200533408 九、發明說明： 【發明所屬之技術領域】 吸收封存於密閉物内 本發明係關於使用氧化丙雄聚合物 之氣體混合物中之氧氣。 【先前技術】 中，氧氣會帶來不利 中保持如所期望低的 品包裝領域，控制氧 質量’並增加食品的 減少廢物處理及補進 衆所周知，在某些工業和商業應用 影響。例如，在製造過程_，在設備 氧氣濃度對控制腐蝕非常重要。在食 氣敏感産品與氧氣的接觸可保持產口 存架壽命，從而延長産品的存貨期， 存貨的相關費用。 在商業應用（如食品包裝）中將與氧氣之接觸降至最低的 方法涉及使用惰性屏障，例如金屬、玻璃或各種塑料（如聚 偏二氯乙稀）。，然而’雖然這些方法可防止食物接觸容器外 存在的氧氣’但不此消除密閉物内材料周圍氣體空間中的 氧氣或者密封物封口或連接處滲漏的氧氣。爲解決上述問 題，已積極地採用多種方法吸收氧氣。在美國專利第 5’958,254號中’於聚合物組合物中納入可被還原的有機化 合物，例如醌類中。美國專利第6,517,776號中描述含有可 氧化有機化合物及光引發劑的氧氣清除層。然而，仍然需 要一種成本有效的氧氣吸收材料。意外地發現，氧化丙烯 聚合物可用於吸收含於密封物内之氡體混合物中之氧氣的 製程。 【發明内容】 98347.doc 200533408 本毛月係關於-種自存在於密 氧氣的方法，該方法包括將^ 物吸收 合物材料中，該氧 ，乳體混合物暴露於氧化丙歸聚 … 烯聚合物材料具有每公斤氧化丙嫌 化物，曲,甘\ _毫莫耳總過氧化物的過氧 化物-度，其中氧氣由氧化丙稀聚合物吸收。 、平飞 【實施方式】 本發明使用氧化丙烯窄人舲 烯“物材料吸收其周圍氣體混合物 乳…化丙婦聚合物材料藉由使丙烯聚合 Γ 隨後氧化來製備或藉助有機過氧化物引發劑來 衣備’如下所述。用你畜外 作虱化丙烯4合物材料之原料的丙烯 聚合物可爲下述幾種·· ㈧丙烯均聚物’其等規指數大於約8G%，大於約㈣ 尤佳； (B) 丙稀與烯煙（選自乙烯及C4_Ci〇a婦旬之無規共聚 ，’其中該烯烴含量爲約i至約3Gwt%，約2jL2Qwt%尤佳， 等規指數大於約60%，大於約70%尤佳； (C) 丙烯與·兩種選自乙烯和C4_C8 α烯烴之烯烴的無規 一元共？κ物，其中該等烯烴含量爲約i至約3〇 wt%，約2至 2〇 Wt %尤佳，等規指數大於約60%，大於約70%尤佳； (D) ~ 聚合物組合物，其包括： (0約10至約60重量份的丙烯均聚物，約15至約55 重里伤尤佳，其等規指數爲至少約80%，大於約9〇〇/〇 尤佳；或者選自下列的晶形共聚物：（a)丙烯與乙烯， (b)丙烯、乙烯與C4-C8 α-烯烴，及（c)丙烯與c4-c8 ^ 98347.doc 200533408 烯烴，該共聚物中，丙烯含量大於約85重量％，約90 重量％至約99重量％尤佳，等規指數大於約60〇/〇; (ii)約3至約25重量份的由乙烯與丙烯或c4-c8 α· 烯烴所形成的共聚物，約5至約20重量份尤佳，該共 聚物室溫下不溶於二曱苯；及 (in)約10至約85重量份的一彈性體，約15至約65 重量份尤佳，該彈性體選自（a)乙烯與丙烯，（b)乙烯、 丙烯與CVCsa·烯烴，（c)乙烯與κ8(χ烯烴，該共聚 物視情況含有約0.5至約1〇重量％的二烯，其中乙烯含 里小於約70重量％，約1〇至約6〇%尤佳，約12至約55% 最佳，該共聚物室溫下可溶於二甲苯，其特性黏度爲 約 1.5至約 6.0 dl/g。 以烯：!：工來合物組合物總量計，（⑴與（丨⑴之總和爲約5〇% 至約90重量％，⑼/(iii)之重量比小於約q 4，約g」至約 尤佳，其中該組合物由至少兩步聚合製備爲宜；及 (E) 其混合物。 隹一氣備氧化丙烯聚合物材料之方法中，丙烯聚合! 料首先在惰性氣體（氮氣爲宜）蒙氣下經電離輻射。該電i 射需有足約能量，以穿透聚合物材料塊，使其得到期 度的輕射。該電離輻射可以爲任意一種電離輻射，但】 包括電子及γ射線。電子發生器發射之電子更佳，加速, 為約刚至約侧千伏。在狀丨至約15兆拉德（「Mra< 之電離輪射劑量下可得到滿意的結果，約0.5至約〇州 電離輻射尤佳。 98347.doc 200533408 術語「拉德（rad)」通常定義爲使用美國專利第5,〇47,446 號所述衣私使母克受輕照材料吸收1 〇 〇爾格能量的電離幸备 射之數量（不考慮輻射源）。自電離輻射吸收之能量可用已知 經典劑量計量測，該量測裝置中之一片含有光敏感染料之 xjX合物膜爲此夏吸收感測部件。因此，該說明書中所用術 語「拉德」係指能導致吸收相當於1〇〇爾格能量/克劑量計 聚合物膜所用電離輻射量，該劑量計放置於受輻照丙烯聚 合物材料（無淪是以粒子床或粒子層、膜或片形式存在）之表 面上。 接下來對輻照後的丙烯聚合物材料實施氧化，較佳分幾 步。根據一較佳實施例，第一步處理包括在一第一控制量 的活潑氧存在下加熱經輻照聚合物至一第一溫度，活潑氧 之量大於約0·_%，但小於約15%，小於約8%較佳，小於 、勺5/〇更锃，約13%到約3〇%最佳（均按體積計），該第一溫 又V爲、力10 C，但低於聚合物之軟化點，約20°C到約 C車乂乜，約25 C到約1〇〇。〇更佳，約仙它到約8〇〇c最佳。 儘快：_期溫度，少於十分鐘爲宜，然後將該聚合物 ;又义/皿度下’通常保持約5至約9〇分锺，以增加聚合物 :之自由基與乳虱反應之程度，#留時間可由熟習此項技 ^ 4疋其取決於原料性質，所用活潑氧之濃度、輻射 I及：度。最大保留時間由流體床之物理限制決定。 ^一第二處理步驟中，將輻照聚合物在-第二控制量之 :二存在下加熱至一第二溫度，其中氧氣量大於約 /〇但小於約15%，小於約8%較佳，小於约5%更佳， 98347.doc 200533408 約 約 約1 · 3 %到約3.0 %最佳（均按體積計），該第二溫度至少爲 25 C ’但低於該聚合物之軟化點。該第二溫度較佳自 l〇(TC到低於該聚合物《軟化點’丨高於該第—步驟之該第 -溫度。然後將該聚合物置於設定溫度及氧氣濃娜下 約至約300分锺，約20至約180分锺尤佳，以增加鏈斷裂 之速率並使用以形成長支鏈的鏈片段之重組降至最低，即 使長支鏈之形成降至最低。保留時間之取決因素與該第一 處理步驟相同。 在任選第三步驟中，將氧化丙烯聚合物材料在惰性氣體 (氮氣較佳）蒙氣中加熱，彳至一第三溫度，該第三溫度至少 爲約80°C，但是低於該聚合物之軟化點，並於該溫产 持大約10到約120分锺，約60分锺尤佳。若實施該步驟，則 會生成-種更穩定的産品。若氧化丙烯聚合物將要儲存而 非^即使用，則較佳使用該步驟。㈣，在從流化床卸下 之4將孩♦合物經約5到30分锺在惰性氣體（氮氣較佳）蒙 氣下冷卻至-第四溫度（大約爲贼）。由此生成可在室溫下 長期儲存而不會進一步降解的穩定中間體。 _ 一貫施該處理之較佳方法爲：將經輻照丙烯聚合物在一 第一控制量的氧氣存在下通過一在一第一溫度下運作之流 體床裝置，再將該聚合物在一第二控制量的氧氣存在下通 過在一第二溫度下運作之第二流體床裝置，然後將該聚合 物在一第三溫度及氮氣蒙氣下置於一第三流體床裝置中。 在商業運作中，前兩步使用分離的流體床而第三步使用一 乎化此口床的連績製程尤佳。然而，該製程亦可在一個流 98347.doc 200533408 體床中分批實施 對各處理步驟使用一加熱至其預定溫度 之々丨L化氣Λ丨L。木同於諸如擠出方法等某些技術，流化床方 ’去不必將經照聚合物轉化纽融狀態及隨後再固化及粉 碎成預期形狀。流體介質可以係（例如）氮氣或不與所含自由 基反應的任何其他惰性氣體（例如氬，氪以及氦）。 形成於聚合物上之過氧化物基團濃度可藉由於經輕照聚 合物之製備過程改變輻射量以及改變該聚合物於輻照後所 =觸氧氣之量來控制。在流體床氣流中之氧氣量可藉由在 流體床人口處加人經過渡的乾燥空氣來控制。必須不斷地 加入空氣以補償聚合物中形成過氧化物對氧氣之消耗。 5 ，丙烯聚合物過氧化物材料可根據下面的程序I 備。在-第-處理步驟中，用01至10_的一有機過氧{ 物起始劑處理丙稀聚合物原料，與此同時加人控制量的車 氣’使丙稀聚合物材料所.接觸氧氣之量大於0 004%，但裏 小於21%’小於15%較佳，小於8%更佳’ 1〇%至5爲最佳(起 按體積計）；處理溫度至少⑽t，但低於該聚合物之軟化 、勺25C到約140C尤佳。在一第二處理步驟中，將該聚 合物在與該處理步驟範圍相同之氧氣濃度下加熱到自 至J 25 C至尚達該聚合物軟化點之間的溫度，自^⑻。匸至小 於該聚合物之軟化點尤佳。通f總反應時間爲狀5小時至 4小時。經氧氣處理後，將該聚合物於至少8代但低於直軟 化點之溫度下處理0.5小時至約2小時，以終止活潑的自由人 基，該處理於惰性氣氛（例如氮氣）下實施。 ’例如過氧化苯甲 適宜有機過氧化物包括醯基過氧化物 98347.doc -10- 200533408 ^與過氧化二苯甲醯；二烴基及芳烷基過氧化物，例如楚 氧化一-第二-丁基，過氧化二枯基）；過氧化枯基丁基，· 1，1 第二-丁基過氧-3,5,5-三甲基環己烷；2,5_二甲基 一^第一-丁基過氧己烷，及雙（仏第三-丁基過氧異丙苯），及 、氧-曰例如雙（α_第二-丁基過氧新戊酸酯，·過苯甲酸第三 一丁基酉曰，2,5-一甲基己基_2,5二（過苯甲酸醋广第三_丁基-=(過鄰笨二甲酸_);過氧士乙基己酸第三_丁基_，及過 5〜▲己酉夂1,1-一 Ρ基-3-經丁基酉旨，及過氧碳酸酉旨例如 過乳二碳酸二（2-乙基己基）酉旨，過氧二碳酸二（正丙基）醋， 及過氧二碳酸二（4_第二 罘一丁基1 衣己基）酯。該等過氧化物可 以砘品形式使用或於稀釋介質中使用。 =發明中所用氧化丙歸聚合物材料中，每公斤聚合 料“約1毫莫耳到約2⑽毫莫耳的總過氧化物。每公斤氧 =聚合物材料包含約5毫莫耳细毫莫耳總二 ^耳:公斤氧化丙稀聚合物材料包含約丨。毫莫耳至約_ 笔莫耳總過氧化物最佳。 