1288767 at B7 五、發明説明（1 ) 本發明係有關一種高汽油滲漏阻隔性塑膠摻合物容器之製備方 法，其包括以價廉之傳統吹瓶成型機使用摻加改質聚醯胺(MPA)的高 密度聚乙烯(HDPE)之適當配方，即PE/MPA組成物，經由積層吹瓶法 製程吹瓶製備得到在HDPE基質中形成MPA積層結構（laminar structure)之高汽油滲漏阻隔性塑膠摻合物容器。 汽油極易從容器滲透出來，目前貯存汽油所用容器(如一般貯裝 容器、及汽機車、汽船、割草機等所用油箱等)均多以價格低廉且兼 具優異加工性，物理及化學性質之高密度聚乙烯(HDPE)爲主要塑膠材 質。唯美中不足的是HDPE容器在貯存汽油時會嚴重滲漏。進而衍生 之環保、公安及因汽油滲透而造成資源大幅損耗問題。近年來，雖已 有成功運用多種技術來‘大幅改善其抗汽油滲漏之阻隔性者，比如，經 表面氟化（J.P Hobbs·，M. Anand. And B. A· Campion, in Barrier Polymer and Structures, W. J. Koros Ed., Chapter 15, American Chemical Society, Washington (1990))或磺化處理（W. E.Walles，in Barrier Polymer and Strutures, W. J. Koros Ed., Chapter 14,. American Chemical Society Washington (1990))之 HDPE 及多層共擠壓（Multi-layer coextrusion)積層 (Laminar)吹瓶法（S· Willian，Chemtech August 481 (1988))等，但表面處 理法有製程危險、污染性高、投資成本較高及廢料難回收等缺點；多 層共擠壓法則有吹瓶成型機台複雜、投資成本較高、投資成本較高及 廢料難回收等缺點。相較於上述兩種技術，積層吹瓶法，除無上述技 術之缺點外，另具有加工簡單(可利用傳統PE吹瓶成型機），廢料可 回收再使用及投資成本較上述二法爲低等優點，因而廣受容器成型業 者的青睐，近年來發展快速。 唯積層法之技術層次極高，必須有效的控制聚醯胺之薄板 (Lamellar)成長層狀平行分布，且需使用杜邦已有專利經特殊設計且價 昂之吹瓶機。其理念層稍早揭露於台灣聚合公司（(台灣聚合化學品股 份有限公司），經濟部中央標準局專利權號數發明第53,999號（1992)) 及 Du Pont( R.C· Diluccio, U.S· Patent 4,416,942 (1983); V. K. Mehra，U.S. 第1頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫1288767 at B7 V. INSTRUCTION DESCRIPTION (1) The present invention relates to a method for preparing a high gasoline leakage barrier plastic blend container, which comprises using a modified polyamine (in the form of a cheap conventional blow molding machine) MPA) high-density polyethylene (HDPE), the proper formulation of PE/MPA composition, is prepared by a laminating bottle blowing process to obtain high gasoline leakage barrier properties for forming a MPA laminar structure in HDPE matrix. Plastic blend container. Gasoline is easily infiltrated from the container. At present, the containers used for storing gasoline (such as general storage containers, fuel tanks for steam locomotives, steamboats, lawn mowers, etc.) are mostly inexpensive and have excellent processability, physical and chemical properties. High density polyethylene (HDPE) is the main plastic material. The only drawback is that HDPE containers can leak heavily when storing gasoline. Further, environmental protection, public security, and the loss of resources caused by gasoline penetration have been caused. In recent years, there have been successful attempts to use a variety of techniques to 'substantially improve their resistance to gasoline leakage, such as surface fluorination (JP Hobbs, M. Anand. And B. A. Campion, in Barrier Polymer and Structures, WJ Koros Ed., Chapter 15, American Chemical Society, Washington (1990)) or sulfonation (WEWalles, in Barrier Polymer and Strutures, WJ Koros Ed., Chapter 14,. American Chemical Society Washington (1990)) HDPE and Multi-layer coextrusion laminar blowing method (S· Willian, Chemtech August 481 (1988)), etc., but the surface treatment method has process hazard, high pollution, and high investment cost. And the disadvantages of difficult recycling of waste materials; multi-layer co-extrusion method has the disadvantages of complicated blow molding machine, high investment cost, high investment cost and difficult recycling of waste. Compared with the above two technologies, the laminated blowing method, in addition to the shortcomings of the above-mentioned technology, has a simple processing (a conventional PE bottle forming machine can be used), the waste can be recycled and reused, and the investment cost is lower than the above two methods. And so on, so it is widely favored by the container molding industry, and has developed rapidly in recent years. The technique of the layered method is extremely high, and it is necessary to effectively control the lamellar layer of Lamamine to grow in parallel, and to use DuPont's patented, specially designed and expensive blow molding machine. Its concept layer was first revealed in Taiwan Polymerization Corporation ((Taiwan Polymerization Chemical Co., Ltd.), Central Standards Bureau of the Ministry of Economic Affairs, Patent No. 53,999 (1992)) and Du Pont (RC·Diluccio, US· Patent 4,416,942 (1983); VK Mehra, US Page 1 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill in the form)
經濟部智慧財產局員工消費合作社印製 1288767 at B7 五、發明説明（2)Printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative 1288767 at B7 V. Invention description (2)
Patent 4,950,513 (1990))等少數專利。唯PA與PE不相容，界面接著 性不佳，往往需在吹押(blow-molding)加工過程中於PE/PA中加入CP 以增加其與HDPE界面接著性。有鑑於此，本案發明人乃經由精深硏 究而發現在選取適當CP及PA組成先以雙螺桿壓出機製成改質尼龍 (MPA)，再以MPA適當配方摻製PE經傳統價廉之吹瓶成型機可製備 PE/MPA摻合瓶。所製備之ΡΕ/MPA摻合瓶可達高汽油滲透阻隔效果， 且僅使用傳統價廉之吹瓶成型機，此項製成不僅成本低廉不侵犯既存 之國內外相關專利。且所得之汽油滲漏阻隔效果在40°C可以達一年僅 滲漏小於容器總貯存汽油量之5%以下。此項阻隔效果更高於上數諸 專利之阻隔滲漏效果。 據此，本發明提出一種高汽油滲漏阻隔性塑膠摻合物容器之製 備方法，其包括以價廉之傳統吹瓶成型機使用摻加改質聚醯胺(MPA) 的高密度聚乙烯(HDPE)適當配方，即PE/MPA組成物，經由積層吹瓶 法製程吹瓶製備得到在HDPE基質中形成MPA積層結構(laminar structure)之高汽油滲漏阻隔性塑膠摻合物容器。 圖式之簡略說明 第1圖爲顯示出如吹塑PE瓶(·)和在不同溫度退火1(〇），2(〇）’ 4(〇），8(〇），16(〇），24(〇)和32(〇）小時後的PE瓶所得汽油滲透速 率之圖形。 圖2爲顯示出如吹塑PE/PA瓶(▲)和在不同溫度退火1(Δ) ’ 2(Δ) ’ 4(Δ)，8(Δ)，16(Δ)，24(Δ)和32(Δ)小時後的PE/PA瓶所得汽油滲 透速率之圖形。 圖3爲顯示出如吹塑PE/MPA瓶(_)和在不同溫度退火1(口）’ 2(口）’ 第2頁，共13頁 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫 .寫 訂 經濟部智慧財產局員工消費合作社印製 A7 B7 1288767 五、發明説明（3 ) 4(C])，8(口），16(口），24(口)和 32(口)小時後的 PE/MPA 瓶所得汽油 滲透速率之圖形。 請 先 閱 讀 背 © 之 注 意 事 項 再 填 圖4爲顯示出如吹塑(a)PE，（b)PE/PA，和(c)PE/MPA瓶及在ll〇°C退 火32小時後的(d)PE，（e)PE/PA和(f)PE/MPA瓶的破裂表面之顯微攝 影圖。 圖5a爲顯示出如吹塑PE瓶(·)和在不同溫度退火1(〇），2(〇）， 4(〇），8(〇），16(〇），24(〇)和32(〇)小時後的PE瓶所得百分結晶度 値之Η形。 圖5b爲顯示出在如吹塑ΡΕ/ΡΑ和在不同溫度下退火1(〇），2(〇）’ 4(〇），8(〇），16(〇），24(〇)和32(〇)小時的PE/PA瓶中所含PEd 的百分結晶度値；及在如吹塑PE/PA瓶和在不同溫度退火1(Δ) ’ 2(Λ)，4(Δ)，8(Δ)，16(Δ)，24(Δ)和 32(Δ)小時的 ΡΕ/ΡΑ 瓶中所含 ΡΑ(Α)的百分結晶度値之圖形。 圖5c爲顯示出在如吹塑ΡΕ/ΡΑ和在不同溫度下退火1(〇），2(〇）， 4(〇），8(〇），16(〇），24(〇)和32(〇)小時的ΡΕ/ΡΑ瓶中所含PEd 的百分結晶度値；及在如吹塑PE/MPA瓶和在不同溫度退火1(口）， 2(口），4(口），8(口），16(口），24(口)和 32(口)小時的 ΡΕ/PA 瓶中所含 mpa(a)的百分結晶度値之圖形。 經濟部智慧財產局員工消費合作社印製 圖6爲顯示出在如吹塑1^瓶和在不同溫下退火32小時的PE瓶中的 戊院（★，☆)，甲苯(♦，◊)，二甲苯(’□)’十氫（▼，▽)，丙 酮(▲，△)和乙醇(籲，〇)之殘留重量％ °實心符號代表如吹塑PE瓶 的殘留重量％。 