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- TW316274B TW316274B TW082109789A TW82109789A TW316274B TW 316274 B TW316274 B TW 316274B TW 082109789 A TW082109789 A TW 082109789A TW 82109789 A TW82109789 A TW 82109789A TW 316274 B TW316274 B TW 316274B
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Description
6274 A6 B6 經濟部中央揉準局貝工消费合作社印製 五、發明説明( ) 發明之领域 本發明爲有關以最廣用聚螗之聚G烯、使激粉與聚已 烯鍵結之如馬來酐、甲基丙烯酑或馬來醢亞胺等偶合刑及 如丙嫌睃及/或甲基丙烯等睃觸媒兼爲相溶則及觸媒,使 激粉化學鍵結於聚G烯蛑之生物可分稃聚L烯組成物及其 製法。 先前技術 合成塱骖克服了天然材料之問题及限制,償廉、質輕 且物理性赏優。開發種種聚合物,尤其塑膠建立塑膠文明 ,此爲現代科學特做之一。但世界各國製造預備多樣對策 ,蓋許多塑膠製品引起之污杂問題全球性曰趨嚴重,在轉 國從無用之塑膠廢物5丨起之污杂問題之解決成爲重要事情 〇 再循環,萸化及掩埋,曾爲主要解決這些包括塑膠之 種種固體廢物所引起之環境污染之問題,但掩埋及再猜環 均不能完全解決環境污染之問題。 故開發本身能降解之塑膠之硏究近年日趄重要。可分 解塑联·在技術上可分爲光分解性,生物分解性及生物光分 解性者,配合光及生物分解性技術ο 雖有多種生物分解性塱膠,如·羥基丁歧错 )等產生撖生物之聚合物,用產生生化橄生物之聚合物, 或具有如殼質或激粉等天然聚合物之聚合物,茲説明有關 {請先閲讀背面之注意事項再填窝本頁} .裝 -訂. i. 本紙張尺度遴用中國國家樓準(CNS)肀4规格(210x297公釐> A6
五、發明説明( ) 經濟部中央櫺準局貝工消费合作社印製 具有漱粉之聚合物之本技術之問題及改良。 G· J· L· Griffin之美國專利4 o^,388揭示以矽垸 «合刑處理澱粉表面之生物分解性薄膜之改良製法,但只 精增加基質樹脂及㈣問之物理作用強度,故難解決加入 澂粉所致之薄腺物理性質之下際。 USDA之F. H. Otey等之美國專利 揭示於G烯-丙烯系共聚物加α _澱粉來製造生物分解性薄 胰,但因ϋ烯·丙烯系共聚物償格高且製成之薄膜之物理 性質會降鮮,故難以市售0 韓國Seonil葡萄糖公司之韓國專利9〇_6336及91_8553 揭示増加基質樹腈與澱粉之間之物理強度之方法,係藉増 加澱粉之珑水性或増加基質樹脂之親水性來増加基質樹腊 與澱粉之相容性。 在本發明,簡化製法來降低生產成本,同時克服添加 濺粉只増加基質樹腊與激粉間物理強度帶來峰低物理性質 之不良影響。 本發明之目的爲提供與濺粉化學鍵結之生物分解性聚 已烯組成物,另一目的爲提供此生物分解性聚〇烯組成物 之製法。 發明之要旨 本發明組成物包含1〇〇重责份基質樹腈,5-400重贵份 生物分解性添加材料,0.01-10重量份偶合則,0.01-10重 量份歧觸媒共單體,0.01-1.0重量份自由根啓始刑, -4 - (請先聞讀背面之注意事項再填窝本買)
本紙張尺度迷用中國國家榣準(CNS)甲4规格(210x297公釐) 經濟郏中央搮準局員工消费合作社印製 316274 A6 _ B6 __--------- 五、發明説明() 0.01-10重量份自氣化剞及0·01_1〇重量份増塑剤,及任意 0.01-10重童份共單«。 «面之簡單説明 圖1爲依本發明之例1之生物分解性薄旗之IR。 固2爲依本發明之例1之生物分解性薄膜之一節之掃 描電子顯橄鏡(X 12〇0)電子顒微照片。 迤宜態樣 基質樹脂爲低密度聚已烽(LDPE),線性低密度聚已嫌 (LLDPE)或高密度聚己煉(HDPE〉,生物分解性添加材料乃 選自漱粉,睃處理湫粉,睹化濺粉、醚化澱粉、陽離子澱 粉及其混合物,如玉米澱粉、湫粉L睃能及激粉磷酸商。 