器系統内保持經控制量之氧，需要將氧恆定 加入反應器中以補償反應中消耗並通風至反應器外側之 氧。 適當有機過氧化物包括醯基過氧化物，如苯甲醯及二笨 98345.doc 13 200534923 甲酉&過氧化物，二烷基及芳烷基過氧化物，二第三丁基過 氧化物、二枯基過氧化物；枯基丁基過氧化物；u_二^三 丁基過乳基-3,5,5-三甲基環己烷；2,5_二甲基]，2,5_三第三 丁基過氧基己烧’及雙（α_第三丁基過氧基異丙基苯: 過氧醋類如雙（α_第三丁基過氧基戊酸S旨，·第三丁基過苯甲 酸二甲基己基_2,5_二（過苯甲酸第三丁基-二（過 酞酉夂酉曰)’第二丁基過氧基_2_乙基己酸酯，及二甲基」_ 經基丁基過氧基·2_乙基已酸醋，及過氧基碳酸醋如二（2_ 過氧基碳酸氫醋、二（正丙基）過氧基碳酸氨醋及 二二丁基％己基)過氧基碳酸氫酯。過氧化物可純粹使 或用於稀釋介質内，其具有活性濃度為㈣至約⑽重量 二較佳為4〇至約80重量％，其中過氧化物 液於p i 心二丁基過辛酸酯作為50重量％分散 人、^ 油内市售商品名稱為LupersolPMS。 义乳化物稀烴聚合物材料之數目平均分 為大於1〇,〇〇〇，雖秋1 ( η)較if土 _ 、在有些情況下可較低。 含過氧化物烯烴聚合物- 1至約200毫莫产 、氧化物浪度較佳範圍為約 笔矣耳過氧化物於1公 (毫莫耳/公斤)，較佳A… 斤3過虱化物烯烴聚合物 孕乂佳為、、、勺5至約150毫墓ι/八a m 10至約100毫莫耳/公斤。 莫耳入斤，彔佳為約 含過氧化物烯烴聚合物材 化合物處理含過氡化物稀溫下用乙稀單體 明確而言，接枝過程包=製備接技共聚物。 10至8〇 pph，土來σ條件下，較佳為约 取“約20至4”沖，在溫度為自至少約50 98345.doc 200534923 U，合物之軟化點以下，用約5至240份（pph)至少一個可 聚合單體處理100份含過氧化物烯烴聚合物。:: The two materials are suitable for * degree. 89 to. 97 g / m3 of ethylene and hDPE. In implementing the present invention. Ethylene polymer is preferably LLD, PE composite material, the material is used as a raw material for the production of peroxide olefin-containing polybutene-1 polymer material is preferably selected from the group of homopolymers; 'Iene :: Copolymer or trimer of ethylene, propylene or C5_C hydrocarbon: use monomer content ranging from about 1 to-; and appropriate polybutene-1 or ugly arm ^ (MFR) A ^. One can be a net gauge or a syndiotactic gauge and has a melt stream) of about 0.1 to 150 dg / min, and about 0.5 to 75 compared to η. The xanthan clay is about 0.3 to 100, and the best of these butene-1 polymer materials is known. The fittest bite, the preparation method and its characteristics are the skills of this technology. Zhou Tianren Butene-1 polymer Ziegler-Natta In WO 99/45043, the bismuth is removed from the metallocene π 1 of Ding Xi-1, as described in WO 02/10281 1, and the matter is incorporated herein by reference. The -1 polymer material is preferably the gas propylene strain θ 3, which has about 4 moles of copolymerized ethylene 4 ene. More preferably, Ding Yuehou uses μ strips of H color Λ 3 material as a homopolymer. The wide-angle X-ray crystallinity at 7 ° C is at least about 45% to about 70%, and the most private inflammation is about 55¾ to about 60%. The method of the present invention can continuously read red ^., The two-blade batch method is used. In continuous or batch mode, the olefin polymer material is another one, the burdock knife 51 ^ ^ ^ ^ ^ is fed into the two-zone reaction chamber for peroxide, preferably in organic peroxygen. The feed rate is 98345.doc 200534923 (PPh) per minute per minute. The compound material is about u to about 1 part per million peroxide, up to about 0.2 to about 2 Pph / min., Thereby forming a dilute hydrocarbon polymer. Mix Thereof. 2: The total amount of the reacted organic peroxide is about (M to about 10% by weight, and the total amount of the polymer material and the organic peroxide is 100% by weight. More than 0.004% by volume, preferably less than 15%, more preferably less than 8%, and most preferably about 10 to about 5 vol. 