Study of Halogen-free Flame Retardant Polycarbonate /Poly(ethylene terephthalte) Blends

本研究中使用聚碳酸酯/聚對苯二甲酸乙二酯(polycarbonate/poly ethylene terephthalte, PC/PET) 透過熔融混練法製備無鹵耐燃合膠，添加的無鹵耐燃劑主要分為兩類: 次磷酸鋁鹽 (aluminum phosphinate) OP1230與亞磷酸鋁鹽 (aluminum phosphonate) EXY。研究目的主要是PC與PET無鹵防火聚摻合物 (halogen-free flame retardant polymer) 之加工性及物理性質探討。此材料可廣泛應用於電子、汽車及建材等產品。 PC與PET酯交換反應發生於熔融狀態下，由紅外光光譜 (infrared spectrum, IR) 分析中可觀察到1070 cm-1 之芳香酯振動峰肩峰證實有酯交換反應發生。微差掃描式熱分析儀(DSC)結果顯示因酯交換反應使PET相玻璃轉移溫度(Tg) 提升、PC相Tg下降，此結果與動態機械分析儀(DMA)相符。 使用OP1230加入於PC，其中的鋁離子會造成PC裂解，使PC之Tg下降。另一方面，OP1230不影響PET之Tg、Tm，但DSC第一段降溫中發現OP1230之冷卻結晶峰，代表OP1230於冷卻時析出於PET相，而析出的OP1230會造成PET材質變脆。添加耐衝擊改質劑:乙烯-甲基丙烯酸缩水甘油酯-丙烯酸丁酯共聚物(ethylene glycidyl methacrylate butylacrylate terpolymer, PTW)與PET和OP1230之三成分混練研究中，利用PTW有助於OP1230分散於PET中達阻燃與增韌之效果，但OP1230會造成PTW裂解導致PET/PTW/OP1230產物易脆。 PC/PET/OP1230無鹵耐燃合膠呈發泡產物，IR分析中可見1070 cm-1 之芳香酯振動峰肩峰證實熔融混練時有酯交換反應發生，樣品經300℃、氮氣環境下熱處理5分鐘後，IR結果顯示PC之1773 cm-1 C=O拉伸振動峰消失，代表OP1230中的鋁離子造成PC裂解，導致PC與PET過度酯交換，故DSC第一段升溫PC/PET/OP1230無鹵耐燃合膠僅具106.4℃之單一Tg且不具PET熔融峰。為了抑制OP1230中鋁離子造成的PC裂解現象，嘗試使用具酸根高分子如Engage-g-MA與離子聚合物 (ionomer) Surlyn，或使用具孤對電子 (nonpaired) 化合物:胺基改質苯乙烯-乙烯-丁烯-苯乙烯共聚物(styrene-ethylene-butylene-styrene copolymer, SEBS) MP-10，或亞磷酸苯酯 (triphenyl phosphite, TPPi) 和三(2,4-第二丁基)磷酸苯酯Irgafos 168 與 PC/PET/OP1230 混練，希望螯合OP1230中鋁離子。但添加上述化合物之PC/PET/OP12330無鹵耐燃合膠，其DSC第一段升溫合膠僅具90.4℃之單一Tg 且PET熔融峰幾乎消失，表示上述方法無法完全螯合OP1230中的鋁離子，導致PC/PET合膠過度酯交換，呈發泡產物。 使用EXY加入PC之合膠其Tg亦下降，添加10 wt% EXY之PC合膠Tg由149.5℃下降至143.3℃。但與PET之合膠並不影響PET之Tg、Tm。PC/PET/EXY無鹵耐燃合膠有些微發泡，表示使用EXY較使用OP1230具較低酯交換程度，故DSC第一段升溫中仍可見74.4℃與136.9℃之兩Tg與PET熔融峰。 以雙螺桿押出機量產PC/PET/MBS-g-GMA/EXY無鹵耐燃合膠，由於PC/PET合膠有模口膨脹現象無法拉條，添加耐衝擊改質劑丙烯酸甲酯-丁烯-苯乙烯共聚物 (methyl methacrylate butadiene styrene terpolymer, MBS) 及其接枝甲基丙烯酸缩水甘油酯共聚物 (MBS-g-GMA) 可改善模口膨脹現象。PC/PET/MBS或(MBS-g-GMA)合膠之DSC第二段升溫結果顯示相對於MBS，使用MBS-g-GMA仍具兩Tg與PET相熔融峰，代表使用MBS-g-GMA酯交換程度較低。這兩種耐衝擊改質劑在添加量達10 wt%時，耐衝擊強度皆約70 kg-cm/cm。由於MBS-g-GMA的熱穩定性與機械性質較佳，配合耐燃劑EXY可製備PC/PET無鹵耐燃增韌合膠。DSC第一、第二段升溫顯示PC/PET/MBS-g-GMA/EXY無鹵耐燃合膠玻璃轉移溫度、熔點與PC/PET/MBS-g-GMA合膠相近。添加10 phr. EXY之合膠可達UL 94 V-0 (1/8’’) 級阻燃，但耐衝擊強度與伸長率亦急遽下降，顯示磷酸鹽系統在PC/PET合膠之機械性質提升並非很有效。In this study, polycarbonate/poly(ethylene terephthlate)/halogen-free flame retardant/impact modified composites were prepared via melt blending. Two flame retardants were utilized in this system. They can be classified into two types: aluminum phosphinate (OP1230) and aluminum phosphonate (EXY). The purpose of this study is to develop PC/PET blends to produce halogen-free flame retardant material. These blends can be applied to manufacture high value-added products like electronic appliances, automobiles and construction materials. PC and PET encounters the transesterification reaction in melt-processing. A band of 1070 cm-1 (aromatic ester vibration) is observed for PC/PET blends in IR spectrograph, and this indicates that transesterification reaction occurring. DSC results comfirms the transesterification reaction that increases the Tg in PET-phase