儘官不欲受理論限制，作 材料含有過仁本發明中所用氧化丙烯聚合物 後與氧氣分子反應，從 /成自由基，然 士 & 將乳氣自周圍氣體混合物中去… 本發明中所用氧化丙烯聚合物氧去除。 的物件形式，例如膜，片或轉模物件 融 聚合物材料可以粒狀形式製備，包括一⑽化丙烯 或微粒。當以粒狀形式製 〇衣體、粉末薄片 用進，融處理較好，因爲-融處理可能導致與= 98347.doc 200533408 义氧化物鏈之降解，從而降低 收氧氣之能力。舍$轰 · 烯聚合物材料吸 時m 烯聚合物材料以球體… 衣體直徑範圍爲約0.01到 形式應用 米更佳。球體具有約。·ζ毫升/克到 宜^以粉末應用時，粉末粒徑分佈以約^之孔料爲 *米爲宜。當以微粒應用時，微粒之標準尺°=到物 米物毫米，毫米到約3毫米尤 粒較佳具有約〇 /刀末，專片或微 _ ^ 、 ·雾升/克到約0·6毫升/克之孔隙率。通當 :氣化丙稀聚合物材料吸收氧氣的量爲每克氧化二二 枓吸收約0.1毫升以上之氧氣。 材 、據本^明自存在於密閉物内之氣體混合物中吸收氧氣 :方，：將有效量的氧化丙烯聚合物材料置於氣體混合： X取σ亥氧化丙稀聚合物材料過氧化物濃度爲每公斤氧化丙 烯“物材料含有約…約綱毫莫耳的過氧化物總量。氧 丙烯來σ物材料過氧化物濃度爲每公斤氧化丙烯聚合物 材料含有大約5到150毫莫耳的過氧化物總量較佳，過氧化 物/辰度爲每公斤氧化丙烯聚合物材料含有約1〇到約1㈧毫 莫耳的過氧化物總量更佳。該說明書所用有效量的氡化丙 烯來合物材料是指，至少吸收按體積計爲〇1%的氣體混合 物中初始氧氣濃度所需的材料數量。 田用於吸收岔閉物内氣體混合物中的氧氣時，聚合過氧 化物通常保持在低於其熔點之溫度下，約2〇°c至約14〇。〇較 仏’約60 C至約120 C更佳，約1 〇〇。〇至約Π〇°C最佳。 製備氧化丙稀聚合物材料的原料較隹係一種丙稀均聚 98347.doc 、12- 200533408 物’其等規指數大於約_宜。氧化两歸聚合物材料如 上述藉由經輻照後再置於氧氣令製備較佳。 本發明之密閉物可爲任何物件，其結構可封存含有一定 氧氣濃度的氣體混合物。該密閉物可由任何材料製成，〇 要其能夠提供實質屏障以阻斷氧氣之自由流動，包括諸如、 塑料 '玻璃、金屬、橡膠、木料、紙板、碎料板、石頭或0 =其組合。該密閉物可具有剛性或半剛性形狀，包括諸如 箱子、容器、瓶子、圓筒、罐；或非剛性形狀，包括諸如 袋子、折疊膜或片及收縮包裝系統。該密閉物可以爲任何 大小，且可包括房間’櫥櫃或下列裝置，例如管子及盆管 道系,、溝道及其管道系統、導管及其管道系統，或容二 與氧化丙烯聚合物材料接觸的氣體混合物 物構成材料相—致的任何成分。儘管可能存在少量 密閉物中所含氣體混合物通常係氮氣與氧氣之混合 。取具代表性的是，該㈣混合物爲按 爲約20.9〇/〇之空氣。 τ 3虱札里 内=!:所用氧化丙稀聚合物材料通常用於減少密閉物 至：第了中氧氣之量，使其從-第-較高氧氣量降低 二：氧氣量。該密閉物有時可能敞口置於較高氧 氣》辰度的3衣境中，//λ .7Γ. ^fr η4- < 而曰呤增加密閉物内氧氣之濃度。該 弟 孕父1¾氣氣量及兮楚_ 數。或者 -車父低氣氣量可係任何氡氣百分 度，在 ^化丙烯聚合物材料可用於保持-定氧氣濃 :中。炎二札“有車父兩量氧氣的外部大氣滲漏到密閉 可發生在密閉物之封口處，或者由物件側壁之 98347.doc -13- 200533408 氧氣滲透性導致。更進一步，渗漏可以通過特意將氧_ 入密閉物内導致’以保持恒定氧氣濃度。最後，本發 程可與在密閉物内維持一惰性氣體模蒙氣(例如氮；: 統系統結合使用。 、寻 密閉物内的氣體混合物與氧化丙烯聚合物材料可以任何 方式接觸。舉例而言，該材料可以直接置於密閉物内部可 或者，該材料可包含在密閉物之結構材料内。該材料 先置於-單獨容器中，然後置於密閉物内。該容器之構、告 可爲與其所存放的密閉物一致的任何類型。該容器本身= 以渗漏氧氣，或者經過改進使氣體混合物可與氧二: 合物材料接觸。 挪來 或者’本發明方法中用於吸收氧氣的氧化丙烯 二=㈣融處理的丙浠聚合物形式，例如根據上述程序 而言，化丙烯聚 W杈成型物件自密閉物内混合氣體吸 =::::述::— 物件。然後將：稀聚合物膜、片或鱗模成型 一定量丙㈣、片或鑄模成型物件暴露於含 物二=混合物内’其中氧氣由該氧化丙稀聚合 版片或㈣成型物件吸收，該 成型物件所含 邓胰片或鑄杈 膜、片或鑄模：：每公斤氧化丙烯聚合物 物，每公斤氧化丙 有約1到約200毫莫耳總過氧化 乎細聚合物膜、片或鑄模成型物件含有約5 98347.doc -14- 200533408 到約150毫莫耳總過氧化物較佳，每公斤氧化丙烯聚合物 膜、片或鑄模咸型物件含有約10到約100毫莫耳總過氧化物 更佳。 在下列實例中，熔體流動速度率（「MFR」）藉由ASTM D123 8於2 · 16公斤測定，測定溫度23 0 °C，單位爲dg/min。 等規指數（「1.1.」）定義爲不溶於二甲苯的丙烯聚合物之百 分數。室溫下不溶於二甲苯中的丙烯聚合物之重量百分數 藉由以下測定：室溫下在一裝有攪拌器的容器内於250毫升 二甲苯中溶解2.5克聚合物，將其於135°C加熱並攪拌20分 鐘。將該溶液冷卻至25°C並同時繼續攪拌，接下來靜置30 分锺，使固體沈澱出來。固體用濾紙過濾，剩餘溶液藉由 用氮氣流處理蒸發，固體殘餘物在80°C真空乾燥，直至達 到恒重。該等值實質與藉由用蒸餾正庚烷萃取測定之等規 指數相一致，其根據定義等同於聚丙烯之等規指數。丙烯 聚合物過氧化物中之過氧化物含量如S. Siggia等人於 Quantitative Organic Analysis via Functional Groups(第 4 版，NY，Wiley 1979，第334-42頁）中所述量測。聚合物孔 隙率如 Winslow，Ν· M.及 Shapiro, J.J·於「An Instrument for the Measurement of Pore-Size Distribution by Mercury Penetration」（ASTM Bull·，TP 49，39-44(1959 年 2 月））及 Rootare，HL M.於「A Review of Mercury Porosimetry」 (225-252， In Hirshhom，J. S.及 Roll，K· H.編輯，Advanced Experimental Techniques in Powder Metallurgy, Plenum Press，New York，1970)所述量測。氧氣濃度用Quanteck氧氣 98347.doc -15- 200533408 分析儀測定’ Cole-Parmer出售該儀器。 除非另有說明，否則本發明中所提及份，百分數及比率〜 均指重量百分數。 製備方法1 將丙烯均聚物（MFR值爲9·4 dg/min，Ι·Ι·爲96·5%，孔隙率 爲〇·51毫升/克，自BasellUSA公司購得）於氮氣蒙氣下經4()200533408 IX. Description of the invention: [Technical field to which the invention belongs] Absorption and sealing in a closed object The present invention relates to the use of oxygen in a gaseous mixture of propylene oxide polymer. [Prior art] In the past, oxygen can bring disadvantages. Keep the product in the packaging field as low as desired, control the oxygen quality ’and increase food waste reduction and replenishment. It is well known that it affects certain industrial and commercial applications. For example, during the manufacturing process, the oxygen concentration of the equipment is very important to control corrosion. The contact of oxygen-sensitive products with oxygen can maintain the shelf life of the production port, thereby extending the product's inventory period and the related costs of inventory. Methods to minimize exposure to oxygen in commercial applications (such as food packaging) involve the use of inert barriers, such as metal, glass or various plastics (such as polyvinylidene chloride). However, 'though these methods can prevent food from contacting the oxygen present outside the container', this does not eliminate the oxygen in the gas