TW201134663A - Method for fire protection and modification of properties of expanded polyesters - Google Patents

Method for fire protection and modification of properties of expanded polyesters Download PDF

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Publication number
TW201134663A
TW201134663A TW100101296A TW100101296A TW201134663A TW 201134663 A TW201134663 A TW 201134663A TW 100101296 A TW100101296 A TW 100101296A TW 100101296 A TW100101296 A TW 100101296A TW 201134663 A TW201134663 A TW 201134663A
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TW
Taiwan
Prior art keywords
items
layer
insulation
outer layer
polyester
Prior art date
Application number
TW100101296A
Other languages
English (en)
Inventor
Juergen Weidinger
Mika Meller
Jie Li
Original Assignee
Armacell Enterprise Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Armacell Enterprise Gmbh filed Critical Armacell Enterprise Gmbh
Publication of TW201134663A publication Critical patent/TW201134663A/zh

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    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/20—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length
    • B29C44/22—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of indefinite length consisting of at least two parts of chemically or physically different materials, e.g. having different densities
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Description

201134663 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種改變膨脹聚酯產品之物理及化學对 抗性質（諸如阻燃性及耐水解性）之易於應用且通用之方 法’其係藉由該等發泡體及海綿之表面層之熔融改變，該 等產品之製法及該等產品之用途。 【先前技術】