圖7爲顯示出在如吹塑PE/PA瓶和在不同溫下退火32小時的PE/PA 瓶中的戊烷（★，☆)，甲苯(♦’◊)，二甲苯(_’□)，十氫（▼’ 第3頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公董） 1288767 A7 B7 五、發明説明ujn ▽)，丙酮(▲，△)和乙醇(籲，〇）之殘留重量％。實心符號代表如吹 塑PE/PA瓶的殘留重量％。 圖8爲顯示出在如吹塑PE/MPA瓶和在不同溫下退火32小時的 PE/MPA瓶中的戊院（★，☆)，甲苯(♦，◊)，二甲苯(’□)，十氫 (▼，▽)，丙酮(▲，△)和乙醇(籲，〇）之殘留重量％。實心符號代 表如吹塑PE/MPA瓶的殘留重量％。 用於本發明高汽油滲漏阻隔性塑膠摻合物容器之製備方法中之 聚烯烴摻合物，係由60至97重量％之聚烯烴與40至3重量％之改質 聚醯胺所組成，該改質聚醯胺則由60至97重量％之聚醯胺與40至3 重量％作爲相容劑先質的烷羧基化聚烯烴，及〇%至3%自由基起始劑 經反應性擠壓而得。 聚烯烴具有低價、質輕、抗環境應力龜裂性佳、耐衝擊性佳、低 吸濕性、易加工性及成型品設計彈性等特性，而成爲最泛用的包裝塑 材。唯在應用於有機液體和蒸氣的包裝時，常受限於低滲透阻隔性。 改良聚烯烴阻隔性之先前技術諸如：美國專利2,811，468號，3,862,284 號，3,998，180 號，4,081，574 號，4，142,032 號，4,394,333 號，與 4,467,075 號等揭示利用氟氣或溴氣等表面處理塑膠薄膜與容器的方法，其可有 效阻隔溶劑之滲透，但對氣體則無此效果；〗K55-80439號揭示以氟碳 化合物電漿處理聚烯烴物件表面的方法，以阻隔汽油等烴類蒸氣之滲 透；美國專利4，182,457號；JK59-103726號與JK59-103727號揭示乙 嫌-乙烯醇共聚物(EVOH)當阻隔層，共擠壓六層結構爲聚丙烯/接著層 /乙烯-乙烯醇共聚物/接著層/二次料/聚丙烯並吹壓成型的方法，其可 有效阻隔氣體之滲透；美國專利3,857,754號與3,975,463號揭示以高 剪力設備均勻混合聚烯烴，乙烯-乙烯醇共聚物與含羧基熱塑性樹脂 摻合物以製成阻隔性三層膜；至於以聚醯胺改善聚烯烴阻隔性之技術 第4頁，共13頁 $^尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫Patent 4,950,513 (1990)) and a few patents. Only PA is incompatible with PE, and the interface is not well connected. It is often necessary to add CP to PE/PA during the blow-molding process to increase its interface with HDPE. In view of this, the inventor of the present invention discovered through the intensive research that in selecting the appropriate CP and PA, the modified nylon (MPA) was first made by twin-screw extruder, and the PE was properly formulated with MPA. A blow molding machine can be used to prepare PE/MPA blending bottles. The prepared bismuth/MPA blending bottle can achieve a high gasoline permeation barrier effect, and only uses a conventional inexpensive blow molding machine, which is not only cost-effective but also infringes on existing domestic and foreign related patents. And the resulting gasoline leakage barrier effect can be as low as 5% or less of the total stored gasoline in the container at 40 ° C for one year. This barrier effect is higher than the barrier leakage effect of the above patents. Accordingly, the present invention provides a method for preparing a high gasoline leakage barrier plastic blend container comprising using a high density polyethylene blended with modified polyamine (MPA) in a conventional blow molding machine at a low cost ( HDPE) A properly formulated, ie, PE/MPA composition, is prepared by a laminating bottle blowing process to obtain a high gasoline leakage barrier plastic blend container that forms a MPA laminar structure in a HDPE matrix. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing a blown PE bottle (·) and annealed at different temperatures (〇), 2 (〇)' 4 (〇), 8 (〇), 16 (〇), 24 A graph of the gasoline permeation rate obtained for PE bottles after (〇) and 32 (〇) hours. Figure 2 shows the annealing of PE/PA bottles (▲) and annealing at different temperatures 1 (Δ) ' 2 (Δ) ' 4 (Δ), 8 (Δ), 16 (Δ), 24 (Δ) and A graph of the gasoline permeation rate obtained for a PE/PA bottle after 32 (Δ) hours. Figure 3 shows the blown PE/MPA bottle (_) and the annealing at different temperatures 1 (mouth) ' 2 (mouth)' Page 2 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back and fill in. Write the Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Co., Ltd. Printed A7 B7 1288767 V. Inventions (3) 4(C)), 8 (mouth), 16 Graph of gasoline penetration rate of PE/MPA bottles after (mouth), 24 (mouth) and 32 (mouth) hours. Please read the notes on the back © first and then fill in Figure 4 to show the blown (a) PE, (b) PE/PA, and (c) PE/MPA bottles and (d) PE after annealing for 32 hours at ll ° ° C, (e) PE/PA and (f) rupture surfaces of PE/MPA bottles Microphotograph. Figure 5a shows the blown PE bottle (·) and annealed at different temperatures 1 (〇), 2 (〇), 4 (〇), 8 (〇), 16 (〇), 24 (〇 And 32 (〇) hours after the PE bottle obtained the percent crystallinity 値 。. Figure 5b is shown in the case of blown ΡΕ / ΡΑ and at different temperatures 1 (〇), 2 (〇) ' 4 (〇), 8 (〇), 16 (〇), 24 (〇) and 32 (〇) hours in PE/PA bottles Percent crystallinity of 含 containing PEd; and annealing 1 (Δ) ' 2 (Λ), 4 (Δ), 8 (Δ), 16 (Δ), 24 (eg, in blown PE/PA bottles and at different temperatures) Δ) and 32 (Δ) hours of ΡΕ/ΡΑ The graph of the percent crystallinity of ΡΑ(Α) contained in the bottle. Figure 5c shows the annealing at 1/〇 at different temperatures such as blown ΡΕ/ΡΑ ), 2 (〇), 4 (〇), 8 (〇), 16 (〇), 24 (〇) and 32 (〇) hours of 结晶/% of the crystallinity of the PEd contained in the flask; Such as blown PE / MPA bottles and annealed at different temperatures 1 (mouth), 2 (mouth), 4 (mouth), 8 (mouth), 16 (mouth), 24 (mouth) and 32 (mouth) hours of ΡΕ / The graph of the percent crystallinity of mpa(a) contained in the PA bottle. Printed by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Figure 6 shows PEs that were annealed for 32 hours at different temperatures, such as blow molding. Residual weight % of the tea (★, ☆), toluene (♦, ◊), xylene ('□) 'decahydrogen (▼, ▽), acetone (▲, △) and ethanol (, 〇, 〇) in the bottle °The solid symbol represents the residual weight % of the blown PE bottle. Figure 7 shows the small annealed in a PE/PA bottle such as a blown bottle at different temperatures. Pentane (★, ☆), toluene (♦ '◊), xylene (_'□), decahydrous (▼', page 3 of 13 in this PE/PA bottle applies to Chinese national standards ( CNS ) A4 specification (210X297 dong) 1288767 A7 B7 V. Invention description ujn ▽), residual weight % of acetone (▲, △) and ethanol (吁, 〇). The solid symbol represents the residual weight % of the blown PE/PA bottle. Figure 8 is a diagram showing the tow (★, ☆), toluene (♦, ◊), xylene ('□) in a PE/MPA bottle such as a blown PE/MPA bottle and annealed at different temperatures for 32 hours. The residual weight % of decahydrogen (▼, ▽), acetone (▲, △) and ethanol (, 〇, 〇). The solid symbol represents the residual