space around the material inside the enclosure or the oxygen leaking from the seal or connection of the seal. To solve the above problems, various methods have been actively adopted to absorb oxygen. In U.S. Patent No. 5'958,254 'is incorporated into polymer compositions that can be reduced organic compounds, such as quinones. U.S. Patent No. 6,517,776 describes an oxygen scavenging layer containing an oxidizable organic compound and a photoinitiator. However, there is still a need for a cost effective oxygen absorbing material. It has unexpectedly been found that propylene oxide polymers can be used in a process for absorbing oxygen in a carcass mixture contained in a seal. [Summary of the Invention] 98347.doc 200533408 The present month is a method of self-existence in dense oxygen, which method comprises exposing the oxygen absorbent material to the oxygen and milk mixture to polymerize propylene oxide ... olefin polymerization The material material has a peroxide-degree of propylene oxide per kilogram of total peroxide, in which oxygen is absorbed by the propylene oxide polymer. [Embodiment] [Embodiment] The present invention uses a propylene oxide narrow human pinene "material to absorb its surrounding gas mixture milk ... The polymer polymer material is prepared by polymerizing propylene and then oxidizing or using an organic peroxide initiator Laiyibei 'is described below. The propylene polymer used as the raw material of the propylene 4 compound material outside your animal can be the following types: ㈧ propylene homopolymer' whose isotactic index is greater than about 8G%, greater than About ㈣ is particularly good; (B) random copolymerization of propylene and ene fume (selected from ethylene and C4_Cioa) More than about 60%, more preferably about 70%; (C) Random random co-polymers of propylene and two olefins selected from ethylene and C4_C8 alpha olefins, wherein the olefin content is from about i to about 30. wt%, about 2 to 20 Wt% is particularly preferred, and the isotactic index is greater than about 60%, more preferably greater than about 70%; (D) ~ polymer composition, including: (0 about 10 to about 60 parts by weight Homopolymer of propylene, particularly from about 15 to about 55, with an isotactic index of at least about 80%, and more preferably about 900 / 〇; A crystalline copolymer selected from: (a) propylene and ethylene, (b) propylene, ethylene and C4-C8 α-olefins, and (c) propylene and c4-c8 ^ 98347.doc 200533408 olefins, in the copolymer, The propylene content is more than about 85% by weight, preferably about 90% by weight to about 99% by weight, and the isotactic index is greater than about 60/0; (ii) about 3 to about 25 parts by weight of ethylene and propylene or c4-c8 α · A copolymer formed from an olefin, preferably about 5 to about 20 parts by weight, the copolymer is insoluble in dibenzobenzene at room temperature; and (in) about 10 to about 85 parts by weight of an elastomer, about 15 to about 65 parts by weight is particularly preferred, and the elastomer is selected from (a) ethylene and propylene, (b) ethylene, propylene, and CVCsa · olefins, (c) ethylene and κ8 (χ olefins, and the copolymer optionally contains about 0.5 to about 1 0% by weight of diene, wherein the ethylene content is less than about 70% by weight, preferably about 10 to about 60%, most preferably about 12 to about 55%, the copolymer is soluble in xylene at room temperature, and Intrinsic viscosity is from about 1.5 to about 6.0 dl / g. Based on the total amount of ene:!: Indole mixture composition, the sum of (⑴ and (⑴) is about 50% to about 90% by weight, and ⑼ / (iii ) Weight Less than about q4, about g "to about preferably, wherein the composition is preferably prepared by at least two steps of polymerization; and (E) a mixture thereof. In a method for preparing propylene oxide polymer materials by air, propylene is polymerized! Ionizing radiation in the presence of an inert gas (nitrogen is preferred). The ionizing radiation needs sufficient energy to penetrate the polymer material block to obtain periodic light emission. The ionizing radiation can be any kind of ionization Radiation, but] includes electrons and γ-rays. The electrons emitted by the electron generator are better, accelerated, and about kV to about kV. Satisfactory results can be obtained at conditions ranging from about 15 megarads ("Mra < ionizing radiation shots, particularly from about 0.5 to about 0 states. 