and decreases the Tg in PC-phase, and is consistent with DMA results. OP1230 is added to PC, it results Tg of PC decreased from PC thermal degradation caused by aluminum ion from itself. On the other hand, OP1230 did not effect Tg, Tm of PET, but we can observed cooling peak of OP1230 from DSC first cooling, indicates that OP1230 separate out PET matrix as cooling process, and the OP1230 makes PET ingredient became brittle. Impact modifier, ethylene glycidyl methacrylate butylacrylate terpolymer (PTW), is used to PET/PTW/OP1230 ternary blends aid OP1230 dispersion in PET matrix to achieve flame retardant and toughening performance, but OP1230 result PTW degradation that PET/PTW/OP1230 composties became brittle. PC/PET/OP1230 blends is a foaming product; in IR spectrograph, a shoulder of aromatic ester vibration of 1070 cm-1 is observed, which illustated transesterification reaction occurring when melt blending. As the sample is heated by annealed 300℃, N2 for 5 min, the IR results showe 1773 cm-1 C=O stretching of PC was gone. This indicates that aluminum ion from OP1230 makes PC thermal degradation, and this causes PC/PET over transesterification. Therefore, DSC first heating PC/PET/OP1230 just had a single Tg 106.4℃ and no melting peak of PET. In order to inhibit the degradation reaction caused by aluminum ion from OP1230 on PC, polymer with acid group, such as Engage-g-MA and ionomer Surlyn are utilized; otherwise, compound with unpaired electron, amine modified styrene ethylene butylene styrene copolymer MP-10 are also used; or using triphenyl phosphite (TPPi) and (Tris(2,4-di-tert.-butylphenyl)phosphit), Irgafos 168 to blend with PC/PET/OP1230, hoping chelated aluminum ion of OP1230. However, while above compounds are blended with PC/PET/OP1230, the DSC first heating result shows a single Tg 90.4℃ and the melting peak of PET is almost invisible, indicates that these formulations can’t chelate aluminum ion of OP1230 completely. This result in PC/PET blends over transesterification, and forms a foamed product. While the EXY is added to PC, the Tg of PC decreases; while 10 wt% EXY is added that Tg is reduced from 149.5℃ to 143.3℃. But the blending of EXY with PET didn''t effect Tg and Tm of PET. PC/PET/EXY blends is slightly foaming, indicates that blending with EXY have lower transesterification level than blending with OP1230, so first heating of DSC is still observed two Tgs and a melting peak of PET. PC/PET/MBS-g-GMA/EXY composites were scaled up by twin-screw extruder. PC/PET blends can’t molding because die swelling phenomenon, adding impact modifier methyl methacrylate- butadiene-styrene (MBS) and MBS graft glycidyl methacrylate product (MBS-g-GMA) improves on die swelling. PC/PET/MBS or (MBS-g-GMA) blends, DSC second heating shows that MBS-g-GMA blends are still observed two Tgs and melting peak of PET compared to MBS blends, indicating that using MBS-g-GMA has lower transesterification