weight % of the blown PE/MPA bottle. The polyolefin blend used in the preparation method of the high gasoline leakage barrier plastic blend container of the present invention is composed of 60 to 97% by weight of polyolefin and 40 to 3% by weight of modified polyamine. The modified polyamine is reacted with 60 to 97% by weight of polyamidamine and 40 to 3% by weight of alkoxylated polyolefin as a compatibilizer, and 〇% to 3% of a radical initiator Sexual extrusion. Polyolefins are the most widely used packaging plastics because of their low cost, light weight, good resistance to environmental stress cracking, good impact resistance, low moisture absorption, easy processing, and design flexibility. It is often limited by low permeability barriers when applied to packaging of organic liquids and vapors. Prior art techniques for improving polyolefin barrier properties include, for example, U.S. Patent Nos. 2,811,468, 3,862,284, 3,998,180, 4,081,574, 4,142,032, 4,394,333, and 4,467,075, et al. A method for surface treating plastic film and container, which can effectively block the penetration of the solvent, but has no effect on the gas; K55-80439 discloses a method for treating the surface of the polyolefin object with a fluorocarbon plasma to block hydrocarbons and the like Vapor-like infiltration; U.S. Patent No. 4,182,457; JK59-103726 and JK59-103727 disclose B-vinyl alcohol copolymer (EVOH) as a barrier layer, co-extruding a six-layer structure of polypropylene/back layer/ethylene - a method for the formation of a vinyl alcohol copolymer/adhesive layer/secondary material/polypropylene and a blow molding process, which is effective for blocking gas permeation; U.S. Patent Nos. 3,857,754 and 3,975,463 disclose the uniform mixing of polyolefins, ethylene with high shear equipment. A blend of a vinyl alcohol copolymer and a carboxyl group-containing thermoplastic resin to form a barrier three-layer film; a technique for improving the barrier property of a polyolefin with polyamine. Page 4 of 13 National Standards (CNS) A4 size (210X297 mm) (Please read the Notes on the back and then fill
經濟部智慧財產局員.工消費合作社印製 1288767 at B7 五、發明説明（¾ ) (請先閲讀背面之注意事項再填寫本頁) 諸如美國專利3,873,667號揭示以熱處理法提高聚烯烴/聚醯胺摻合 物，美國專利3,373,222，3,373,223與3,373,224號等則揭示使用羧基 化聚乙烯-不飽和羧酸共聚物等分散劑以提高聚烯烴/聚醯胺摻合物之 阻隔性與機械強度，但這些專利都著重於均相聚烯烴/聚醯胺摻合物 之製備技巧，而無法有效提昇聚烯烴之阻隔性。 美國專利4,410,482，4,416942與4,444,817號揭示含有相容劑之 聚醯胺分佈於聚烯烴基材的異相積層摻合物，其對烴類化合物據高滲 透阻隔性，但由於該摻合物的製備係將組成物乾混，需利用特殊擠壓 設備，且極爲小心地避免高剪切力及高能量，才得以熔融加工而成； 中華民國發明專利53,999號則揭示利用脂肪族聚醯胺與半芳香族聚 醯胺以相容劑進行反應性擠壓製備改質聚醯胺’於一般擠壓設備製備 聚醯胺/改質聚醯胺摻合物，但其阻隔改善程度未能符合環保滲漏法 規之要求，而不利於商業化生產。 經濟部智慧財產局員工消費合作社印製 關於本發明組成物之比例，構成連續相的聚烯烴百分率以介於 6〇至97重量％爲佳，並以介於80至96重量％爲較佳，構成不連續相 的改質聚醯胺重量百分率以介於40至3重量％爲佳，並以介於20至 4重量％爲較佳。當本發明之組成物以積層法吹壓成型時’若改質聚 醯胺與聚烯烴之熔融粘度比太大或太小，改質聚醯胺之熔融強度相較 隨之變差或提高，均不利於拉伸成積層狀。熔融粘度以恆定應力毛細 管粘度計於23(TC測定，吾人可得該熔融粘度比宜介於〇·6至丨·5並以 介於於0.8至1.3爲較佳。任何不會影響成型品物性的惰性添加劑或 塡充劑均可加入本組成物中。但在計算含量時，則未將該惰性物列入。 關於本發明組成物中之聚烯烴可爲烯烴均聚物與共聚物，適當者 包括聚乙烯(諸如高密度聚乙烯、中密度聚乙烯、線型低密度聚乙嫌 及低密度聚乙烯），聚丙烯，聚正丁烯’聚異丁烯’乙嫌/丙嫌共聚物， 乙烯/正丁烯共聚物及乙烯/丙烯/正己烯參聚物等’並以聚乙烯及聚丙 烯爲較佳。 第5頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐Γ 1288767 A7 B7__ 五、發明説明（G ) (請先閱讀背面之注意事項再填寫本頁) 關於本發明中之改質聚醯胺，其成分包括60至9重量7%的聚醯 胺’ 40至3重量％作爲相容劑先質的烷羧基化聚烯烴，〇至3重量％ 的自由基起始劑(佔聚醯胺及相容劑先質總重)及5〇〇ppm至3000ppm 的抗氧化劑。考量改質聚醯胺之阻隔性，聚醯胺含量以70至95重量 %及烷羧基化聚烯烴以30至5重量％爲較佳。適於製備本發明中之改 質聚醯胺的聚醯胺主材包括脂肪族聚醯胺和半芳香族聚醯胺。適當之 專利技術諸如美國專利2,071，251號，2，130,523號，2,241，322號， 2,312,966 號，2,512,606 號，3,393,210 號，及 4,369,305 號。脂肪族聚 醯S女可由內醯胺(lactam)，胺基殘酸(aminocarboxylic acid)或C4-C14之二 元竣酸與C4-C14之二元胺經聚縮合反應或由內醯胺經開環反應而製 得。該內醯胺諸如己內醯胺；該胺基羧酸諸如11_胺基十一烷酸；該 二元羧酸諸如丙二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、 2-胺基戊二酸及十二烯酸等；該二元胺則諸如丁二酸、戊二胺、己二 胺及辛二胺等。所製得聚醯胺包括聚己二醯戊二胺、聚己二醯己二 胺、聚壬二醯己二胺、聚癸二醯己二胺、聚十二烷醯己二胺、聚己內 醯胺，由11-胺基十一烷酸所製得者，與由至少兩種以上述之酸或胺 所共聚合而成者，其中並以聚己內醯胺，聚己二醯己二胺及聚己內醯 胺與聚己二醯己二胺之摻合物或共聚物爲較佳。 經濟部智慧財產局員工消費合作社印製 半芳香族聚醯胺由任一含有環狀構造之二元酸與二元胺所聚合 而成。適當的二元酸諸如己二酸、壬二酸、對苯二甲酸、間苯二甲酸 及環己基-1,4，-二羧酸；適當的二元胺諸如己二胺，三甲基_ι，6-六亞甲 基二胺，4,4’-二胺基-二環己烯甲烷及4,4’-二胺-3,3’-二甲基-二環己烯 甲烷等醯胺，和己內醯胺及月桂內醯胺等內醯胺。典型的半芳香族聚 醯胺諸如對苯二甲酸/己二酸/己二胺參聚物及對苯二甲酸/4,4，-二胺 基-二環己烯甲烷/己內醯胺參聚物等。爲製得高分子量之半芳香族聚 醯胺，所使用之二元酸總莫耳數應等於二元胺總莫耳數。其製法可採 用熔融、溶液或介面等熟知的聚合方式，並以熔融聚合法爲佳，反應 溫度可介於170°C至300°C，壓力可介於1大氣壓至300大氣壓。 第6頁，共13頁 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 一 1288767 at B7 五、發明説明（7) 此處之烷羧基化聚烯烴係指以烷羧基取代之聚烯烴，該取代基爲 附著在聚烯烴主鏈或側鏈，可選自酸、酯、酸酐或鹽^1。若烷羧基化 (請先閱讀背面之注意事項再填寫本莧) 聚嫌烴所採用之竣酸鹽爲以金屬離子中和過之竣酸，即爲所謂的「離 子型聚合物」。 、 ~ σ 羧酸基化聚烯烴可用直接合成法或接枝法製得。直接合成法諸如 α-烯烴與含有羧基之烯烴單體行聚合反應；接枝法諸如將含有羧基 之單體導入聚烯烴主鏈中。對於以接枝法製成之烷羧基化聚烯烴，聚 烯烴爲聚乙烯或聚丙烯，或乙烯與至少一種C3-C8的α -烯烴(例如丙烯) 之共聚物，或乙嫌與至少一種的G-Cs的α-燦烴及二嫌烴(例如ι，4-己二烯）之共聚物。該聚烯烴與不飽和羧酸，酸酐或酯等單體反應而 得接枝聚合體。典型的適當羧酸，酸酐與酯諸如：甲基丙烯酸，丙烯 酸，乙基丙烯酸，順式丁烯二酸，反式丁烯二酸，二亞甲基丁二酸， 順式丁烯二酐，十二碳烯丁二酸酐，5-原冰片烯-2,3-酐，3,6-內亞甲 基-1，2,3,6-四氫鄰苯二甲酸酐，甲基丙烯酸縮水甘油酯，丙烯酸2-羥 基乙酯，甲基丙烯酸2-羥基乙酯，順式丁烯二酸二乙酯，順式丁烯二 酸乙酯，順式丁烯二酸二正丁酯，及該二羧酸之單酯等。其中以順式 丁烯二酸酐’反式丁烯二酸，丙烯酸及甲基丙烯酸爲較佳。通常此接 枝聚合體所含接枝單體之重量百分率介於0.01%至20%，以0.1%至 10%爲宜，並以0.2%至5%爲最佳。 經濟部智慧財產局員工消費合作社印製 至於以直接合成法製成之烷羧基化聚烯烴，其爲CVCh)之α -烯烴 與含有1或2個羧基的α j _乙烯型不飽和羧酸，酯，酸酐或鹽之共 聚物或參聚物，烯烴成分之重量百分率至少爲60%，羧基成份之重量 百分率則介於0.3%至40%。典型例諸如乙烯/順式丁烯二酐共聚物， 乙烯/順式丁烯二酸酐/丙烯酸正丁酯參聚物。 離子型聚合體以直接合成法爲宜，並以烯烴的重量百分率爲80% 至90%，含有羧基不飽和單體的重量百分率爲20%至2%較佳，所製 得聚合體再以1至3價金屬離子中和而成。此金屬離子含量需爲能充 第7頁，共13頁 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1288767 at B7 五、發明説明（8 ) 分中和至少10%以上之羧基，以控制該中和度。典型的α-烯烴，不 飽和羧酸，酸酐及酯單體可爲如前述者。 (請先閲讀背面之注意事項再填寫本頁) 烷羧基化聚烯烴可藉由自由基起始劑的存在，進行分支或有限度 的交聯，以提高改質聚醯胺的阻隔性及熔融粘度與熔融強度。適當的 自由基起始劑包括過氧化物(諸如過氧化二異丙苯基，α，α 雙-(第三 丁烷過氧化物二異丙基），偶氮化合物(諸如偶氮二異丁腈)及硫化合物 等，其中過氧化物或偶氮化合物的使用量約爲改質聚醯胺重量的 0.01%至0.5%，及硫化合物的使用量約爲0.5%至3%。 至於本發明中改質聚醯胺的製備，係將聚醯胺，烷羧基化聚烯烴 或自由基起始乾混後，進行反應性擠壓而得，並以雙螺桿擠壓機趁g 剪力及擠壓溫度介於220°C至250t的條件佳製備爲佳，所製得改質 聚醯胺之分散相亦宜均勻且微小。 所製得改質聚醯胺與聚烯烴之間具有良好的相容性及接著力。 再者，本發明的聚烯烴/改質聚醯胺摻合物之擠壓加工，擠壓機 螺桿可爲聚乙烯型、聚氯乙烯型及阻隔型(barrier type)，並以具較低 剪切力的後二者爲較佳；螺櫸轉„速宜介於15rpm至80rpm以利形成積 層，並以介於20rpm至60rpm爲較佳。 經濟部智慧財產局員工消費合作社印製 依據本發明的聚烯烴/改質聚醯胺摻合物，其對許多有機液體， 諸如脂肪族烴類化合物(如汽油，庚烷），芳香族烴類化合物(如甲苯， 二甲苯），鹵化烴類化合物(如三氯乙烷，鄰二氯苯)及油漆稀釋劑等具 有極佳的滲透阻隔性，亦對上述有機液體的蒸氣具有良好的阻隔性。 本發明要用下列非限制性實施例予以進一步說明。 