'At temperatures above hunger but below the softening point of the polymer, Better 80C to about 140C or softening point 'no matter how low, thereby forming a chemical-containing women's tobacco polymer. The reaction temperature in the first and second reaction zone is different. U, and according to the batch method, containing peroxide The temperature of the olefin polymer as required is at least, C but below the softening point of the polymer in an inert atmosphere with an oxygen concentration of 0: 04% by volume or less. The reactor is deoxidized to eliminate any reaction. And remove the degradation by-products from the organic compounds. Or the peroxide-containing polymer, if necessary, is below the softening point of the compound at a temperature of up to 50 C and the compound is fed into the two-zone reaction by the monomer. Contact with at least one polymerizable ethylene monomer. According to a continuous process, the peroxide-containing olefin polymer is decanted. If necessary, the temperature is at least about c, but in the polymer = two I: there are = degrees. A. 4 volume MM inert atmosphere treatment to 'kill any reactive free radicals' and move from the second reaction r In addition to degradation by-products. Or, peroxide-containing hydrocarbons are polymerized = two polymerizable ethylene monomers must be softened at a temperature of at least about 5 (rc to polymer, in contact with the reactor 98345.doc 200534923 * section Reaction B. It can be a two-zone reactor, autoclave, or other reaction known to those skilled in the art. The n 1 two-reactor is preferably a two-zone reactor. The two-zone reactor is a type with two interconnections. The reactor of the reaction zone includes a first interconnected reaction zone through which the polymer mixture flows under rapid fluidization conditions, leaving the first reaction zone and entering the second interconnected reaction zone, and the polymer mixture passes through the zone. Move by gravity in the plug flow mode, leave the second reaction zone and re-introduce the first reaction zone, so the cycle of the dilute smoke polymer in the two reaction zones is established. Indeed, σ, the hydrate particles are flowing rapidly Through the reaction zone-through the reaction zone The connector leaves the first reaction zone and enters the gas / solid separation member such as cyclone H. It can separate the radon particles from the gaseous material and the particles leave the gas / solid separation member and enter the second zone of the reaction zone, which passes through the zone. The plug-in mobile nuclear type is moved by gravity, and another tube connector is used to leave the second anti-money and guide the first reaction zone, so the cycle of the polymer in the two reaction zones is established. The gas introduced into the reactor The flow has a flow rate high enough to cycle the polymer particles at a rate of about G 5 to 1 G cycles per minute, preferably about 1 to 4 cycles per minute. The reactor design and its operating conditions are disclosed in US Patent 5,696, No. 023, which is incorporated herein by reference. In order to maintain a controlled amount of oxygen in the reactor system, it is necessary to constantly add oxygen to the reactor to compensate for oxygen consumed in the reaction and vented to the outside of the reactor. Suitable organic peroxides include fluorenyl peroxides such as benzamidine and dibenzyl 98345.doc 13 200534923 formamidine & peroxides, dialkyl and aralkyl peroxides, di-tert-butyl peroxide Compounds, dicumyl peroxide; cumyl butyl peroxide; u_di ^ tributylperlactyl-3,5,5-trimethylcyclohexane; 2,5_dimethyl], 2,5_tri-tert-butylperoxyhexane 'and bis (α_tert-butylperoxycumene: peroxy vinegars such as bis (α_tert-butylperoxyvaleric acid) The purpose is, the third butyl perbenzoic acid dimethylhexyl_2,5_di (the third butyl perbenzoic acid bis-di (perphthalate) said the second butyl peroxy_2_ Ethylhexanoate, and dimethyl "_Ethylbutylperoxy · 2-ethylhexanoate, and peroxycarbonate such as di (2-peroxybicarbonate, di (n-propyl) ) Peroxy urethane carbonate and didibutyl% hexyl) peroxy hydrogen carbonate. The peroxide can be used purely or in a diluting medium, and it has an active concentration of ㈣ to about ⑽ by weight, preferably 4 〇 to about 80% by weight, wherein the peroxide solution is 50% dibutyl peroctanoate as 50 Weight percent dispersion, ^ oil sold in the market under the trade name LupersolPMS. The average number of dilute hydrocarbon polymer materials is greater than 10,000, although autumn 1 (η) is more than if soil _, in some cases It can be lower. Peroxide-containing olefin polymer-1 to about 200 millimoles, the preferred range of the oxide range is about 1 milligram of peroxide (millimoles / kg), preferably A … 3 pounds per alkene olefin polymer is preferably 、, 、, 5 to about 150 milligrams / eight am 10 to about 100 millimoles / kg. Moore into the pounds, 彔 佳 is about peroxide Treatment of olefin polymer materials with perylene compounds at dilute temperatures. Using vinyl monomers, specifically, the grafting process includes preparation of graft copolymers. 10 to 80 pph, preferably ≈ "About 20 to 4" punch, at a temperature of at least about 50 98345.doc 200534923 U, below the softening point of the compound, treat 100 parts of peroxide-containing with about 5 to 240 parts (pph) of at least one polymerizable monomer Olefin polymer.
乙烯單體具有一個以上不飽和鍵，單體可包含c2-c20直鏈 ^支鏈脂肪鏈或經取代或未經取代芳香族、雜環或脂環於 早或多環化合物内。較佳的是，乙稀單體為C2-C20乙稀單 體。乙烯之例為:苯乙烯、乙烯萘、乙烯吡啶、乙烯吡咯烷 酮、乙浠卡巴唾、甲基苯乙烯、甲基氣苯乙稀、對第三丁 基苯乙稀、甲基乙烯吼。定、乙基乙烯D比咬、丙稀赌、甲基 丙烯腈、丙稀酸醋、甲基丙稀酸醋、不飽和酸酐、不飽和 酸之金屬鹽及其混合物、特別是笨乙烯、丙烯睛、丙烯酸 丁醋、丙烯酸2-乙基己醋、甲基丙稀酸"旨、丙浠酸甲醋、 甲基丙烯酸丁酯及其混合物。 除非另予指明，以下實例所述之稀烴聚合物材料之特 性、組合物及其他特徵係根據以下試驗方法決定： 熔物流速（’’MFR，，）： ASTM D1238，單元為dg/分鐘；23(Γ(： ; 216公斤； 具有MFR在1〇〇以下之聚合物材料，使用全模； 具有MFR等於或在1〇〇以上之聚合物材料，使用 模；除非另予指明。 等規指數（，，Ι·Ι·”）： 界定為不溶於二曱苯内之烯烴聚合物之百分比。 在室温下可溶於二曱苯内之稀烴聚合物之重量％係 在室溫下於設有攪拌器之容器内溶解2·5克聚合物 於250毫升二甲苯内並在135。。下攪拌加熱2〇分鐘測 98345.doc 15 200534923 定。溶液冷卻至25°C同時持續攪拌，然後靜置而不 ㈣30分鐘，使固體可沉降。固體用濾紙過濾，殘 餘溶液係用氮流處理而蒸發，固體殘餘物係在8(rc 下真工乾燥，直到到達恆定重量為止。此等值實質 上對應由沸騰正庚烧萃取測定之等規指數，在定義 上其構成聚丙稀之等規指數。 過氧化物濃度： 藉由官能基之定量有機分析，S· Siggia等人，4th Ed·， NY, Wiley 1979, ρρ· 334-42。 分子量與分子量分布（MWD) 樣品係在濃度為70毫克/50毫升安定化三氯苯 (25〇极克/毫升BHT)下製備。然後，樣品加熱至17〇 C歷2.5小時以溶解化。然後，樣品係在145<^，流 速為ι·ο毫升/分鐘下，使用相同安定化溶劑在Waters 〇?(^\^2000上進行。三個聚合物乙仏管柱以串聯使用 (Plgel，20微米混合的 ALS，300X7.5 毫米）。 氣恶色層分離術 低聚物含量之測定： 精確地秤重7-8克聚合物樣品進入5〇毫升血漿瓶 内。藉吸管加入25毫升二氯甲烷並用鐵氟隆襯底隔 片欲封物緊密地蓋住小瓶（緊密地壓扁蓋部以確保 密封物固定）。在室溫下放置小瓶於超音波浴内。除 去部分萃取物並藉氣態色層分離術（Agilent 5890 或相等物）分析。 98345.doc -16- 200534923 在此說明書中，除非另予指明，所有份、百分比及比率 皆依重量計。根據下列程序製備含過氧化物稀煙聚合物。 【實施方式】 實例1 含過氧化物浠烴聚合物係自具有熔物流速(MFR)為94 dg/分鐘及I.I.為96.5%之丙稀的結晶均聚物製備，市面上可 得自Basell USA Inc•。丙稀⑽〇克）之均聚物加入7升雙區 式反應H内，如美國專利5,696，加號之—般程序所述。反 應内之全部氣體流速保持在每小時Μ」標準公升 (SLH)。有機過氧化物（1〇〇克），Lupers〇ipMs，其為第三丁 基過軋基-2-乙基己酸酯於無氣味礦油精（〇ms)内之％重量 %溶液’獲自Atofina North America，Inc.，在進料速率為4 克:分鐘下泵抽入反應器内。然後，反應器在經控制量之氧 於氮乱内加熱至100°c，如表⑽紀錄。反應器保持在⑽。C下 歷⑽鐘，然後，在14〇t下歷另外⑼分鐘。然後，除去氧， 反應器在14Gt下在氮氣之覆蓋下歷另外⑼分鐘。最後，將 所得稀烴聚合物冷卻、排放並收集。稀烴聚合物之MFR及 其過氧化物濃度概述於表1。 /反應條件係與所得聚合物材料之特徵相關，如在反應前 後由炼物抓速改變證貫。聚合物之溶物流速及過氧化物含 量隨著氧濃度之增加而增加。 ，比較樣^概述於表2。比較樣品1及2顯示在才目同溫度處理 型材:在氧處理後聚合物之特徵，如未加入有機過氧化物 之樣口口者。比卓父樣品1-2顯示其mfRs無顯著增力口，指出在 98345.doc 200534923 此等條件下無顯著氧化反應。比較樣品3係由使用照射法製 備。聚合物原料係在氮覆蓋物下在0·5 Mrad下照射。然後， 經照射聚合物係在80°c下用1.45體積％氧處理6〇分鐘，然後 在140°C下用1.45體積％氧處理另外60分鐘。然後除氧。將 聚合物在140°C下在氮覆蓋物下加熱6〇分鐘、冷卻並收集。 表1及2紀錄之數據顯示在雙區式反應器實施之本發明方 法，比較於其他此技藝已知之方法，可產生具有高量過氧 化物官能度之含過氧化物烯烴聚合物。 