使湫粉與基質樹脂化學鍵結之偶合則爲馬來酑,甲基丙珠 酑或馬來鳐亞胺,同時兼當觸媒及相容刑之睃觸媒共卑《 爲丙烯睃,及/或甲基丙烯睃。而自由根啓始刑爲遇氣化 辛鑌基、遇氣化二第三丁基、偶氮雙異丁猜、氩過氧化第 三丁基過化氪、遇氧化二異丙笨基 、Lupersol 101 (Pennwalt公司)或Perkadox(Akzo公司)〇自氣化則爲一種 以上遴自油睃錳、硬腈睃鏟、油睃亞鐵(π )、硬腌睃亞鐵 (Π)及其混合物,増塑則爲如油雄胺、vit〇n或Erucamide 袂單體爲一種以上遴自今烯猜,笨L雉及丙烯睃LS旨。 達成本發明之另一目的之化學鍵結激粉之生物分鮮性 眾G烯組成物之製法包括诋合一定量基質樹腈,生物分解 -5 - 中國國家樣準(CNS)甲4规将^10X 297公藿了 ~ <請先閲讀背面之注意事項再填寫本頁) ( -訂 A6
五、發明説明( 經濟部中央櫺準局貝工消费合作社印製 性添加付料,偶合刑,睃觸媒共單體自氣化則、増塱則 、,及自由根啓始劑,而將此混合物予以反應性擠壓。 採用雙螺旋擠壓機之反應性擠壓法來簡化褽法以吟低 生產成本,並減少混合澱粉後之物理性赏下峰。即將聚匕 蛾、自由根啓始則、偶合则(如馬來酑、甲基丙烯酑或馬 來雄亞胺),玉米澱粉或溉粉衍生物及睃觸媒共單體同時 引入,而在15〇_22〇。〇以5〇-3〇〇 rpm之螺旋速度予以反應 将恩使激粉晻化,其當中發生偶合則接枝於聚己烯鍵。 用如馬來酑,甲基丙烯矸或馬來鑌亞胺等偶合則 〇·〇1-10重量份,如丙烯睃或甲基丙烯睃等睃觭媒共單髏 0·01-10重量*,自由根啓始刻0.01-1.0重量份,及生物分 解性添加衬料5_8〇重量%。 生物分解性添加材料爲如玉米激粉,修飾澱粉如澱扮 已歧睹,激粉磷睃碏、氧化激粉、陽離子湫粉等,湫粉吏 乾燥至水分低於Μ。 欲製造生物分解性樹脂粒吁將一定量基質樹腊 珠〉,生物分解性添加材料(湫粉或濺粉衍生物)、偶合刑( 馬來野、甲基丙烯酑或馬來醢亞胺)、自氧化則(油睃、油 歧金屬里)、増塑刻(油醢胺)、睃觸媒共單體(丙烯酸或甲 基丙烯睃〉、及自由根啓始剂混合,而在塑骖混合機熔融 、或將各成分放在配合機而予以熔融後、用造粒機擠壓、 造粒。捋此粒用熱壓機及製膜擠壓機壓製成膜或吹成膜來 製造生物分解性薄胰。此壓製膜或吹製胰也可製自於此粒 中加低密度聚ϋ烯、缘性低密度聚G烯或高密度聚G烯後 -6 - 本紙張尺度遑用中困國家樣準(CNS)甲4規格(210X297公梦) f碕先聞讀背面之注意事^再#窝本買·- -裝 -訂 線 A6
五、發明説明( ) 經濟部中央棵準局貝Η消费合作社印製 ,予以乾式混合及擠壓。此生物分解性樹膾粒也可棋製成 激G烯瓶。 依下述例1 一 1 3製造之生物分解性薄膿之如抆拉強 度及伸長率等機械性質乃以UTM(萬用測試機)測定,物理 性質則由ASTM之標準儀器測定。表面及斯面也由掃插電子 顯撖鏡檢査。生物分解性乃由將竣基之吸收峰在i中生 物乃解性膜之IR顯示在l,7Q〇_lg〇〇 cm 1 ,固2中择描電子 顯撖鏡之生物分解性膜之斯面圖,澂粉粒斯切現象,及激 粉粒與基質樹脂間之境界不明之事實,確趄聚已烯鏈笋激 粉化學鍵結。 生物分解性乃由將薄胰埋在土壤後用;^·^ G 21-70方 法檢査變形及物理性質之經時變化。 下面舉例説明本發明,但不限於此〇 例 1 以馬來酑爲偶合則丙烯睃爲睃觸媒共單體,及笨已蛛 爲改善保合刑之反應效能之共單體使濺粉與眾G烽鍵化學 鏈結來製造生物分解性薄膜。 將37.5克馬來酑、I2·5克丙烯睃、37·5克笨已烯、5克 邁氧化苄鵷基,5〇克油醯胺、50克油睃錳分別溶在SO ml 丙銅。將5公斤低密度聚匕嫌(MI-3,密度0.919〉投入 Henschel混合器後,以上述溶液被復。 將此被復聚已烯粒與按上述低密度聚已烯之6〇重量* 之玉米湫粉在維持ΠΟΙΟ之挤赓機以MO rpm螺旋速度反應 本紙張尺度適用中国國家揉準(CNS)甲4规格(210x297公釐f {請先閲讀背面之注意事項再填窝本頁) .裝 訂 i A6 B6 經濟部中央樣準局貝工消费合作社印製 五、發明説明( ) 择壓製成生物分解性主料粒,其中濺粉與苽乙蛛鏈化學鍵結。 將1.7公斤生物分解性主料及8.3公斤低密度聚G烯 (MI-3,密度o.wg〉予以虼式混合而通經製膜機來製成吹 踅膜。 