98347.doc 200533408 The term" rad "is generally defined In order to use the material described in U.S. Patent No. 5,047,446 to make the mother gram lightly irradiated material absorbs 100 ergs of ionizing radiation (regardless of the radiation source). The energy absorbed by ionizing radiation can be known Classic dosimetry, one of the xjX compound films containing a light-sensitive dye in this measuring device is an absorption sensing element for summer. Therefore, the term "rad" used in this specification means that it can cause absorption equivalent to 10%. 〇erg energy per gram dose of ionizing radiation used on polymer film, which is placed on the surface of the irradiated propylene polymer material, which is in the form of a particle bed or particle layer, film or sheet. Next Oxidation of the irradiated propylene polymer material is preferably divided into several steps. According to a preferred embodiment, the first step treatment includes heating the irradiated polymer to a first controlled amount in the presence of a first controlled amount of active oxygen. One temperature The amount of active oxygen is greater than about 0 ·%, but less than about 15%, preferably less than about 8%, less than, spoon 5 / 〇, more preferably, about 13% to about 30% (all by volume), The first temperature is V and the force is 10 C, but it is lower than the softening point of the polymer, about 20 ° C to about C, about 25 C to about 100 °, and more preferably, about 50 to about 100 ° C. 8〇c is the best. As soon as possible: the period temperature, preferably less than ten minutes, and then the polymer; also meaning / dish temperature 'usually maintained about 5 to about 90 minutes, to increase the polymer: of The degree of reaction between free radicals and milk lice, #Retention time can be familiar with this technique ^ 4 疋 It depends on the nature of the raw materials, the concentration of active oxygen used, radiation I and: degrees. The maximum retention time is determined by the physical limitations of the fluid bed. ^ In a second processing step, the irradiated polymer is heated to a second temperature in the presence of a second controlled amount: two, wherein the amount of oxygen is greater than about / 0 but less than about 15%, and preferably less than about 8%, It is more preferably less than about 5%, 98347.doc 200533408 is about about 1.3% to about 3.0% (all by volume), and the second temperature is at least 25 C 'but lower than the softening of the polymer The second temperature is preferably from 10 ° C. to below the polymer “softening point” above the first temperature of the first step. The polymer is then placed under the set temperature and oxygen concentration to about About 300 minutes, preferably about 20 to about 180 minutes, in order to increase the rate of chain breakage and use to form long branched chain fragments to minimize reorganization, even if the formation of long branched chains is minimized. Retention time It depends on the same factors as the first treatment step. In the optional third step, the propylene oxide polymer material is heated in an inert gas (preferably nitrogen) and heated to a third temperature, which is at least About 80 ° C, but below the softening point of the polymer, and at this temperature, about 10 to about 120 minutes, preferably about 60 minutes. If this step is carried out, a more stable product will be produced. This step is preferably used if the propylene oxide polymer is to be stored rather than used immediately. Alas, after removing from the fluidized bed, the mixture is cooled to a fourth temperature (approximately thief) under an inert gas (preferably nitrogen) for about 5 to 30 minutes. This results in stable intermediates that can be stored at room temperature for extended periods without further