膨脹聚酯聚合物（即聚酯發泡體或海綿）於與例如溫度梯 度之隔絕、噪聲屏蔽、振動阻尼、輕量化結構等相關之眾 多應用極其重要。然而，由於其等之因聚合物主鏈導致之 有機性質’及由於對安定性具有額外負面效應之雜原子 (諸如氧）為聚合物之一部份之事實，其等基本上極敏感於 與例如水解或由氧起始之燃燒有關之分解。使情境更糟的 係以下事實：泡孔聚酯當然不如塊狀材料牢固，表面積更 大，因此，侵蝕性物質更易接近，且在點火或鹼或酸侵蝕 時，泡孔（cell)内獲有空氣/濕度。因此，聚酯基本上易燃 且一經點火則趨於持續燃燒，且其等一旦發生鍵裂則將因 水解而持續分解。已作出不同努力以改良聚合物化合物本 身之女疋性，諸如，將齒化及非函化阻燃劑、不燃性填充 劑等混合於化合物中。然而，由於聚酯發泡體之製程為反 應性發泡製程（參見’例如Ep 0866089、US 5288764、JP 5117501 、 JP 62004729 、 WO 2001051549 ; JP 8151470提 及利用再循環材料來發泡），外來物質可嚴重影響聚合物 之膨脹或發泡以及針對預期應用之其他最終性質。另，在 152873.doc 201134663 論及聚對苯二曱酸乙二酯時，該等外來物質將需耐受可能 為例如約300°C之處理條件。大多數標準阻燃劑無法幸存 於該等溫度並於處理期間發生分解。諸如無機填充劑、纖 維等之其他更為安定的物質會負面影響聚合物之鏈長或泡 孔結構或無法簡單地複合成一定程度上可實現有效作用之 基質。爲了克服該等問題’關於其中未給出膨脹聚酯之處 理所呈現之限制之塗覆及層壓技術領域，已作了 一些工 作。KR 1 0070 1 274揭示一種具有鱗作為阻燃劑之聚對笨一 曱酸乙一酯（PET)地毯層。在jp 2008201079、jp 10119219 、 JP 8068164 、 JP 1261588 、 GB 2344834 、 GB1 161045、GB 882296 及 US 6066580 中，聚酯、聚醋纖 維或聚酯/玻璃纖維叠層係用以保護由其他聚合物組成之 更具可燃性之發泡體核；GB 2222185主張將該系統作爲一 種「炼融」防火措施；GB 2122232討論利用鹵素/錄化合 物處理發泡體或其保護層《特定言之jp 2006077551係處理 作為内部防火劑之聚酯纖維，然而，覆有金屬箔且使用黏 結劑以將該等層黏結在一起。該金屬（主要為紹）箔法的確 為一種相當廣泛之方法，參見，例如JP 2215521、jp 4347252、JP 8199709、US 4459334、CH 650196 等。然 而’該等多層法存在一些失敗來源，諸如必要黏結劑所提 供之額外不確定性（可燃性、耐久性、相容性等）。DE 100117177提及PET發泡體窗檻，其中藉由熔融而封閉表面 以達到裝飾目的，然未提出其他措施或優點，於JP 6170999亦如此，其中，將聚酯（稱為PET)層共擠壓於聚酯 152873.doc 201134663 發泡體核上以提供可熱成型板。但是，並不徹底明瞭一些 前述方法之組合之可能性。然而，此點爲發展將可滿足目 則有關如下證明之需求之材料所需：例如，建築產業領域 内之與可燃性試驗相關之驗證變得越來越全球化，亦及更 精確且更具應用相關性而因此更具挑戰性（例如astme_84 「tunnel burn test」，UL 94 「h〇riz〇mal/vertical b_」， ΕΝ 13823「round Corner burn test」，FM「r〇〇m burn test」）。 【發明内容】 因此，本發明之一主要目標係提供一種膨脹聚酯材料及 易製造該膨脹聚酯材料而得到具阻燃性及耐水解之一种化 〇物的通用、可靠及易於應用之相關方法，吟未捨棄聚酉旨 (即聚對苯二甲酸亞烷酯）發泡體的任一有益性質，諸如經 濟性、低密度、高Tg、受控結晶度等。 令人驚訝地，發現可藉由塗層或層壓件將保護及功能層 置於恥脹聚酯上而得到未顯示上述缺點之此種材料，該塗 層或層壓件主要係由作為基質之各自聚酯聚合物本身組成 且虽集添加劑。此不僅有利於使層體黏結於泡孔基質，而 且明顯增大改變功能層之防火及耐化學及物理侵餘及其一 般性質之自由度，此點於下文詳述。藉由該方法於主要 發生物理或化學侵蝕且可得以控制並甚至最佳可停止之必 要處（即於表面上），有效富集化學物質（諸如阻燃劑及/或 防水解劑）。 所主張之材料包括為一種膨脹聚酯基化合物之化合物 152873.doc 201134663 (A) ’參見圖1。該膨脹聚酯可顯示具任意泡孔尺寸及分佈 之敞開式或封閉式泡孔結構（即，可為海綿或發泡體）。較 佳為聚對苯二甲酸亞烷酯聚合物發泡體，尤佳為基於聚對 苯二甲酸乙二雖(ΡΕΤ)之此等者。