由上述生物分解性主料與低密度聚G烯(MI-3,密度 〇·9ΐ9)之乾式混合來製成之生物分解性胰之物理性赏及生 物分解性如表1〇 生物分解性乃依ASTM G 21-7〇法測定。經一定等待期 間(至少21)日後,生長速度乃依被復真菌菌裳之聚合物表 面之部分來分等: 0% : 0 少於1(H : 1 10-30% : 2 30-60% : 3 60-100% : A 例2 — 6 仿例1,惟用依聚已烯之下列重量%之澂粉,依例1 之方法測定結果,如表1。 本紙張尺度適用中國國家樣準(CNS)甲4規格(210x297公釐) t請先閲讀背面之注意事項再填窝本頁) .訂. C0 4- 7 6 B6 五、發明説明( 表 例 澱粉含量 (重量*) 抗拉強度 ,2、 (kg/cm ) 伸長牟 (%> 生物分解性 比較例1 * 0 330 600 0 1 10 315 560 3 2 20 295 530 4 3 30 215 450 4 4 40 153 270 4 5 50 124 140 4 6 60 87 80 4 *比較例1:仿例1評價,但未加激粉0 (請先閲讀背面之注意事項再填窝本頁) Λ 訂 例 7 以甲基丙烯酑爲偶合刻及以甲基丙烯睃爲睃觸媒共單 體使聚已烯鏈與激粉化學鍵結來製造生物分解性薄膜0 捋5〇克甲基丙嫌酑、25克甲基丙烯睃、5〇克油睃廷。 50克油鑲胺及5克遏氧化苄錶基各溶在5〇 «^丙鲖。將5公 斤線性低密度聚C*烯(MI-1,密度0.919)投入Henschel泯合 器丙以前述溶液被復。 捋此被復聚已雉粒與依上述線狀低密度聚乙烯之60重 陽雜子激粉在維持175<C之擠蜃機以200 rPm螺旋速度予以 -9 - 本纸張尺度逍用中國國家樣準(CNS)甲4规格(210X297公釐) i 經濟部中央標準局貝工消费合作社印製 A6 B6 五、發明説明( ) 反應擠壓來製備澱粉與聚已烯化學鍵結之生物分解性主料 粒。 捋k7公斤生物分解·性主料粒及8.3公斤緣性低密度聚 G蝻(ΜΙ-0.28,密度〇.945〉予以粑式混合而通絰褽胰機製 成吹髮膜。 由上述生物分解性主料及線性低密度聚已嫌(ΜΙ-0.28 ,密度〇·945)乾式混合製造之生物分解性胰之物理性質及 生物分解性如下表2 〇 例 8 - 1 2 仿例7,惟用依聚已烯之如下重量%濺粉,仿例7測 定結果如下表2。 <請先W讀背面之注意事項再填窵本筲1 f 装 經濟部中央橒準局貝工消費合作社印製
ο X 準 搮 家 國 國 中 用 適 度 尺 張 紙 本 格 規 4 甲
* 公 7 9 2 X A6 B6 五、發明説明( ) 表 2 例 澱粉含量 (重量《) 扰拉強度 (kg/cm^) 伸長率 (%) ------—_ 生物分解性 比较例2 * 0 640 600 0 7 10 635 580 3 8 20 614 555 4 9 30 516 454 4 10 40 * 321 335 4 11 50 189 215 4 12 60 106 123 4 (請先閱讀背面之注意本項再填窝本頁} *比较例2 :仿例7評償,但未加澱粉。 含2〇重量%澱粉之生物分解性膜與基材樹腊相较,由 Instr〇n^定之物理性質無差異。本生物分解性膜之製法 發現爲依加入澱粉以滅少物理性質下吟之最佳方式,此可 由生物分解性化學鍵結使基質樹腊與澱粉粒之界限不清 來増強,而澱粉粒斯面切開之現象顒示於用掃插電子顯橄 鏡之旗斯面之觀察。濺粉10重量*以上時生物分解性最佳〇 -11 - 本紙張尺度遑用中Η國家樣苹(CNS)甲4規格(210X297公釐) -訂 經濟部中央標準局負工消费合作社印製
Claims (1)
- 麵 BBS 麵 BBS Α8 Β8 C8 D8輕濟部中央搮準局貝工消費合作社印氧 公告 六、申請專利範困 1·—種與澱粉化學鍵結之生物分解性聚乙烯組成物, 包含100重置份聚乙烯,5_400重量份的一種選自澱粉、 酸處理澱粉、酯化澱粉、醚化澱粉、陽離子澱粉及其混合 物之生物分解性添加材料,o.oi-io重量份的一種選自馬 來酐,甲基丙烯酐及馬來醯亞胺的偶合劑,0.01-10重量份 的一酸觸媒共單體,0.01-1.0重量份的一自由根啓始劑, 0-01-10重量份的一自氧化劑及0.01-10重量份的一增塑 劑。 