表1 反應條件與聚合物特徵 樣品1 樣品2 樣品3 用於反應之氧濃度(體積％) 0.4' 0.8 6.0 所得ί 氏合物材料之特糌 MFR(dg/分鐘） 666 「1665 16000 過氧化物含量(毫莫耳/公斤） ΤΣΠ~— 30.1 171 表2 反應條件與聚合物特徵 比較性 樣品1 比較性 樣品2 比較性 樣品3 用於反應之氧濃度(體積％) 0 5.0 1.45 所得3 氏合物材料之特徵 MFR(dg/分鐘） 11.0 11.6 325 過氧化物含量(毫莫耳/公斤） 0 0 12.3 實例1製備之含過氧化物烯烴聚合物之活性可在乙烯單 體存在下藉測量聚合反應性測定。約85 pph苯乙烯單體， 市面上可獲自Aldrich Chemical Company，Inc.，加入含過氧 化物烯烴聚合物内而混合物密封於高壓不繡鋼盤内。然 後，此盤放入差示掃描熱量計（DSC)，型號DSC 7，由 Perkin-Elmer Corporation製造。混合物係在加熱速率為2 0 °C /分 98345.doc -18 - 200534923 鐘下自25°C加熱至70°C，然後在加熱速率為1°C /分鐘下自 70°C加熱至170°C。表3概述樣品1-3及比較例1-2之聚合焓及 反應轉化率。 表3 聚合物 焓(J/g) 轉化率(％) 樣品1 -446.9 63.8 樣品2 495.8 70.7 樣品3 -610.3 87.1 比較樣品1 0 0 比較樣品2 -152.5 21.8 實例1製備之含過氧化物聚烯烴之活性亦係在等溫條件 下藉DSC分析。約85 pph苯乙烯單體，市面上可獲自Aldrich Chemical Company，Inc.，加入含過氧化物聚稀烴内而混合 物密封於高壓不繡鋼盤内。然後，此盤放入差示掃描熱量 計（DSC)，型號 DSC 7，由 Perkin-Elmer Corporation製造。 混合物係在加熱速率為40°C/分鐘下自25t加熱至14(TC， 然後在該溫度下保持120分鐘。表4概述樣品1-3及比較例1-2 之聚合焓及反應轉化率。 表4 聚合物 焓(J/g) 轉化率(％) 樣品1 -360.4 51.4 樣品2 -426.7 60.9 樣品3 -617.7 88.1 比較樣品1 -19.1 2.7 比較樣品2 -308.2 44.0 98345.doc -19- 200534923 實例2 含過氧化物烯烴聚合物係自具有熔物流速（MFR)為9·8 dg/分鐘及Ι.Ι.為96.5%之丙烯的結晶均聚物製備，市面上可 得自Basell USA Inc·。丙烯（2000克）之均聚物加入7升雙區 式反應器内，具有如實例1所述之設備，在表5概述之各種 全部氣體流速下。定量Lupersol PMS在進料速率為4克/分鐘 下泵抽入反應器内供製造樣品1 -4。然後，反應器在表5紀 錄之具有經控制量氧於氮中之氣體混合物下加熱至100 °C。反應器保持在l〇〇°C下一段特定時間，然後加熱至140 °C並在相同溫度下保持60分鐘。然後，除去氧，反應器在 140°C下在氮氣之覆蓋下保持另外60分鐘。最後，將烯烴聚 合物冷卻、排放並收集。所得聚合物之特徵概述於表5。 比較樣品1為用作樣品1 -4之聚合物原料之丙烯之結晶均 聚物。表5之含過氧化物聚合物顯示其溶物流速、分子量、 分子量分佈（MWD)及低聚物含量之顯著改變，如由本文界 定之氣態色層分離法測定。樣品1 -4比較於原料者具有較高 MFR、較低分子量、分子量分佈及較低的低聚物含量。Ethylene monomers have more than one unsaturated bond. The monomers may include c2-c20 straight-chain branched aliphatic chains or substituted or unsubstituted aromatic, heterocyclic, or alicyclic compounds in early or polycyclic compounds. Preferably, the ethylene monomer is a C2-C20 ethylene monomer. Examples of ethylene are: styrene, vinylnaphthalene, vinylpyridine, vinylpyrrolidone, acetcarbazide, methylstyrene, methyl styrene, p-tert-butylstyrene, and methylethylene. Specific, ethyl vinyl D ratio, acrylic, methacrylonitrile, acrylic acid, methyl acrylic acid, unsaturated acid anhydride, unsaturated acid metal salts and mixtures thereof, especially stupid ethylene, propylene Eye, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, and mixtures thereof. Unless otherwise specified, the properties, composition, and other characteristics of the dilute hydrocarbon polymer materials described in the following examples are determined according to the following test methods: Melt flow rate ('' MFR ,,): ASTM D1238, unit is dg / min; 23 (Γ (:; 216 kg; with polymer materials with MFR below 100, use full mold; with polymer materials with MFR equal to or above 100, use mold; unless otherwise specified. Isotactic index (,, Ι · Ι · "): Defined as the percentage of olefin polymers that are insoluble in xylene. The weight% of dilute hydrocarbon polymers that are soluble in xylene at room temperature are at room temperature. In a container with a stirrer, dissolve 2.5 grams of polymer in 250 ml of xylene and stir under heating at 135 ° C for 20 minutes and measure 98345.doc 15 200534923. The solution is cooled to 25 ° C while stirring continuously, and then it is allowed to stand still. Leave it for 30 minutes to allow the solids to settle. The solids are filtered with filter paper, the residual solution is evaporated with nitrogen treatment, and the solid residue is dried at 8 ° rc until it reaches a constant weight. This value is essentially Corresponding by boiling n-geng Take the measured isotactic index, which by definition constitutes