degradation. _ The preferred method of consistently applying this treatment is to pass the irradiated propylene polymer in the presence of a first controlled amount of oxygen through a fluid bed device operating at a first temperature, and then polymerize the polymer in a first Two controlled quantities of oxygen are passed through a second fluid bed device operating at a second temperature, and then the polymer is placed in a third fluid bed device at a third temperature and nitrogen blanket. In commercial operations, the first two steps use a continuous fluid bed and the third step uses a continuous bed process that uses this bed. However, the process can also be implemented in batches in a stream of 98347.doc 200533408 bed. For each processing step, a 々L chemical gas Λ 丨 L heated to its predetermined temperature is used. As with certain technologies such as extrusion methods, the fluidized bed side eliminates the need to transform the photopolymer into a molten state and subsequently re-solidify and crush it into the desired shape. The fluid medium can be, for example, nitrogen or any other inert gas (such as argon, krypton, and helium) that does not react with the contained radicals. The concentration of the peroxide groups formed on the polymer can be controlled by changing the amount of radiation and changing the amount of oxygen that the polymer is exposed to after irradiation. The amount of oxygen in the fluid bed stream can be controlled by adding transitional dry air to the fluid bed population. Air must be continuously added to compensate for the oxygen consumption of peroxides formed in the polymer. 5, propylene polymer peroxide material can be prepared according to the following procedures. In the -step-treatment step, the acrylic polymer raw material is treated with an organic peroxy {} initiator from 01 to 10_, and at the same time, a controlled amount of vehicle gas is added to make the acrylic polymer contact. The amount of oxygen is greater than 0 004%, but less than 21%, preferably less than 15%, more preferably less than 8%, 10% to 5 is the best (from volume basis); the processing temperature is at least ⑽t, but lower than Polymer softening, 25C to about 140C is preferred. In a second processing step, the polymer is heated to a temperature from to J 25 C to the softening point of the polymer at a concentration of oxygen in the same range as that of the processing step, from ⑻ to ⑻.匸 to less than the softening point of the polymer is particularly preferred. The total reaction time is 5 hours to 4 hours. After oxygen treatment, the polymer is treated at a temperature of at least 8 generations but below the direct softening point for 0.5 hours to about 2 hours to terminate the active free radicals. The treatment is performed under an inert atmosphere (such as nitrogen). 'For example, benzoyl peroxide suitable organic peroxides include fluorenyl peroxide 98347.doc -10- 200533408 ^ and dibenzoylperoxide; dihydrocarbyl and aralkyl peroxides, such as Chu-O-Second -Butyl, dicumyl peroxide); cumyl butyl peroxide, · 1,1 second-butylperoxy-3,5,5-trimethylcyclohexane; 2,5-dimethyl 1 ^ first-butylperoxyhexane, and bis (仏 third-butylperoxycumene), and oxygen-such as bis (α-second-butylperoxypivalate, · The third monobutyl perbenzoate is 2,5-monomethylhexyl_2,5-di (perbenzoate, the third _butyl-= (per-ortho-dicarboxylic acid)); peroxyethyl Tertiary butyl hexanoate, and 5 ~ ▲ hexamethylene 1,1--P-3-yl butyl group, and peroxycarbonate group such as di (2-ethylhexyl) perlactate Purpose, di (n-propyl) peroxydicarbonate, and bis (4-secondary monobutyl 1-hexyl) peroxydicarbonate. These peroxides can be used in the form of fakes or in dilution media Used in the invention = per kilogram of polymer material in the propylene oxide polymer material used in the invention Total peroxide from about 1 millimolar to about 2 millimoles. Per kilogram of oxygen = polymer material contains about 5 millimoles thin millimoles total two ^ ear: kilograms of propylene oxide polymer material contains about 丨. Millimoles to about _ penmoles is the best total peroxide. Without wishing to be bound by