2·如申請專利範圍第1項之組成物,其中更含0.01-10 重量份的一共單體。 3. 如申請專利範圍第2項之組成物,其中該共單體係 —種或多種選自丙烯腈,苯乙烯及丙烯酸乙酯所組成族群 考。 4. 如申請專利範圍第〗項之組成物,其中該聚乙烯係 選自低密度聚乙烯,線性低密度聚乙烯或髙密度聚乙烯所 組成族群》 5. 如申請專利範圍第〗項之組成物,其中該自由·根啓 始劑爲過氧化苄醯基、過氧化二第三丁基、偶氮雙異丁腈、 氫過氧化第三丁基、過氧化二異丙苯基、2,5-二甲基-2,5-二(t-丁基過氧)甲烷或ι,3-雙-(t,丁基過氧異丙基苯)。 12 ΜΛ張尺度逋用中國·家鏢车(CNS ) A4規格(210X297厶釐) (請先閱讀背面之注$項再壤寫本頁)S16S74 iS η! (1997年7月修正) 六、申請專利範国 6·如申請專利範園第1項之組成物,其中該自氧化劑 乃一種或多種選自油酸錳、硬脂酸錳、油酸亞鐵(II)、硬脂 酸亞鐵(Π)及其混合物所組成族群者。 V. 7.如ΐ請專利範圍第1項之組成物,其中該增塑劑爲 一種選自油醯胺、聚(六氟伸丙基)-共-聚(偏氟乙烯)及順-Π-廿二醯胺所組成族群者。 8·如申請專利範圔第1項之組合物,其中該酸觸媒共 單體爲同時兼當觸媒及相容劑且選自丙烯酸及/或甲基丙 烯酸所組成族群者。 9. 一種與澱粉化學鍵結之生物分解性聚乙烯物品,係 將如申請專利範圍第1項之聚乙烯組成物混合,並予以反 應擠屋並造粒爲主料粒者。 I . 輕濟部中央樣率局—工消費合作杜印衷 (請先W讀背面之注項再填寫本頁} 10. 如申請專利範圍第10項之生物分解性聚乙烯物 品,其中於此主料粒進一步加入低密度聚乙烯,線性低密 度聚乙烯或高密度聚乙烯,並予以乾式混合及擠壓。 11. 如申請專利範圍第10項之生物分解性聚乙烯物 品,其中該生物分解性聚乙烯物品爲薄膜或瓶。 ' 12.—種與激粉化學鍵結之生物分解性聚乙烯組成物 13 私紙張尺度逋用中《國家揉率(〇奶)八4规格(210><297公釐) I, Α8 Β8 C8 08 (1997年7月修正) 、申請專利範国 之製法,包含將100重置份聚乙烯,5-400重量份的一種 選自澱粉、酸處理澱粉、酯化澱粉、醚化澱粉、陽離子澱 粉及其混合物之生物分解性添加材料,0.01-10重量份的 一種選自馬來酐,甲基丙烯酐及馬來醯亞胺的偶合劑, 0.01-10重量份的一酸觸媒共單髅,0.01-1.0重量份的一自 由根啓始劑,0.01-10重量份的一自氧化劑及0.01-10重量 份的一>塑劑混合,並予.以反應擠壓。 13. 如申請專利範圔第12項之製法,其包含進一步混 合0.01-10重量份的一種或多種選自丙烯腈、苯乙烯及丙 烯酸乙酯所組成族群的共單體。 14. 如申請專利範圍第12項之製法,其中進一步包含 在該混合物被反應擠壓前將該生物分解性添加材料乾燥至 水分3%以下。 15. 如申請專利範圔第12項之製法,其中該混合物於 150-220°C以50-300rpm螺桿速度予以反應擠壓。 經濟部中央棣率扃貞工消费合作社印*. (請先《讀背面之注$項再填寫本頁)表紙張尺度逋用中國《家輮準(CNS ) A4规格(210X297公簸)
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US4337181A (en) * | 1980-01-17 | 1982-06-29 | The United States Of America As Represented By The Secretary Of Agriculture | Biodegradable starch-based blown films |
US4375535A (en) * | 1980-04-28 | 1983-03-01 | Standard Brands Incorporated | Stable liquid, amylopectin starch graft copolymer compositions |
BR8405354A (pt) * | 1983-02-14 | 1985-02-12 | Amf Inc | Suportes polissacaridicos modificados |