第8頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1288767 at B7 五、發明説明（9) 實施例 材料與樣品製備 使用不同的相容劑先質經由與聚醯胺摻合來製備不同的經改質 聚醯胺。實施例中所用相容劑先質爲經鋅-中和的乙烯/丙烯酸共聚 物(台灣化學纖維公司）。所用聚醯胺爲耐綸6,共亦得自台灣化學纖 維公司，商品名爲Sunylon 6N。實施例中所用聚乙烯(HDPE Taisox 9003) 與抗氧化劑(Irganox B225)分別得自台塑公司與Ciba_Beigy公司。 在熔融摻合之前，將PA與CP分別置於80°C乾燥16小時及在60 °C下乾燥8小時。將約1500 ppm的抗氧化劑與經乾燥的PA/CP成分 以85:15的重量比例乾摻後，給入Ekegai PCM 45共同轉動雙螺桿擠 壓機內製造MPA樹脂。擠壓機係於進料區的220°C朝向擠壓模頭的 240°C之溫度下，以100 rpm螺桿速度操作。將雙螺桿擠壓機的經CP 改質聚醯胺置於約15°C的冷水中驟冷並切割成九粒形式。將各種改質 聚醯胺九粒置於80°C下乾燥16小時後，與PE以10:90重量比乾摻合。 然後在Jonh Huah TPH-550擠壓吹塑機內以230°C的擠壓溫度和 400 rpm的螺桿溫度將混合PE/MPA和PE/PA摻合物吹塑。在吹塑之 前用一習用的聚乙烯螺桿擠壓ΡΕ/MPA摻合物。吹塑瓶重量爲約100 克，且具有約750毫升的容量極約2毫米的壁厚。爲比較目的，也甩 基本PE樹脂使用相同的螺桿與吹塑機，但在190°C的積壓溫度，及 400 rpm的螺桿速度下操作。 上面所製的如吹塑成PE，PE/PA和PE/MPA瓶子都在不同溫度下 退火不同的時間。所用退火溫度分別爲60、70、80、90、100和120 °C。於各退火條件溫度下，分別將瓶子退火1、2、4、8、16、24和 36小時。表1摘列出所用的熱處理條件及PE，PE/PA與PE/MPA瓶子 的樣品編號。 第9頁，共13頁 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1288767 at B7 五、發明説明（10) 滲透試驗 將上面所致如吹塑成瓶子及經退火瓶子經由測量瓶中所裝汽油 的重量減損予以評估。PE，PE/PA與PE/MPA瓶子於起始處皆經裝塡 380克的汽油。將塡充瓶置於40°C下14天之後測定汽油的重量減損。 另一方面，也基於熱壓片測定PA與MPA樹脂旳滲透阻隔性質。將 PA與MPA乾粒熱壓成約2毫米厚片並切成14公分直徑的圓片。將 圓形PA和MPA片作爲蓋子封蓋在裝有250客汽油的試驗燒瓶頂端。 然後，將燒瓶置於40°C下14天’再測定圓片的滲透阻隔性質。根據 至少三個瓶子或熱壓片樣品的平均滲透率分別估測各種瓶子或熱壓 片的汽油滲透率。 滲透試驗之前與之後的汽油燃料組成 使用裝有氫火焰游離偵檢器的China 8900氣體層析儀(GC)在瓶子 滲透試驗之前與之後測定無鉛汽油燃料的組成。使用Restek Alumina Plot毛細管柱來分離甲醇/汽油燃料。該毛細管的內徑爲約0.53毫米 且其長度爲30米。在滲透試驗之前與之後將汽油燃料於230°C下注射 到GC內以測定組成。使用20立方厘米/分的氦氣在220°C下作爲載 氣。爲了改良分離效率，以4°C/分的加熱速率將毛細管從30°C提升 到210t。偵檢器溫度爲230°C。無鉛汽油中所含主要成分爲非極性 線形，環狀和芳族烴類(約5至10個碳者)及某些極性液體，如丙酮， 乙醇，及其他添加劑。爲比較與方便目的，選擇汽油燃料中有5至10 個碳主鏈的烴成分(亦即.，正戊烷，二甲苯和十氫）及極性成分（亦 即，丙酮和乙醇)並用GC測定其殘留重量％來代表滲透試驗後的殘留 汽油燃料組成。各種溶劑的殘留重量％係以滲透試驗後的各溶劑峰對 滲透試驗前的各溶劑峰之面積比來測定。 熱性質 第10頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 1288767 at B7 五、發明説明（fl) (請先閲讀背面之注意事項再填寫本頁) 對PE，PE/PA與PE/MPA瓶子中的PE，PA，CP與MPA所具熱 性質係用Du Pont 2010差式掃描熱量計(DSC)分別測定。所有掃描都 在流速25毫升/分的氮氣流下以10°C/分的加熱速率進行的。儀器係 經用純銦校準過。將重約15毫克的樣品置於標準鋁樣品盤中。使用 從30°C拉到160°C的基線及293焦耳/克的PE完全熔融熱來{古測| pE 與CP的結晶度値。使用170至250t的基線及190焦耳/克的完全熔 融熱來估計PE/CP/PA與PE/MPA中所含PA或MPA的結晶度値。實 驗中所用的基線皆經調整到在標的溫度範圍內具有低於〇.〇4 mw 0¾ 大起伏。使用彼等基線時，熔融熱的最大變異通常是在約±3焦/克， 其在估測結晶度値中導致1%的誤差。 如吹塑瓶和經退火瓶的型態學 爲了觀察再如吹塑及經退火ΡΕ/PA和PE/MPA瓶中所含MpA與 PA樹脂之個別變形構造，先將這些瓶子用解剖刀割切後，用甲酸鈾 刻。接著將經触刻的樣品鍍金並用Joel TSM-5200掃描電子顯微術 (SEM)予以檢驗。爲比較目的，也對如吹塑瓶和經退火瓶的經蝕刻樣 品用SEM檢驗。 結果 經濟部智慧財產局員工消費合作社印製 PE，PA，CP和MPA熱壓片海PE，PE/PA和PE/MPA如晚塑瓶夕汽油 滲漏件晳 表II摘列出PE，PA，CP和MPA熱壓片之汽油滲透率。於三種 基質樹脂，亦即，PE，CP，和PA中，PA片展現出最佳的抗汽油滲 海胜，而CP片表現出最差的抗汽油滲漏性。改値聚醯胺(MPA)片則 展現出比PA片遠較爲佳的抗汽油滲漏性。MPA的汽油滲透率比PE 片和PA片分別較慢約49倍和7倍(參看表II)。類似於對熱壓片所得 結果，於PE，PE/PA和PE/MPA瓶中如吹塑PE瓶具有最差的汽油滲 ^ 第11頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1288767 五、發明説明 (12) (請先閱讀背面之注意事項再填寫本頁) 透抗性。如表II中所示者，於吹塑中在PE內摻入PA或MPA後，可 大幅地改善汽油滲透抗性，且阻隔裝改良順序對應於在PE中所佳阻 隔性樹脂的阻隔改良順序。在PE中摻加10重量％的“？人或PA後， 如吹塑PE/MPA或PE/PA瓶的汽油滲透率比如吹塑PE瓶分別較慢約 130倍或15倍。 經退火PE，PE/PA與PE/MPA瓶的汽油渗漏件質 頗令人訝異者，在將如吹塑PE瓶在60至120°C溫度下退火不同 時間之後，其汽油滲透速率竟有明顯地增加(參看圖1)。事實上，彼 等的汽油滲透率係隨著退火溫度與時間而一致地增加。例如’在120 °C退火32小時的PE瓶所具汽油滲透速率比如吹塑PE瓶較快約30%。 類似地，當PE/PA瓶在90°C或更高溫度退火時，其汽油滲透速率也 隨退火溫度與時間明顯地增加(參看圖2)。不過，PE/PA瓶在60°C退 火各種時間時，其滲透速率會稍微減低。在將ΡΕ/MPA瓶置於120°C 退火32小時後，其汽油滲透速率比如吹塑PE/MPA瓶減低約32%，相 當於比如吹塑PE瓶和相應的經退火PE瓶分別較慢約190倍和240倍。 如吹塑和經拫火PE，PE/PA和PE/MPA瓶的型熊璺 經濟部智慧財產局員工消費合作社印製 圖4槪示出PE，PE/PA和PE/MPA瓶子破裂表面的典型顯微攝影 圖。可看到許多淸晰確定的MPA層在PE基質內沿著如吹塑PE/MPA 瓶的壁厚方向分佈著(參看圖4c)。於如吹塑PE/PA瓶的破裂表面上可 看到略爲斷裂但較不淸晰的PA層(參看圖4b)。據推論PE/MPA與 PE/{A瓶子的阻隔改良水平明顯決定於基質阻隔樹脂的阻隔性質。再 者，分割淸晰且伸長的MPA層可更延長滲透分子的阻隔期且改良 PE/MPA瓶的汽油滲透抗性。 相反地，可以有趣地發現在經退火的pE ’ ΡΕ/PA和PE/MPA瓶上 相對於彼等的如吹塑瓶而言沒有觀察到在破裂表面型態學上的明顯 第12頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210Χ297公釐） 1288767 at B7 五、發明説明 (13) 變化(參看圖4d至4f)。根據這些前提，可推測經退火的PE，PE/PA 和PE/MPA瓶之汽油滲透抗性上的明顯變化可能不是來自退火的型態 學變化。 PE，PE/PA和PE/MPA瓶的熱件菅 圖5a至5c槪示出在如吹塑及經退火的PE，PE/PA和PE/MPA瓶 中所含PE的結晶度値(Wc)。於所示溫度下，在經退火瓶中所含PE的 結晶度値皆高於如吹塑瓶，且隨退火時間而明顯增加。事實上可看 出，在固定退火時間下，經退火PE，PE/PA和PE/MPA瓶中所含PE 的Wc値會隨退火溫度增高而明顯增加。如圖5a至5c所示者，經退 火瓶所含PE的Wc在120°C退火32小時後分別增加約6和5%。 逡诱試験夕前與之後的汽油燃料組成 圖6至8槪示出如吹塑瓶與經退火瓶在滲透試驗之前和之後的汽 油燃料典型組成。在40°C，14天後汽油燃料所含具有5至10主鏈碳 原子的烴成分(如正戊烷，甲苯，二甲機和十氫）有明顯量會穿過如 吹塑瓶，而極性成分(如丙酮和乙醇)保留幾乎不變地，沒有滲透(參看 圖6)。相反地，將阻隔樹脂摻入PE基質後，汽油燃料中所含相當非 極性的烴成分於滲透試驗期間被明顯地阻斷而無滲透，其中如吹塑 PE/MPA瓶比如吹塑PE/PA更成功地阻斷烴成分的滲透(參看圖7和 8)。不過，川透過如吹塑PE/PA瓶和PE/MPA瓶的極性成分(如丙酮和 乙醇)之量則非常少且約爲川透過如吹塑PE瓶者。頗令人驚認者，經 退火PE瓶所得非極性烴成分和極性成分兩者的滲透量皆高於如吹塑 PE瓶；且隨著退火溫度和時間一致地增加（圖6)。如圖7中所示者， 對於在90°C或更高溫度下退火不同時間的PE/PA瓶也有類似的趨 勢。相反地，在對PE/MPA瓶施以任何退火處理後，相當非極性烴成 分與極性成分兩者的滲透量都隨退火溫度和時間而一致地減少（參看 圖8)。 第13頁，共13頁 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫·Ministry of Economic Affairs Intellectual Property Bureau. Workers' Consumption Cooperatives Printed 1288767 at B7 V. Invention Description (3⁄4) (Please read the note on the back and fill out this page). For example, US Patent No. 3,873,667 discloses the improvement of polyolefin/polyamide by heat treatment. Blends, U.S. Patent Nos. 3,373,222, 3,373,223 and 3,373,224 disclose the use of dispersants such as carboxylated polyethylene-unsaturated carboxylic acid copolymers to enhance the barrier properties and mechanical strength of polyolefin/polyamine blends, but these The patents focus on the preparation of homogeneous polyolefin/polyamine blends and do not effectively enhance the barrier properties of polyolefins. U.S. Patent Nos. 4,410,482, 4,416,942 and 4,444,8, the disclosure of each of each of each of each of each of The preparation system dry-mixes the composition, requires special extrusion equipment, and is extremely careful to avoid high shear force and high energy before being melt processed. The Republic of China invention patent No. 53,999 reveals the use of aliphatic polyamines and Semi-aromatic polyamides are prepared by reactive extrusion of compatibilizers to prepare modified polyamines to prepare polyamine/modified polyamine blends in general extrusion equipment, but the degree of barrier improvement is not environmentally friendly. The requirements of leakage regulations are not conducive to commercial production. The percentage of the polyolefin constituting the continuous phase is preferably from 6 〇 to 97% by