除了聚醋聚合物本身之 外，化合物（Α)可包括其他組分’諸如，但不完全為：填 充劑、其他聚合物（熱塑物、熱固&、τρΕ、彈性體）、纖 維、添加劑、色料、交聯劑、竞化或成炭劑、膨脹系統、 安定劑、阻燃劑等。 所主張之材料包括至少一外層(Β)，其係由塊狀因此未 膨脹之聚醋基質組成，該基質較佳係基於ρΕτ，由於經濟 及生態原目’亦由於消費後ΡΕΤ具有較低熔點以及較低溶 融黏度之利於本發明之事實’特佳為再循環ρΕτ。（β)之 PET之形態及性質將使其易與多種物質或添加劑（諸如阻燃 劑（C)及/或防水解化學品（D))複合（即混合）。可以「乾燥」 狀〜、進行該混合，意指於低溫下，例如在標準混合器中， 、得到僅，機械混合之化合物。在添加劑對溫度敏感時， ，具有利性，因將（B)施用於（A)(參見以下）時其等將僅 H所有其他情況τ ’可例如在複合擠壓 ，中’將添加劑複合至熔融態ΡΕΤ中以得到物理混合物或 :液。將層體（Β)溶融至⑷上以實現極佳結合。此可藉由 、夕種方法以在線或離線製程連續或不連續地實現，該等方 ^諸如’但不完全為：均可利用⑻之預製片狀㈣粉末 ::之共擠壓、共模製或多重模製 '層壓，或喷霧及燒結 …專片或粒化等。以如下製程為較佳：使⑻以粉末形 152873.doc 201134663 式至（A)上且隨後藉由施加溫度及低壓（諸如使用加熱板或 較佳使用移動加熱帶或加熱筒）’分別地熔融於（A)上或（A) 中。特佳為發泡體擠壓之後在線應用之較佳連續之此種加 速燒結製程。除了聚酯聚合物及提及之添加劑之外，化合 物（B)可包括額外成分，諸如，但不完全為：填充劑、其 他聚合物（熱塑物、熱固物、TPE、彈性體）、纖維、色 料、交聯劑、膨脹劑、安定劑等等，以提供材料經改變之 性能及/或額外之性能◊若（A)所提供之部份為平面，則可 將塗層（B)施加於該部份之至少一側上。 此外，所主張之材料中 添加劑⑹，其可選自諸如但不完全為以下之類別：含函 素物質、碟化合物、釋水化學品、自纽、成炭或膨腸物 質、及其混合⑼。由於其等於處理條件下之安定性及其等 與聚醋基質之相容性，及由於其等之成炭潛在性，較佳為 非i素化合物’特佳為磷化合物，諸如但不完全為： (聚）鱗自曰、紅鱗、（聚）碟酸自旨、（聚）膦酸g旨及（聚）亞膦酸 醋。添加劑（C)可以極高含量（視物質而定，高達> 50重量 %)複合至層（B)中，此在發泡體㈧中將不可行，其中，依 ^驗’該等化學品之最大劑量為約5%，且相對於經發泡 法本身保護之表面’此劑量將額外地減小。 所主張之材料中之化合物⑻可包括防止水解性鍵裂之 :加劑⑼’諸如，但不完全為：鹽、緩衝液 化劑或吸收劑、及其混合物。 ”，、轧淨 物質(諸如無機吸收劑及緩 於所給條件下安定之 則及緩衝系統），由於其等之安定性、 152873.doc 201134663 其等之寬性能範圍及與（B)之基質及（c)之相容性特佳為 基於(聚)亞磷酸、其酸酐類及其鹽類之磷系統。添加劑⑼ 可以極尚含量（視物質而定，高達>5〇重量％)複合於層（B) 中，此在發泡體（A)中將不可行。 此外，參見圖1，所主張之材料可包括額外之功能層 ⑻，該層係由例如金屬、纖維或塑料 復以擔任例如屏蔽層、強化層或裝飾層。以本爲身 性、或具膨脹性及/或成戾性或易燃燒或熔融而不影塑 (a)(b)阻燃系統的功能之層體為較佳。化合物 結齊K較佳具阻燃性）或自身點結至⑻。 藉由黏 此外’參見圖！ ’所主張之材料可包括預期應用所需之 任何其他元件（jp) 諸 旰諸如，但不完全為··由木材、 金屬或混凝土等製得之部件、用於建築目的之結構物等。 可藉由黏結劑（較佳具阻燃性）或自身點結至材料 之其他化合物^ ^ n 所主張之材料之—主要優點 多種物質封閉於外層内之"農度將 層内之事貫，諸如將使得該層難以點火 一，此會得龍添加料體 仔到之性質。 火".、/2: 者=Γ主張之材料之另一傑出優點，該優點為研發 者及有效製程可獨立地隼中 赞 等性能及製法之事膏：層或膨脹核、其 繫，而嘗試直接添加添加劑之膨脹材料並非如2間無聯 此點係有關於所主張之材料之另—優點，該優點為藉由 I52873.doc 201134663 核（A)及/或層（B)之關於各自 晶度等之可能獨立的改 度、添加劑之負裁量、結 於力學、阻尼、隔絕性 #適於所期性質情況(關 所主張之材料之另— 了 ^生 再循環材料之事實。 