level. When both impact modifying contents reach 10 wt%, the impact strength is about 70 kg-cm/cm. Since MBS-g-GMA had better thermal stability and mechanical properties than MBS, it can be used to prepared PC/PET/halogen-free flame retardant composites while EXY is added. DSC first heating and second heating results show that the Tg and Tm of PC/PET/MBS-g-GMA/EXY are similar to the PC/PET/MBS-g-GMA blends. Adding 10 phr. EXY, the flammability test of composites reaches UL 94 V-0 (1/8’’), but the impact strength and strain rate reduced dramatically, which indicates that phosphorous salt system is not effective in raising the mechanical properties of PC/PET blending.中文摘要 i 英文摘要 iii 謝誌 v 目錄 vi 表目錄 x 圖目錄. xii 一、緒論 1 1.1 前言 1 1.2 PC/PET合膠簡介 1 1.3 耐燃劑簡介 2 1.4 研究動機與目的 6 1.5 研究方法 7 1.6 研究架構與流程 8 二、文獻回顧 12 2.1 PC相關文獻 12 2.1.1 PC增韌相關文獻 12 A. 使用ABS(Acrylonitrile-Butadiene-Styrene)橡膠增韌 12 B. PC/HDPE使用SurlynR 8940 增韌 12 2.1.2 PC阻燃相關文獻 13 2.1.3 PC相關專利 15 2.2 PET(PBT)相關文獻 20 2.2.1 PET增韌相關文獻 20 2.2.2 PET阻燃相關文獻 21 A. 磷系耐燃劑 21 A.1次磷酸鋁鹽(aluminum phosphinate) 21 A.2 10-(2,5-2羥基苯基)-10-氫-9-氧雜-10-磷雜菲-10-氧 化物(10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-xa-10 -phosphaphenanthrene-10-oxide, DOPO-HQ) 22 B. 氮系耐燃劑,氰尿酸三聚氰胺(melamine cyanurate) 26 2.3 PC/PET(PBT)相關文獻 27 2.3.1 PC/PET(PBT)酯交換行為及反應機構 27 2.3.2 PC/PET(PBT)添加酯交換觸媒系統 31 2.3.3 PC/PET(PBT)添加穩定劑(酯交換抑制劑)系統 33 2.3.4 PC/PET/MDI 鏈增長劑系統 35 2.3.5 PC/PET(PBT)增韌系統 35 A. PC/PET(PBT)使用PTW增韌 35 B. PC/PET使用SEBS增韌 36 2.3.6 PC/PET阻燃相關文獻 36 2.3.7 PC/PET(PBT)相關專利 38 三、實驗 45 3.1 實驗儀器 45 3.2 實驗藥品 47 3.3 實驗步驟 53 四、結果與討論 59 4.1 PC/PET合膠物性分析與酯交換分析 59 4.1.1 PC/PET合膠DSC分析 59 4.1.2 PC/PET合膠DMA分析 61 4.1.3 PC/PET合膠TGA分析 61 4.1.4 PC/PET合膠酯交換FTIR分析 62 4.2不同耐燃劑對PC、PET和PC/PET合膠物性分析 63 A. 次磷酸鋁鹽(aluminum phopsphinate), OP1230 63 A.1 次磷酸鋁鹽(aluminum phopsphinate), OP1230 63 A1.1 OP1230鑑定與分析 63 A1.2 OP1230對PC Tg之影響 64 A1.3 OP1230對PET熱性質與DMA性質之影響 65 A1.4 OP1230對PC/PET合膠熱性質之影響與IR分析 66 A2. 添加耐衝擊改質劑PTW與PET和OP1230三成分混 練 67 A2.1 PET/PTW/OP1230無鹵增韌材料DSC熱性質分 析 68 A.3 抑制OP1230鋁離子造成PC/PET合膠發泡現象 68 A3.1 製備耐衝擊改質劑/OP1230濃縮母粒 69 A3.1.1 Engage-g-MA/OP1230系統 69 A3.1.2 MP-10/OP1230 系統 69 A3.1.3 PC/(PET/MP-10濃縮母粒)無鹵耐燃增韌 合膠 71 A3.2 添加金屬離子螯合劑 71 A3.2.1 離子聚合物(ionomer), SurlynR 8940 71 A3.2.2 亞磷酸苯酯(triphenyl phosphite), TPPi 73 A3.2.2.1 添加TPPi對PC/OP1230無鹵 耐燃材料熱性質之影響 73 A3.3 製備耐衝擊/酯交換抑制劑/金屬螯合劑/耐燃濃縮母粒, MIF 74 A3.3.1 MIF DSC熱性質分析 74 A3.3.2 PC/PET/MIF合膠熱性質分析 74 B. 亞磷酸鋁鹽(aluminum Phopsphonate), EXY 74 B.1 EXY鑑定與分析 75 B.2 EXY對PC Tg之影響 75 B.3 EXY對PET DSC熱性質之影響 75 B.4 EXY對PC/PET合膠熱性質之影響 76 4.3 押出混練製備PC/PET無鹵耐燃增韌合膠 76 4.3.1 PC/PET/MBS、MBS-g-GMA增韌合膠 77 4.3.1.1押出混練製備PC/PET合膠 77 4.3.1.2 低含量(5 wt%)耐衝擊改質劑對PC/PET DSC熱 性質影響之分析 77 4.3.1.3高含量(10 wt%)耐衝擊改質劑對PC/PET DSC熱 性質影響之分析 78 4.3.1.4 PC/PET/MBS、MBS-g-GMA增韌合膠酯交換IR 分析 78 4.3.1.5機械性質分析 78 4.3.2 PC/PET/MBS-g-GMA/EXY無鹵耐燃增韌合膠 79 4.3.2.1 熱性質分析 79 4.3.2.1 酯交換IR分析 80 4.3.2.2 機械性質與UL 94分析 81 五、結論 82 六、參考文獻 84 附錄(A)、樣品代號說明 87 附錄(B)、OP1230 中鋁離子高溫下造成 PC 裂解導致加速酯交換反應 式 90 附錄(C)、具孤對電子或酸根化合物螯合鋁離子示意圖 9