weight, and preferably from 80 to 96% by weight, based on the ratio of the composition of the present invention printed by the Ministry of Economic Affairs Intellectual Property Office employee consumption cooperative. The weight percent of the modified polyamine which constitutes the discontinuous phase is preferably from 40 to 3% by weight, and more preferably from 20 to 4% by weight. When the composition of the present invention is formed by a laminate method, if the melt viscosity ratio of the modified polyamine and the polyolefin is too large or too small, the melt strength of the modified polyamine decreases or increases. It is not conducive to stretching into a laminate. The melt viscosity is measured by a constant stress capillary viscometer at 23 (TC, which is preferably obtained by a ratio of 〇·6 to 丨·5 and preferably between 0.8 and 1.3. Any influence of the physical properties of the molded article is not affected. The inert additive or the chelating agent may be added to the composition, but the inert content is not included in the calculation of the content. The polyolefin in the composition of the present invention may be an olefin homopolymer and a copolymer, suitably Including polyethylene (such as high density polyethylene, medium density polyethylene, linear low density polyethylene and low density polyethylene), polypropylene, poly n-butene 'polyisobutylene' B / C copolymer, ethylene / Non-butene copolymer and ethylene/propylene/n-hexene reference polymer, etc., and polyethylene and polypropylene are preferred. Page 5 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297) PCT 1288767 A7 B7__ V. INSTRUCTIONS (G) (Please read the note on the back and fill out this page.) About the modified polyamine in the present invention, the composition includes 60 to 9 wt% of polyamine. 40 to 3% by weight of the alkaryl group as a precursor to the compatibilizer Polyolefin, 〇 to 3% by weight of free radical initiator (accounting for the total weight of polyamine and compatibilizer precursor) and 5 〇〇 to 3000 ppm of antioxidant. Consider the barrier properties of modified polyamine, poly The content of the decylamine is preferably from 70 to 95% by weight and the alkoxylated polyolefin is from 30 to 5% by weight. The polyamine amine suitable for the preparation of the modified polyamine of the present invention comprises an aliphatic polyamine and Semi-aromatic polyamines. Suitable patented techniques such as U.S. Patent Nos. 2,071,251, 2,130,523, 2,241,322, 2,312,966, 2,512,606, 3,393,210, and 4,369,305. A lactam, an aminocarboxylic acid or a C4-C14 dicarboxylic acid and a C4-C14 diamine are obtained by a polycondensation reaction or a ring-opening reaction of an indoleamine. A guanamine such as caprolactam; the amino carboxylic acid such as 11-aminoundecanoic acid; the dicarboxylic acid such as malonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, hydrazine Diacid, 2-aminoglutaric acid, dodecenoic acid, etc.; such diamines such as succinic acid, pentane diamine, hexamethylene diamine and octane diamine. The polyamines obtained include polyhexamethylene pentane diamine, polyhexamethylene diamine, polyphthalamide, polydecyl hexamethylene diamine, polydodecane hexamethylene diamine, polyhexene Guanamine, which is prepared from 11-aminoundecanoic acid, and is obtained by copolymerizing at least two of the above acids or amines, wherein polycaprolactam, polyhexamethylene A blend of amine and polycaprolactam and polyhexamethylene adipamide is preferred. The semi-aromatic polyamine printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs is composed of any cyclic structure. The dibasic acid is polymerized with a diamine. Suitable dibasic acids such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid and cyclohexyl-1,4,-dicarboxylic acid; suitable diamines such as hexamethylene diamine, trimethyl _ ι,6-hexamethylenediamine, 4,4'-diamino-dicyclohexenemethane and 4,4'-diamine-3,3'-dimethyl-dicyclohexenemethane Amine, and indoleamine such as caprolactam and laurylamine. Typical semi-aromatic polyamines such as terephthalic acid/adipic acid/hexanediamine reference and terephthalic acid/4,4,-diamino-dicyclohexenemethane/caprolactam Polymer, etc. To produce a high molecular weight semi-aromatic polyamine, the total number of moles of dibasic acid used should be equal to the total moles of diamine. The preparation method may be a well-known polymerization method such as melting, solution or interface, and is preferably a melt polymerization method, the reaction temperature may be from 170 ° C to 300 ° C, and the pressure may be from 1 atm to 300 atm. Page 6 of 13 This paper scale applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1288767 at B7 V. Inventive Note (7) The alkylated carboxylated polyolefin here refers to the substitution of alkylcarboxyl The polyolefin is attached to the polyolefin main chain or side chain and may be selected from the group consisting of an acid, an ester, an acid anhydride or a salt. If the alkanolation is carried out (please read the precautions on the back side and fill in this section). The phthalate used in the polyene hydrocarbon is a ruthenium acid neutralized with a metal ion, which is a so-called "ion-type polymer". , ~ σ Carboxylated polyolefin can be obtained by direct synthesis or grafting. A direct synthesis method such as an α-olefin is polymerized with an olefin monomer having a carboxyl group; and a grafting method such as introducing a monomer having a carboxyl group into the polyolefin main chain. For an alkoxylated polyolefin prepared by a grafting process, the polyolefin is polyethylene or polypropylene, or a copolymer of ethylene and at least one C3-C8 alpha-olefin (for example, propylene), or B and at least one A copolymer of an alpha-teronol of G-Cs and a second suspected hydrocarbon such as iota, 4-hexadiene. The