』為功能層之基質材料可為 所主張之材料之-極其傑出之優點為“ 泡體核在進行塗覆之前顯示開放式泡 全封閉且均勻。 人二丨皁寻，表面完 所主張之材料之另—傑出 何其他措施下，⑻將為下事貫：在不採取任 合物將作爲「-m )之優異點結性，及所得複 所主張之材料之另一優點為可在製程期間，藉 (A)表面之溫度及⑻之溫度及施加之厂堅力而輕易地影響外 層（B)滲入（A)之泡孔結構内之程度。 所主張之材料之另一優點為以下事實：由於（b)之複人 及施用製程，既無令(B)中之重要成分分離之風險亦不； 對核發泡體產生任何負面影響。 所主張之材料之另-優點為以下事實：無須將添加劑放 於最終部件（即發泡體）之主體積内，從而得到較「清潔 產品。 ί '」 此點得出所主張之材料之另一優點為再循環適用性，因 為純聚酯係在移除頂層之後獲得之事實。甚 ^ 土〗貝層再循 環物可再次用於類似之目的。 所主張之材料之一基本優點為以下事實：在其較佳之組 152873.doc -9· 201134663 合物中’其不含纖維、溴化物質及pvc，其等均進行調查 並進行環境及徤康問題之討論。 所主張之材料之另一優點為其阻燃1生幾乎與待防火之部 件之幾何結構無關。 ° 所主張之材料之—傑出優點為其可利用連續製程以經濟 方式製得’例如藉由上述之擠壓及共層壓。其顯示製法及 應用可m之通用性。其可以多層系統直接進行擠壓、 八擠壓、層壓、模製、共模製、乡重模製、焊接等，且因 此，其可以任意形狀施覆於汽車、運輸、航空、建築及結 構、傢具、機械工程、及其他許多產#之各種表面上，甚 至藉由材料製程之後之加熱成型或其他成型方法。額外層 甚至將改良熱成型性質以及其他加工性質（例如適印性、 固定性及安裝性等）。 所主張之材料之另一優點為其可藉由該產業已知的標準 方法加以轉變並顯示形狀及不需專用設備。 所主張之材料之另一優點為其適於隔熱及隔音/防振， 例如於建築產業中，因PET發泡體已知為一種極高強度的 材料，十为適合於需結構支樓之此類應用。文中層體（B) 可作為蒸氣障壁及防水面。 【實施方式】 實例 在以下實例及比較實例中，將具65 kg/m3密度之標準 PET 隔絕發泡體（ArmaStruct®，Armacell GmbH，Miinster，
Germany)切成25 mm厚及500 mm寬之樣品。保護層係藉由 152873.doc ⑤ 201134663 以下置於發泡體部分上：採用平模/刮刀系統使其等以粉 末母料形式均勻分佈於發泡體表面上，然後，使製得之部 件於600 mm寬及200 mm半徑之熱（280°C)鍍鉻筒下緩慢運 行，施加恒定低壓（相對發泡體厚度之壓縮因子< 0.5%)。 自初始PET(Sabic, Genk，Belgium)、内製造後之再循環 殘塊（Armacell)或於市場上購買之再循環薄片研磨成塗層 之 PET ° 用於塗覆之粉末的製法如下：使冰冷狀態之各添加劑及 PET粉末在攪拌混合器中進行混合或藉由使PET於混合擠 壓機中熔融且將該等添加劑添加於該熔體中，接著，藉由 再粒化所得母料。表1提供粉末母料及所用成分（阻燃劑）之 資料。 表1 :粉末母料之成分 母料 PET類型 FR添加劑及母料劑量 供應商 1 原始 40% Firebrake® 500 (删酸鹽） Borax Europe ltd., Guildford, UK 2 原始 40% Melapur® 200 (三聚氰胺） Ciba, Grenzach, Germany 3 原始 50%ExolitwOP 1200(磷） Clariant，Muttenz， Switzerland 4 原始 60% Saytex® 8010 (溴化） Albemarle, Louvain, Belgium 1A 再循環(Armacell) 40% Hrebrake® 500 (领酸鹽） Borax Europe ltd., Guildford, UK 2A 再循環(Armacell) 40% Mehpur® 200 (三聚氰胺） Ciba, Grenzach, Germany 3A 再循環(Armacell) 50% Exolit® OP 1200 (磷） Clariant，Muttenz， Switzerland 