the isotactic index of polypropylene. Peroxide concentration: by quantitative organic analysis of functional groups, S. Siggia et al., 4th Ed., NY, Wiley 1979, ρρ · 334-42. Molecular weight and molecular weight distribution (MWD) The samples were prepared at a concentration of 70 mg / 50 ml of stabilized trichlorobenzene (25 0 g / ml BHT). Then, the samples were heated to 170 C for 2.5 hours to Dissolve. Then, the sample was performed at 145 < ^ at a flow rate of ι · ο ml / min using the same stabilizing solvent on Waters 〇 (^ \ ^ 2000). Three polymer ethyl acetate columns were used in series (Plgel, 20 micron mixed ALS, 300X7.5 mm). Determination of oligomer content by gas chromatography: accurately weigh 7-8 g of polymer sample into a 50 ml plasma bottle. Add by pipette 25 ml of dichloromethane and tightly cover the vial with the Teflon substrate septum to seal (squeeze the cap tightly to ensure that the seal is fixed). Place the vial in an ultrasonic bath at room temperature. Remove part of the extraction Gas chromatography (Agilent 5890 or equivalent) ) Analysis. 98345.doc -16- 200534923 In this specification, unless otherwise specified, all parts, percentages, and ratios are by weight. Peroxide-containing thin-smoke polymers are prepared according to the following procedure. [Embodiment] Example 1 Peroxide-containing hydrocarbon polymers are prepared from crystalline homopolymers having a melt flow rate (MFR) of 94 dg / min and II of 96.5%, and are commercially available from Basell USA Inc. 0 g) of the homopolymer was added to 7 liters of dual-zone reaction H, as described in U.S. Patent 5,696, plus. The total gas flow rate in the reaction was maintained at M "standard liters per hour (SLH). Organic peroxide (100 g), LupersOipMs, which is a% by weight solution of the third butyl peroxy-2-ethylhexanoate in odorless mineral spirits (0 ms). From Atofina North America, Inc., pumped into the reactor at a feed rate of 4 grams: minutes. The reactor was then heated to a temperature of 100 ° C in a nitrogen blanket with a controlled amount of oxygen, as shown in Table ⑽. The reactor was kept at ⑽. C for a quarter of an hour, and then for 14 minutes at 14t. Then, the oxygen was removed and the reactor was under a blanket of nitrogen at 14 Gt for another ⑼ minutes. Finally, the resulting dilute hydrocarbon polymer is cooled, discharged, and collected. The MFR of the dilute hydrocarbon polymer and its peroxide concentration are summarized in Table 1. / Reaction conditions are related to the characteristics of the resulting polymer material, such as the change in the rate of grasping by the refining material before and after the reaction. The polymer flow rate and peroxide content increase with increasing oxygen concentration. The comparison samples are summarized in Table 2. Comparative samples 1 and 2 show the same temperature treatment profile: the characteristics of the polymer after oxygen treatment, such as those without the addition of organic peroxide. Beetho parent samples 1-2 showed no significant increase in mfRs, indicating that there was no significant oxidation reaction under these conditions. Comparative sample 3 was prepared by the irradiation method. The polymer raw material was irradiated under a nitrogen blanket at 0.5 Mrad. Then, the irradiated polymer was treated with 1.45% by volume of oxygen at 80 ° C for 60 minutes, and then treated with 1.45% by volume of oxygen at 140 ° C for another 60 minutes. Then remove oxygen. The