polyolefin is reacted with a monomer such as an unsaturated carboxylic acid, an acid anhydride or an ester to obtain a graft polymer. Typical suitable carboxylic acids, anhydrides and esters such as: methacrylic acid, acrylic acid, ethacrylic acid, maleic acid, trans-butenedioic acid, dimethylene succinic acid, maleic anhydride, Dodecene succinic anhydride, 5-norbornene-2,3-anhydride, 3,6-endomethyl-1,2,3,6-tetrahydrophthalic anhydride, glycidyl methacrylate Ester, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethyl maleate, ethyl maleate, di-n-butyl maleate, and a monoester of a dicarboxylic acid or the like. Among them, cis-butylene anhydride 'trans-maleic acid, acrylic acid and methacrylic acid are preferred. Generally, the weight percentage of the graft monomer contained in the graft polymer is from 0.01% to 20%, preferably from 0.1% to 10%, and most preferably from 0.2% to 5%. The Ministry of Economic Affairs, the Intellectual Property Office, and the Employees' Cooperatives, print the alkylated polyolefins produced by direct synthesis, which are CVCh) α-olefins and α j _ ethylenically unsaturated carboxylic acids containing 1 or 2 carboxyl groups. The copolymer or the reference copolymer of the ester, anhydride or salt has a weight percentage of the olefin component of at least 60% and a weight percentage of the carboxyl component of 0.3% to 40%. Typical examples are copolymers such as ethylene/maleic anhydride, ethylene/maleic anhydride/n-butyl acrylate. The ionic polymer is preferably a direct synthesis method, and the weight percentage of the olefin is 80% to 90%, and the weight percentage of the carboxyl group-containing unsaturated monomer is preferably 20% to 2%, and the obtained polymer is further 1 It is neutralized to a trivalent metal ion. This metal ion content needs to be able to charge the 7th page, a total of 13 pages of this paper scale applicable to China National Standard (CNS) A4 specification (210X297 mm) 1288767 at B7 V. Invention description (8) Minute and at least 10% The carboxyl group to control the degree of neutralization. Typical α-olefins, unsaturated carboxylic acids, acid anhydrides and ester monomers may be as described above. (Please read the notes on the back and fill out this page.) Alkylated carboxylated polyolefins can be branched or limitedly crosslinked by the presence of a free radical initiator to improve the barrier properties and melting of the modified polyamine. Viscosity and melt strength. Suitable free radical initiators include peroxides (such as dicumyl peroxide, alpha, alpha bis-(tert-butane peroxide diisopropyl), azo compounds (such as azobisisobutyl) Nitrile) and a sulfur compound, etc., wherein the peroxide or azo compound is used in an amount of from 0.01% to 0.5% by weight based on the weight of the modified polyamine, and the sulfur compound is used in an amount of from about 0.5% to 3%. The preparation of the medium-modified polyamine is carried out by reactively extruding the polyamidamine, the alkoxylated polyolefin or the free radical, and then performing the reactive extrusion, and the twin-screw extruder is used for shearing and squeezing. The pressure is preferably between 220 ° C and 250 t, and the dispersed phase of the modified polyamine is also uniform and minute. The modified polyamine and the polyolefin have a good phase. Capacitance and adhesion. Further, in the extrusion processing of the polyolefin/modified polyamine blend of the present invention, the extruder screw may be a polyethylene type, a polyvinyl chloride type, and a barrier type. And the latter two with lower shear force are preferred; the snail turn „ speed should be between 15 rpm and 80 rpm to form a laminate, and between 20 Rpm to 60 rpm is preferred. The Ministry of Economic Affairs Intellectual Property Office staff consumption cooperative prints a polyolefin/modified polyamine blend according to the present invention for many organic liquids, such as aliphatic hydrocarbon compounds (eg, gasoline, G Alkane), aromatic hydrocarbon compounds (such as toluene, xylene), halogenated hydrocarbon compounds (such as trichloroethane, o-dichlorobenzene) and paint thinners, etc., have excellent osmotic barrier properties, and also for the above organic liquids. The vapor has good barrier properties. The invention is further illustrated by the following non-limiting examples. Page 8 of 13 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1288767 at B7 V BRIEF DESCRIPTION OF THE INVENTION (9) Example Materials and Sample Preparation Different modified polyamines were prepared by blending with polyamines using different compatibilizer precursors. The compatibilizer used in the examples was zinc. - Neutralized ethylene/acrylic acid copolymer (Taiwan Chemical Fiber Co., Ltd.) The polyamine used is Nylon 6, also available from Taiwan Chemical Fiber Co., Ltd. under the trade name Sunylon 6N. Polyethylene used in the examples (HDPE Taiso) x 9003) and antioxidants (Irganox B225) were obtained from Formosa Plastics Co. and Ciba_Beigy, respectively. Prior to melt blending, PA and CP were dried at 80 ° C for 16 hours and at 60 ° C for 8 hours. About 1500 ppm of antioxidant and dry PA/CP component were dry blended in a weight ratio of 85:15, and then fed into an Ekegai PCM 45 co-rotating twin-screw extruder to make MPA resin. The extruder was placed in the feed zone. The 220 ° C is operated at a screw speed of 100 rpm toward the extrusion die at 240 ° C. The CP modified polyamine of the twin screw extruder is quenched in cold water at about 15 ° C and Cut into nine forms. The various modified polyamido nine particles were dried at 80 ° C for 16 hours and then dry blended with PE at a weight ratio of 10:90. The mixed PE/MPA and PE/PA blends were then blow molded in a Jonh Huah TPH-550 extrusion blow molding machine at an extrusion temperature of 230 ° C and a