theory, the material contains propylene oxide polymer used in the present invention and reacts with oxygen molecules to form / free radicals. To remove milk gas from the surrounding gas mixture ... The propylene oxide polymer used in the present invention is oxygen-removable. Object forms, such as films, sheets, or transfer objects, can be prepared in granular form, including polymerization. Propylene or fine particles. When the body and powder flakes are used in granular form, the melting treatment is better, because -melting treatment may cause the degradation of the meaning oxide chain with = 98347.doc 200533408, thereby reducing the ability to collect oxygen. When the olefin polymer material is absorbed, the olefin polymer material is in the form of a sphere ... The body diameter ranges from about 0.01 to about 0.1 meters. The sphere has a diameter of about. · Ζ ml / g to 宜. Particle size distribution The porous material of ^ is suitable for rice. When applied with microparticles, the standard scale of microparticles is to millimeters to millimeters, millimeters to about 3 millimeters, especially grains preferably have about 0 / knife, special film or micro_ ^ · · The porosity of mist l / g to about 0.6 ml / g. Tongdang: The amount of oxygen absorbed by the vaporized acrylic polymer material is about 0.1 ml of oxygen per gram of dioxin. ^ Obviously absorb oxygen from the gas mixture existing in the airtight: square,: put an effective amount of propylene oxide polymer material in the gas mixture: X take σ oxidized propylene polymer material peroxide concentration per kg of oxidation The propylene material contains a total of about ... about a millimolar of peroxide. The oxypropylene material has a peroxide concentration of about 5 to 150 millimoles per kilogram of propylene oxide polymer material. The total peroxide content is preferred, and the peroxide / degree is contained per kilogram of propylene oxide polymer material. The total amount of peroxide is about 10 to about 1 millimolar. The effective amount of tritiated propylene acrylate material used in this specification refers to the amount of material required to absorb at least the initial oxygen concentration in the gas mixture of 0.001% by volume. When a field is used to absorb oxygen in a gas mixture in a bifurcation, the polymerized peroxide is usually maintained at a temperature below its melting point, from about 20 ° C to about 14 °. 〇 is better than about 60 C to about 120 C, and about 1000. 0 to about Π ° C is optimal. The raw material for preparing the propylene oxide polymer material is a kind of propylene homopolymer 98347.doc, 12-200533408, and its isotactic index is greater than about _. The oxidized two-homing polymer material is prepared as described above by irradiating and then placing in oxygen. The enclosure of the present invention can be any object, and its structure can seal a gas mixture containing a certain oxygen concentration. The enclosure may be made of any material that is capable of providing a substantial barrier to the free flow of oxygen, including such materials as plastic, glass, metal, rubber, wood, cardboard, particle board, stone, or a combination thereof. The enclosure may have a rigid or semi-rigid shape, including such as boxes, containers, bottles, cylinders, cans; or a non-rigid shape, including such as bags, folding films or sheets, and shrink packaging systems. The enclosure can be of any size and can include room 'cabinets or the following devices, such as pipes and basin piping, trenches and their piping systems, ducts and their piping systems, or containers that are in contact with propylene oxide polymer materials A gaseous mixture constitutes any component of the same material. Although there may be a small amount of gas contained in the enclosure, a mixture of nitrogen and oxygen is usually used. Typically, the thorium mixture is air at about 20.9 / 0. τ 3 Lizzari Inside = !: The propylene oxide polymer material used is usually used to reduce the amount of oxygen in the enclosure. ^ Fr η4- < and the pyridine may increase the oxygen concentration in the enclosure. The