polymer was heated at 140 ° C for 60 minutes under a nitrogen blanket, cooled and collected. The data recorded in Tables 1 and 2 show that the method of the present invention, implemented in a two-zone reactor, produces a peroxide-containing olefin polymer having a high amount of peroxide functionality compared to other methods known in the art. Table 1 Reaction conditions and polymer characteristics Sample 1 Sample 2 Sample 3 Oxygen concentration (vol%) used for the reaction 0.4 '0.8 6.0 The special MFR (dg / min) of the obtained compound material 666 "1665 16000 peroxide Content (mmol / kg) ΤΣΠ ~ — 30.1 171 Table 2 Reaction conditions and polymer characteristics Comparative sample 1 Comparative sample 2 Comparative sample 3 Oxygen concentration (vol%) for reaction 0 5.0 1.45 Material properties MFR (dg / min) 11.0 11.6 325 Peroxide content (mmol / kg) 0 0 12.3 The activity of the peroxide-containing olefin polymer prepared in Example 1 can be measured by polymerization in the presence of ethylene monomer. Reactivity measurement. About 85 pph styrene monomer, commercially available from Aldrich Chemical Company, Inc., was added to the peroxide-containing olefin polymer and the mixture was sealed in a high-pressure stainless steel disc. Then, this disc was placed Differential scanning calorimeter (DSC), model DSC 7, manufactured by Perkin-Elmer Corporation. The mixture was heated from 25 ° C to 70 ° C at a heating rate of 20 ° C / min 98345.doc -18-200534923 minutes. And then at the heating rate Heating from 70 ° C to 170 ° C at a rate of 1 ° C / min. Table 3 summarizes the polymerization enthalpy and reaction conversion of samples 1-3 and comparative examples 1-2. Table 3 Polymer enthalpy (J / g) conversion Rate (%) Sample 1 -446.9 63.8 Sample 2 495.8 70.7 Sample 3 -610.3 87.1 Comparative sample 1 0 0 Comparative sample 2 -152.5 21.8 The activity of the peroxide-containing polyolefin prepared in Example 1 was also borrowed from DSC under isothermal conditions Analysis. Approximately 85 pph styrene monomer, commercially available from Aldrich Chemical Company, Inc., added to a peroxide-containing paraffin, and the mixture was sealed in a high-pressure stainless steel disc. The disc was then placed in a differential Scanning calorimeter (DSC), model DSC 7, manufactured by Perkin-Elmer Corporation. The mixture was heated from 25t to 14 ° C at a heating rate of 40 ° C / min, and then maintained at this temperature for 120 minutes. Table 4 summarizes Enthalpy of polymerization and reaction conversion of samples 1-3 and comparative examples 1-2. Table 4 Polymer enthalpy (J / g) Conversion (%) Sample 1 -360.4 51.4 Sample 2 -426.7 60.9 Sample 3 -617.7 88.1 Comparative sample 1 -19.1 2.7 Comparative sample 2 -308.2 44.0 98345.doc -19- 200534923 Example 2 Peroxide-containing Hydrocarbon-based polymers have a melt flow rate from (MFR) of 9 · 8 dg / min and Ι.Ι. 96.5% of a crystalline propylene homopolymer prepared, commercially available from Basell USA Inc ·. A homopolymer of propylene (2000 g) was charged into a 7-liter two-zone reactor having the equipment described in Example 1 at various overall gas flow rates as outlined in Table 5. Quantitative Lupersol PMS was pumped into the reactor at a feed rate of 4 g / min for making samples 1-4. The reactor was then heated to 100 ° C in a gas mixture recorded in Table 5 with a controlled amount of oxygen in nitrogen. The reactor was held at 100 ° C for a specific time, then heated to 140 ° C and held at