screw temperature of 400 rpm. The ruthenium/MPA blend was extruded using a conventional polyethylene screw prior to blow molding. The blow molded bottle weighs about 100 grams and has a wall thickness of about 750 milliliters and a capacity of about 2 millimeters. For comparison purposes, also the basic PE resin used the same screw and blow molding machine, but operated at a backlog temperature of 190 ° C and a screw speed of 400 rpm. The above-made bottles, such as blown into PE, PE/PA and PE/MPA, are annealed at different temperatures for different periods of time. The annealing temperatures used were 60, 70, 80, 90, 100 and 120 °C, respectively. The bottles were annealed for 1, 2, 4, 8, 16, 24 and 36 hours, respectively, at each annealing temperature. Table 1 summarizes the heat treatment conditions used and the sample numbers for PE, PE/PA and PE/MPA bottles. Page 9 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back and fill out this page) Order Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed 1288767 At B7 V. INSTRUCTIONS (10) The penetrant test evaluates the weight loss of the gasoline contained in the measuring bottle, such as blow molding into bottles and annealed bottles. PE, PE/PA and PE/MPA bottles are loaded with 380 grams of gasoline at the beginning. The weight loss of the gasoline was determined after the bottle was placed at 40 ° C for 14 days. On the other hand, the osmotic barrier properties of PA and MPA resins were also determined based on hot press sheets. The PA and MPA dry pellets were hot pressed into a sheet of about 2 mm thick and cut into discs of 14 cm diameter. Round PA and MPA sheets were capped on top of a test flask containing 250 passengers of gasoline. Then, the flask was placed at 40 ° C for 14 days' to measure the osmotic barrier properties of the wafer. The gasoline permeability of each bottle or hot plate is estimated based on the average permeability of at least three bottles or hot plate samples, respectively. Gasoline fuel composition before and after the permeation test The composition of the unleaded gasoline fuel was determined before and after the bottle penetration test using a China 8900 gas chromatograph (GC) equipped with a hydrogen flame free detector. The Restek Alumina Plot capillary column was used to separate the methanol/gasoline fuel. The capillary has an inner diameter of about 0.53 mm and a length of 30 meters. The gasoline fuel was injected into the GC at 230 ° C before and after the penetration test to determine the composition. Helium at 20 cm 3 /min was used as a carrier gas at 220 °C. In order to improve the separation efficiency, the capillary was raised from 30 ° C to 210 t at a heating rate of 4 ° C / min. The detector temperature is 230 °C. The main components contained in unleaded gasoline are non-polar linear, cyclic and aromatic hydrocarbons (about 5 to 10 carbons) and certain polar liquids such as acetone, ethanol, and other additives. For comparison and convenience, select hydrocarbon components (ie, n-pentane, xylene, and decahydro) and polar components (ie, acetone and ethanol) with 5 to 10 carbon backbones in gasoline fuel and determine by GC. The residual weight % represents the residual gasoline fuel composition after the penetration test. The residual weight % of each solvent was determined by the ratio of the area of each solvent after the penetration test to the area ratio of each solvent peak before the penetration test. Thermal Properties Page 10 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back and fill out this page) Printed by the Intellectual Property Office of the Ministry of Economic Affairs 1288767 at B7 V. INSTRUCTIONS (fl) (Please read the note on the back and fill out this page). For PE, PE, PA and PE/MPA bottles, PE, PA, CP and MPA have thermal properties. The Pont 2010 differential scanning calorimeter (DSC) was measured separately. All scans were carried out at a heating rate of 10 ° C/min under a nitrogen flow rate of 25 ml/min. The instrument was calibrated with pure indium. A sample weighing approximately 15 mg was placed in a standard aluminum sample pan. The baseline from 30 ° C to 160 ° C and the complete heat of fusion of 293 Joules / gram of PE were used to calculate the crystallinity of pE and CP. The crystallinity of PA or MPA contained in PE/CP/PA and PE/MPA was estimated using a baseline of 170 to 250 t and a total melting heat of 190 Joules/g. The baselines used in the experiments were adjusted to have a maximum fluctuation of less than 〇.〇4 mw 03⁄4 within the target temperature range. When using these baselines, the maximum variation in heat of fusion is typically around ±3 J/g, which results in a 1% error in estimating crystallinity. For example, the shape of blown bottles and annealed bottles. To observe the individual deformation configurations of MpA and PA resins contained in blown and annealed ΡΕ/PA and PE/MPA bottles, first cut these bottles with a scalpel. After that, engraved with uranyl formate. The etched samples were then plated with gold and examined using a Joel TSM-5200 scanning electron microscopy (SEM). For comparison purposes, etched samples such as blow molded bottles and annealed bottles were also examined by SEM. Results The Ministry of Economic Affairs, Intellectual Property Bureau, Staff and Consumers Cooperatives printed PE, PA, CP and MPA hot-pressed sea PE, PE/PA and PE/MPA, such as the late plastic bottle, the gasoline leaking parts, Table II, listed PE, PA, Gasoline permeability of CP and MPA hot pressed tablets. Among the three matrix resins, namely PE, CP, and PA, the PA sheet exhibited the best resistance to gasoline penetration, while the CP sheet exhibited the worst resistance to gasoline leakage. Poly-polyamine (MPA) tablets showed a better resistance to gasoline leakage than PA tablets. The gasoline permeability of MPA is