younger brother's pregnant father had 1 ¾ of Qi and Qi Chu. Or-The low gas volume of the driver ’s car can be any percentage of radon gas. The polymerized propylene polymer material can be used to maintain-constant oxygen concentration. Yan Erzha "The leakage of the external atmosphere with two amounts of oxygen from the driver ’s car to the seal may occur at the seal of the seal, or it may be caused by the permeability of 98347.doc -13- 200533408 on the side wall of the object. Further, the leakage can be passed through The deliberate introduction of oxygen into the enclosure results in 'to maintain a constant oxygen concentration. Finally, this process can be used in conjunction with maintaining an inert gas mold (such as nitrogen; system) in the enclosure. Finding the inside of the enclosure The gas mixture and the propylene oxide polymer material can be contacted in any manner. For example, the material can be placed directly inside the enclosure or the material can be contained in the structure material of the enclosure. The material is first placed in a separate container , And then placed in a closed container. The container may be constructed of any type consistent with the closed container it is stored in. The container itself = leaks oxygen, or has been modified so that the gas mixture can be mixed with oxygen: Come in or 'propylene oxide polymer used for absorbing oxygen in the method of the present invention = melt-processed acrylic polymer form, for example, according to the procedure described above, Acrylic poly-w-shaped molded objects absorb gas from the airtight mixture in the closed object ::::: 述 :: — The object is then exposed to: a thin polymer film, sheet or scale mold is formed into a certain amount of acrylic, sheet or mold-molded object to Object 2 = In the mixture 'where oxygen is absorbed by the propylene oxide polymer plate or rhenium molding, which contains Deng pancreas film or cast film, sheet or mold: per kg of propylene oxide polymer, per kg Propylene oxide has about 1 to about 200 millimolars of total peroxide, and a thin polymer film, sheet or molded article contains about 5 98347.doc -14- 200533408 to about 150 millimoles of total peroxide, preferably per kilogram. A propylene oxide polymer film, sheet, or molded salty article preferably contains about 10 to about 100 millimolars of total peroxide. In the following examples, the melt flow rate ("MFR") is determined by ASTM D123 8 in 2 · Determination of 16 kg at a measurement temperature of 230 ° C in dg / min. The isotactic index ("1.1.") Is defined as the percentage of propylene polymer insoluble in xylene. Propylene insoluble in xylene at room temperature The weight percent of the polymer is determined by: room temperature In a container equipped with a stirrer, 2.5 g of polymer was dissolved in 250 ml of xylene, and it was heated and stirred at 135 ° C for 20 minutes. The solution was cooled to 25 ° C while continuing to stir, and then allowed to stand 30 minutes, the solid precipitated out. The solid was filtered with filter paper, the remaining solution was evaporated by treatment with a stream of nitrogen, and the solid residue was dried under vacuum at 80 ° C until a constant weight was reached. The isotactic index determined by the extraction of alkane is the same, which is equivalent to the isotactic index of polypropylene by definition. The peroxide content in propylene polymer peroxides is as described in S. Siggia et al. In Quantitative Organic Analysis via Functional Groups (No. 4 Edition, NY, Wiley 1979, pp. 334-42). Polymer porosity such as Winslow, NM, and Shapiro, JJ. "An Instrument for the Measurement of Pore-Size Distribution by Mercury Penetration" (ASTM Bull., TP 49, 39-44 (February 1959)) And Rootare, HL M. as described in "A Review of Mercury Porosimetry" (225-252, In Hirshhom, JS and Roll, KH. Editor, Advanced Experimental Techniques in Powder Metallurgy, Plenum Press, New York, 1970) Measurement. Oxygen concentration was measured with a Quanteck oxygen 98347.doc -15-200533408 analyzer ', which is sold by Cole-Parmer. Unless otherwise stated, parts, percentages and ratios mentioned in the present invention all refer to weight percentages. Preparation method 1 A propylene homopolymer (MFR value is 9.4 dg / min, Ι ·· is 96 · 5%, and the porosity is 0.51 ml / g, purchased from BasellUSA) under a nitrogen blanket. 4 ()