the same temperature for 60 minutes. Then, the oxygen was removed and the reactor was kept under a blanket of nitrogen at 140 ° C for another 60 minutes. Finally, the olefin polymer is cooled, discharged, and collected. The characteristics of the resulting polymer are summarized in Table 5. Comparative sample 1 is a crystalline homopolymer of propylene used as a polymer raw material for samples 1-4. The peroxide-containing polymers in Table 5 show significant changes in the flow rate, molecular weight, molecular weight distribution (MWD), and oligomer content of the solution, as determined by the gaseous chromatographic separation method defined herein. Samples 1-4 had higher MFR, lower molecular weight, molecular weight distribution, and lower oligomer content than the raw materials.
表5 反應條件與聚合物 樣品 1 樣品 2 樣品 3 樣品 4 比較性特徵 樣品1 用於反應之氧濃度 (體積％) 0.8 0.8 0.8 0.8 N/A 在100°C下保持時間 60 60 60 120 N/A Lupersol PMS 之量 (克） 100 30 65 30 N/A 全部氣體流速 (SLH)1 56.6 113.2 113.2 28.3 N/A 98345.doc -20- 200534923 所得聚合物材料之特徵 MFR(dg/分鐘） 918 81 118 478 9.8 Mw(xl03) 83 142 121 81 308 Μη(χ103) 27 36 32 26 45 MWD 3.1 3.9 3.8 3.1 6.8 低聚物(ppm重量） 778 927 887 827 1462 Wlh :每小時標準公升。 實例3 含過氧化物烯烴聚合物係自具有熔物流速（MFR)為9.8 dg/分鐘及I.I.為96.5%之丙烯的結晶均聚物製備，市面上可 得自Basell USA Inc.。丙烯（2000克）之均聚物加入7升雙區 式反應器内，具有如實例1所述之設備，在各種全部氣體流 速為113.2每小時標準公升（SLH)下。Lupersol PMS(100克） 在進料速率為4克/分鐘下泵抽入反應器内供製造樣品1-3。 然後，反應器在表6紀錄之具有經控制量氧於氮中之氣體混 合物下加熱至l〇〇°C。反應器保持在l〇〇°C下歷60分鐘，然 後加熱至140°C並保持60分鐘。然後，除去氧，反應器在140 X：下在氮氣之覆蓋下保持另外60分鐘。最後，將烯烴聚合 物冷卻、排放並收集。含過氧化物烯烴聚合物材料之特徵 概述於表6。 比較樣品1除了未加入有機過氧化物以外，以如上述相同 條件下製備。表6之所得聚合物材料之特徵顯示氧濃度在所 得聚合物上之功效。 98345.doc -21 - 200534923 表6 反應條件與聚合物 樣品1 樣品2 樣品3 比較性特徵 樣品1 用於反應之氧濃度 (體積％) 0.8 0.8 0.8 5.0 在100°C下保持時間 60 60 60 60 Lupersol PMS之量 (克） 100 30 65 0 全部氣體流速 (SLH) 56.6 113.2 113.2 113.2 MFR(dg/分鐘） 918 81 118 9.8 Mw(xl03) 83 142 121 308 Μη(χ103) 27 36 32 45 MWD 3.1 3.9 3.8 6.8 低聚物(ppm重量） 778 927 887 1462 實例4 含過氧化物烯烴聚合物係自具有熔物流速（MFR)為9.8 dg/分鐘及I.I.為96.5%之丙烯的結晶均聚物製備，市面上可 得自Basell USA Inc·。丙烯（2000克）之均聚物加入7升雙區 式反應器内，具有如實例1所述之設備，在全部氣體流速為 4.0 SCFH下。Lupersol PMS(100克）在進料速率為4克/分鐘 下泵抽入反應器内供製造樣品1-2及比較性樣品1。然後， 反應器在表7紀錄之具有經控制量氧於氮中之氣體混合物 下加熱至100°C。反應器保持在l〇〇°C下歷60分鐘，然後加 熱至140°C並保持60分鐘。然後，除去氧，反應器在140°C 下在氮氣之覆蓋下保持另外60分鐘。最後，將烯烴聚合物 冷卻、排放並收集。所得聚合物材料之特徵概述於表7。 比較樣品1除了未加入氧至反應器以外，以如上述相同條 件下製備。 98345.doc -22- 200534923 含過氧化物聚合物之炫物流速及分子量之改變對應反應 所用之氧濃度。 表7 反應條件與聚合物 樣品1 樣品2 比較性特徵 樣品1 用於反應之氧濃度(體積％) 0.2 0.4 0 所习 寻聚合物材剩 l·之特徵 MFR(dg/分鐘） 84 294 14 Mw(xlOJ) 137 107 268 Μη(χ103) 35 30 45 MWD 3.9 3.6 6.0 低聚物(ppm重量） 805 907 793 熟悉此技藝者在讀取前述揭示物後當可更加明白本文所 揭示之本發明之其他特性、優點及具體例。關於此，雖然 本發明之特定具體例已詳述，惟在不脫離所述及所請求之 本發明之精神及範圍以外可對此等具體例作各種改變及修 正。 98345.doc -23-Table 5 Reaction conditions and polymer Sample 1 Sample 2 Sample 3 Sample 4 Comparative characteristics Sample 1 Oxygen concentration (vol%) for reaction 0.8 0.8 0.8 0.8 N / A Hold time at 100 ° C 60 60 60 120 N / A Lupersol PMS (g) 100 30 65 30 N / A Total gas flow rate (SLH) 1 56.6 113.2 113.2 28.3 N / A 98345.doc -20- 200534923 Characteristic MFR of the obtained polymer material (dg / min) 918 81 118 478 9.8 Mw (xl03) 83 142 121 81 308 Mη (χ103) 27 36 32 26 45 MWD 3.1 3.9 3.8 3.1 6.8 Oligomer (ppm by weight) 778 927 887 827 1462 Wlh: Standard liter per hour. Example 3 A peroxide-containing olefin polymer was prepared from a crystalline homopolymer of propylene having a melt flow rate (MFR) of 9.8 dg / min and an I.I. of 96.5%, and is commercially available from Basell USA Inc. A homopolymer of propylene (2000 grams) was charged into a 7-liter dual zone reactor having the equipment described