4A 再循環(Armacell) 60% Saytex® 8010(溴化） Albemarle, Louvain, Belgium 1R 再循環(自由市場） 40% Firebrake® 500(蝴酸鹽） Borax Europe ltd” Guildford, UK 2R 再循環(自由市場） 40% Melapur® 200(三聚氰胺） Ciba, Grenzach, Germany 3R 再循環(自由市場） 50% Exolit® OP 1200(磷） Clariant, Muttenz, Switzerland 4R 再循環(自由市場） 60% Saytex*1 8010(溴化） Albemarle, Louvain, Belgium 5R Γ再循環(自由市場） —· 一 30%三水合氧化鋁，20% Saytex* 8010 Albemarle; Bergheim, Germany 152873.doc -II - 201134663 依據ΕΝ 13823/EN 13501-1(單體燃燒試驗/圓角試驗）、 DIN 4102、及UL 94(水平/垂直燃燒），對所製得的複合物 之阻燃行爲進行部分檢查。表2顯示與具相同厚度之未經 處理之發泡體板（比較實例，由星號標記）比較之結果。無 星號之實例包括所主張之材料。 表2 :可燃性試驗結果（n.e.:未檢查） 母料 EN 13823/13501-1 DIN 4102 UL94·塗覆於 一面/兩面 評價 無* E 不合格 不合格 易燃 1 D 不合格 HB 可燃 2 CS3 d0 B1 V-2/V-1 阻燃 3 BS3dl B1 V-l/V-0 阻燃性更佳 4 CS3dl B2 V-2/V-1 阻燃 1A D 不合格 HB 阻燃 2A CS3 dO B1 V-2/V-2 阻燃 3A BS3dl B1 V-l/V-0 阻燃性更佳 4A CS3 dl B2 V-2/V-2 阻燃 1R n.e. 不合格 HB 可燃 2R n.e. n.e. V-2/V-1 阻燃 3R BS3dl B1 V-l/V-0 阻燃性更佳 4R n.e. n.e. HB/V-2 阻燃 5R BS3 dO B1 V-l/V-0 阻燃性更佳 【圖式簡單說明】 圖1顯示以膨脹聚酯為主的化合物。 【主要元件符號說明】 A 化合物 B 外層/塗層/化合物 E 功能層/化合物 F 元件/化合物 152873.doc -12-

Claims (1)

  1. 201134663 七、申請專利範圍： 1 ·種由作爲核之膨脹聚酯組成之材料，該核係覆有由包 含低至高濃度之功能性添加劑之未膨脹聚酯組成之至少 一外保護層。 如哨求項1之材料’其中該核係由聚對苯二甲酸亞烷酯 所組成。 3. 如。青求項1之材料，其中該外層係由聚對苯二甲酸亞烷 酯所組成。 4. 如吻求項1之材料，其中該核及該外層均係由聚對苯二 甲酸亞烷酯所組成。 汝月长項1至3中任一項之材料，#中該外層係添加有〇 $ 至60重量％之功能性化學品。 月长項1至4中任一項之材料，其中該外層係添加有阻 燃劑及/或抗水解劑。 7·如睛求項6之材料’纟中該阻燃劑及該抗水解劑係 爲主。 8. 如請求項1至4中任—焐 ^ , ^ t 項之材科，其中施加額外層以達到 保護、強化及裝飾之目的。 9. 一種以連續法製造如請求項 法。 1至8中任一項之材料之方 10. -種以連續兩步驟擠壓及層壓/塗覆法製造如請求 中任一項之材料之方法。 11· 一種以使料循環㈣苯二甲❹㈣料㈣ 之基質之連續在線擠屢及粉末熔融塗覆法製造如請: 152873.doc 201134663 1至8令任一項之材料之方法。 12 】3. 14. .如請求項】0之製造材料之方法 f粉末係藉由利用至少-熱旋轉筒：至：層：係藉由其 直接加熱㈣融並施用之粉末熔融法進；4㈣帶之 一種以如請求項！至8中任—項之材料於隔熱及/或隔音及/ 或聲阻尼及/或振動阻尼上之用途。 一種以如請求項1至8中任一項之材料於諸如牆壁、天花 板、地板、屋頂、容箱、導管、及管道之結構、器孤、 容器及管之内側及外側之隔熱及/或隔音上之用途。 152873.doc
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