about 49 times and 7 times slower than that of PE and PA sheets (see Table II). Similar to the results obtained by hot pressing, PE, PE/PA and PE/MPA bottles, such as blown PE bottles, have the worst gasoline penetration. Page 11 of 13 This paper scale applies to China National Standard (CNS). A4 size (210X297 mm) 1288767 V. Description of invention (12) (Please read the note on the back and fill out this page). As shown in Table II, after incorporation of PA or MPA in PE during blow molding, gasoline penetration resistance can be greatly improved, and the barrier improvement order corresponds to the improved barrier sequence of the barrier resin in PE. . After adding 10% by weight of "People or PA" in PE, the gasoline permeability of blown PE/MPA or PE/PA bottles such as blown PE bottles is about 130 times or 15 times slower respectively. After annealing PE, The gasoline leakage of PE/PA and PE/MPA bottles is quite surprising. After annealing the PE bottles at 60 to 120 °C for different time, the gasoline penetration rate has increased significantly. (See Figure 1.) In fact, their gasoline permeability increases consistently with annealing temperature and time. For example, 'PE bottles that are annealed at 120 °C for 32 hours have gasoline penetration rates such as blown PE bottles. Approximately 30% faster. Similarly, when PE/PA bottles are annealed at 90 ° C or higher, the gasoline permeation rate also increases significantly with annealing temperature and time (see Figure 2). However, PE/PA bottles are in When the temperature is annealed at 60 ° C for various times, the permeation rate is slightly reduced. After the bismuth/MPA bottle is annealed at 120 ° C for 32 hours, the gasoline permeation rate such as blown PE / MPA bottle is reduced by about 32%, which is equivalent to The blown PE bottle and the corresponding annealed PE bottle are about 190 times and 240 times slower respectively. For example, blow molding and bonfire PE, PE/PA and PE/MPA bottles Figure 4 shows a typical photomicrograph of the ruptured surface of PE, PE/PA and PE/MPA bottles. It can be seen that many well-defined MPA layers are in the PE matrix. For example, the wall thickness of the blown PE/MPA bottle is distributed (see Figure 4c). A slightly broken but less clear PA layer can be seen on the ruptured surface of a blown PE/PA bottle (see Figure 4b). It is inferred that the improvement level of PE/MPA and PE/{A bottle is obviously determined by the barrier properties of the matrix barrier resin. Furthermore, the segmentation of the clear and elongated MPA layer can extend the barrier period of the permeation molecule and improve the PE/MPA. The gasoline penetration resistance of the bottle. Conversely, it can be interesting to find that on the annealed pE 'ΡΕ/PA and PE/MPA bottles, no fracture surface morphology was observed relative to those such as blow molded bottles. Obviously page 12 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210Χ297 mm) 1288767 at B7 V. Invention description (13) Change (see Figures 4d to 4f). It is speculated that the annealed PE, PE/PA and PE/MPA bottles have significant changes in gasoline penetration resistance. May not be a change in morphology from annealing. PE, PE/PA and PE/MPA bottles are hot parts. Figures 5a to 5c show in PE, PE/PA and PE/MPA bottles such as blown and annealed. The crystallinity of the contained PE is 値(Wc). At the indicated temperature, the crystallinity of the PE contained in the annealed bottle is higher than that of the blown bottle, and increases significantly with the annealing time. At the fixed annealing time, the Wc値 of the PE contained in the PE/PA and PE/MPA bottles after annealing PE will increase significantly with the increase of annealing temperature. As shown in Figures 5a to 5c, the Wc of the PE contained in the retort was increased by about 6 and 5% after annealing at 120 ° C for 32 hours, respectively. Gasoline fuel composition before and after the sputum test. Figures 6 to 8 show typical compositions of gasoline fuels such as blown bottles and annealed bottles before and after the penetration test. At 40 ° C, 14 days after the gasoline fuel contains hydrocarbon components with 5 to 10 main chain carbon atoms (such as n-pentane, toluene, dimethyl and decahydro), a significant amount will pass through, for example, a blow molded bottle. Polar components such as acetone and ethanol remain almost unchanged and have no penetration (see Figure 6). Conversely, after the barrier resin is incorporated into the PE matrix, the relatively non-polar hydrocarbon components contained in the gasoline fuel are significantly blocked during the penetration test without penetration, such as blown PE/MPA bottles such as blown PE/PA. The penetration of hydrocarbon components is more successfully blocked (see Figures 7 and 8). However, the amount of polar components (such as acetone and ethanol) that pass through, for example, blown PE/PA bottles and PE/MPA bottles is very small and is about to pass through, for example, blown PE bottles. It is quite surprising that the amount of penetration of both the non-polar hydrocarbon component and the polar component obtained by annealing the PE bottle is higher than that of a blown PE bottle; and it increases uniformly with annealing temperature and time (Fig. 6). As shown in Fig. 7, there is a similar tendency for PE/PA bottles which are annealed at 90 ° C or higher for different times. Conversely, after any annealing treatment of the PE/MPA bottle, the amount of penetration of both the relatively non-polar hydrocarbon component and the polar component decreases consistently with the annealing temperature and time (see Figure 8). Page 13 of 13 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill in again)
訂 經濟部智慧財產局員工消費合作社印製Printed by the Intellectual Property Office of the Ministry of Economic Affairs