in Example 1 at various overall gas flow rates of 113.2 standard liters per hour (SLH). Lupersol PMS (100 g) was pumped into the reactor at a feed rate of 4 g / min for making samples 1-3. The reactor was then heated to 100 ° C under a gas mixture with a controlled amount of oxygen in nitrogen as recorded in Table 6. The reactor was held at 100 ° C for 60 minutes, then heated to 140 ° C and held for 60 minutes. Then, the oxygen was removed and the reactor was kept under a blanket of nitrogen at 140 X: for another 60 minutes. Finally, the olefin polymer is cooled, discharged, and collected. The characteristics of the peroxide-containing olefin polymer materials are summarized in Table 6. Comparative sample 1 was prepared under the same conditions as above except that no organic peroxide was added. The characteristics of the obtained polymer materials in Table 6 show the effect of oxygen concentration on the obtained polymers. 98345.doc -21-200534923 Table 6 Reaction conditions and polymer Sample 1 Sample 2 Sample 3 Comparative characteristics Sample 1 Oxygen concentration (vol%) for reaction 0.8 0.8 0.8 5.0 Hold time at 100 ° C 60 60 60 60 Lupersol PMS (g) 100 30 65 0 Total gas flow rate (SLH) 56.6 113.2 113.2 113.2 MFR (dg / min) 918 81 118 9.8 Mw (xl03) 83 142 121 308 Μη (χ103) 27 36 32 45 MWD 3.1 3.9 3.8 6.8 oligomer (ppm by weight) 778 927 887 1462 Example 4 A peroxide-containing olefin polymer was prepared from a crystalline homopolymer of propylene having a melt flow rate (MFR) of 9.8 dg / min and an II of 96.5%. Commercially available from Basell USA Inc. A homopolymer of propylene (2000 g) was charged into a 7 liter dual zone reactor having the equipment described in Example 1 at a total gas flow rate of 4.0 SCFH. Lupersol PMS (100 g) was pumped into the reactor at a feed rate of 4 g / min for manufacturing samples 1-2 and comparative sample 1. The reactor was then heated to 100 ° C under a gas mixture with a controlled amount of oxygen in nitrogen as recorded in Table 7. The reactor was held at 100 ° C for 60 minutes and then heated to 140 ° C and held for 60 minutes. Then, the oxygen was removed and the reactor was kept at 140 ° C under a blanket of nitrogen for another 60 minutes. Finally, the olefin polymer is cooled, discharged, and collected. The characteristics of the resulting polymer material are summarized in Table 7. Comparative sample 1 was prepared under the same conditions as above except that oxygen was not added to the reactor. 98345.doc -22- 200534923 The changes in the flow rate and molecular weight of the peroxide-containing polymer correspond to the oxygen concentration used in the reaction. Table 7 Comparison of reaction conditions with polymer sample 1 Sample 2 Comparative characteristics Sample 1 Oxygen concentration (vol%) used for the reaction 0.2 0.4 0 Characteristic MFR (dg / min) of the remaining l · of the polymer material sought 84 294 14 Mw (xlOJ) 137 107 268 Mn (χ103) 35 30 45 MWD 3.9 3.6 6.0 oligomers (ppm by weight) 805 907 793 Those skilled in the art will understand more about other aspects of the invention disclosed herein after reading the foregoing disclosure. Features, advantages and specific examples. In this connection, although specific specific examples of the present invention have been described in detail, various changes and modifications can be made to these specific examples without departing from the spirit and scope of the present invention as described and claimed. 98345.doc -23-