Mrad輻照。該均聚物呈球體形式，其直徑在約〇1毫米到約 3宅米之間。然後經輻照的聚合物於密封於密閉鋁袋中前在 室溫下用空氣（氧氣含量以體積計爲20.9%)處理一小時。所 _ 生成聚合物材料之MFR爲3073 dg/min。 製備方法2 丙浠均聚物（MFR值爲9.4 dg/min，I.I.爲96·5%，孔隙率爲 0.51¾升/克，講自BasellUSA公司）在氮氣蒙氣下室溫下經 〇·5 Mrad輻照。該均聚物呈球體形式，其直徑在約〇1毫米 到約3毫米之間。然後將輻照後的聚合物用以體積計145% 的氧氣於140°C下處理60分锺，然後移除氧氣。接下來將該 鲁 聚合物在氮氣蒙氣下於140°C加熱60分锺，冷卻後收集。所 生成聚合物材料之MFR爲325 dg/min。過氧化物濃度爲每公 斤氧化聚合物含12.3毫莫耳總過氧化物。 製備方法3 丙烯均聚物1000克（MFR值爲9·4 dg/min，Ι·Ι·爲96.5%，孑L 隙率爲0.5 1毫升/克’睛自BasellUSA公司）加入到>—7 · 6公升 高壓反應器中。該均聚物呈球體形式，其直徑在約〇 · 1毫米 到約3毫米之間。將一有機過氧化物Lupersol PMS(其係過氧 98347.doc -16- 200533408 -2-乙基己酸第三丁基酯溶於無臭礦油精（OMS)中的一 50 wt%溶液，自 Atofina North America公司得到）l〇〇g以 6.5 毫升/分锺之加料速率泵入反應器中。然後將該均聚物加熱 到100°C，置於在氮氣中含0.8%氧氣（以體積計）之氣體混合 物中。100°C反應60分锺，然後將該均聚物加熱至i4(rc， 在該溫度下保持60分锺。接下來將該均聚物冷卻至室溫， 收集於岔閉的鋁袋中。所生成聚合物材料iMFR. 2412 dg/min 〇 的=出2。。。下氧化丙埽聚合物材料氧㈣Mrad irradiation. The homopolymer is in the form of a sphere with a diameter between about 0.01 mm and about 3 m. The irradiated polymer was then treated with air (oxygen content 20.9% by volume) for one hour at room temperature before being sealed in a sealed aluminum bag. The MFR of the resulting polymer material was 3073 dg / min. Preparation method 2 Propionate homopolymer (MFR value is 9.4 dg / min, II is 96 · 5%, porosity is 0.51 ¾ liter / gram, from BasellUSA) under nitrogen blanket at room temperature through 0.5 Mrad irradiation. The homopolymer is in the form of a sphere with a diameter between about 0.01 mm and about 3 mm. The irradiated polymer was then treated with 145% oxygen by volume at 140 ° C for 60 minutes, and then the oxygen was removed. Next, the Lu polymer was heated at 140 ° C for 60 minutes under a nitrogen blanket, and collected after cooling. The MFR of the resulting polymer material was 325 dg / min. The peroxide concentration was 12.3 millimoles of total peroxide per kg of oxidized polymer. Preparation method 3 1000 g of propylene homopolymer (MFR value is 9.4 dg / min, Ι ·· is 96.5%, 孑 L clearance rate is 0.5 1 ml / g 'eyes from BasellUSA) Add to> -7 · In a 6-m elevated reactor. The homopolymer is in the form of a sphere with a diameter between about 0.1 mm to about 3 mm. An organic peroxide Lupersol PMS (which is peroxy 98347.doc -16- 200533408 -2-ethylhexanoic acid third butyl ester) was dissolved in a 50 wt% solution of odorless mineral spirits (OMS). 100 g from Atofina North America was pumped into the reactor at a feed rate of 6.5 ml / min. The homopolymer was then heated to 100 ° C and placed in a gas mixture containing 0.8% oxygen (by volume) in nitrogen. The reaction was conducted at 100 ° C for 60 minutes, and then the homopolymer was heated to i4 (rc, and maintained at that temperature for 60 minutes. The homopolymer was then cooled to room temperature and collected in a closed aluminum bag. The resulting polymer material iMFR. 2412 dg / min 〇 = out of 2 ...
在表I至V中，上述製劑之氧氣吸收性質使用5克該聚合物 於密封的，毫升含空氣破璃瓶中評價。聚合物/瓶放在可 控溫的加熱爐中。按1至3方法製備的氧化丙烯聚合物 材料之乳孔吸收里於不同溫度下在不同時間點上量測。 98347.doc 200533408 表III列出60°C下氧化 的數值。 两稀XK合物材料氧氣吸收量對時間In Tables I to V, the oxygen absorption properties of the above formulations were evaluated using 5 g of this polymer in a sealed, ml air-containing glass breaking bottle. The polymer / bottle is placed in a temperature-controlled oven. The pore absorption of the propylene oxide polymer material prepared according to the methods 1 to 3 is measured at different times at different temperatures. 98347.doc 200533408 Table III shows the oxidation values at 60 ° C. Oxygen uptake of two dilute XK complex materials versus time
98347.doc Ί8, 20053340898347.doc Ί8, 200533408
當詳細地闡述本發明之具體實施例’但可對該等具體實施 例予以變更及修改，此並不背離所述及提出申請之本發明 之精神及範圍。 98347.doc -19-While the specific embodiments of the present invention are explained in detail, changes and modifications can be made to these specific embodiments without departing from the spirit and scope of the present invention as described and claimed. 98347.doc -19-