CH671961A5 (zh) * | 1987-02-27 | 1989-10-13 | Amrotex Ag | |
US5162392A (en) * | 1989-05-19 | 1992-11-10 | Agri-Tech Industries, Inc. | Injection moldable biodegradable starch polymer composite |
US5026745A (en) * | 1989-06-12 | 1991-06-25 | Aristech Chemical Corporation | Biodeteriable plastics and blends |
IT1240503B (it) * | 1990-07-25 | 1993-12-17 | Butterfly Srl | Miscela polimerica amidacea particolarmente per la produzione di film e simili e procedimento per la sua produzione. |
BE1005694A3 (fr) * | 1992-02-07 | 1993-12-21 | Solvay | Composition a base d'amidon. |
US5321064A (en) * | 1992-05-12 | 1994-06-14 | Regents Of The University Of Minnesota | Compositions of biodegradable natural and synthetic polymers |
-
1993
- 1993-07-23 KR KR1019930014073A patent/KR960012445B1/ko not_active IP Right Cessation
- 1993-11-20 TW TW082109789A patent/TW316274B/zh active
- 1993-11-22 CA CA002109657A patent/CA2109657A1/en not_active Abandoned
- 1993-11-23 US US08/156,371 patent/US5461094A/en not_active Expired - Lifetime
- 1993-11-23 GB GB9324058A patent/GB2272699B/en not_active Expired - Fee Related
- 1993-11-24 IT IT93MI002486A patent/IT1265219B1/it active IP Right Grant
- 1993-11-24 JP JP5317408A patent/JPH06316655A/ja active Pending
- 1993-11-24 CN CN93121455A patent/CN1037352C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
IT1265219B1 (it) | 1996-10-31 |
GB2272699B (en) | 1997-04-02 |
US5461094A (en) | 1995-10-24 |
GB2272699A (en) | 1994-05-25 |
ITMI932486A1 (it) | 1995-05-24 |
CA2109657A1 (en) | 1994-05-25 |
KR960012445B1 (ko) | 1996-09-20 |
CN1037352C (zh) | 1998-02-11 |
CN1092083A (zh) | 1994-09-14 |
KR940011556A (ko) | 1994-06-21 |
ITMI932486A0 (it) | 1993-11-24 |
GB9324058D0 (en) | 1994-01-12 |
JPH06316655A (ja) | 1994-11-15 |
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