TW201932536A - 具良好機械性質的礦物填充之熱塑性組成物 - Google Patents
具良好機械性質的礦物填充之熱塑性組成物 Download PDFInfo
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Classifications
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Abstract
本發明係關於用於製造熱塑性模塑料的組成物,其中組成物含有下列成分:A)至少一聚合物,選自由芳族聚碳酸酯、芳族聚酯碳酸酯和聚酯所組成的群組,B)至少一酸酐官能化乙烯-α-烯烴共聚物或乙烯-α-烯烴三元共聚物,依高溫凝膠滲透層析測定,使用鄰二氯苯做為溶劑並對照聚苯乙烯標準,具有50000至500000克/莫耳的重量平均分子量Mw,C)滑石基礦物填料,亦關於製造模塑料的方法、模塑料本身、組成物或模塑料用於製造模製品的用途,及模製品本身。
Description
本發明係關於熱塑性組成物,特別係熱塑性聚碳酸酯組成物,用於製造熱塑性模塑料,及關於製造熱塑性模塑料的方法、模塑料本身、組成物或模塑料用於製造模製品的用途和模製品本身。
聚碳酸酯組成物已知曉很長的時間,這些材料用於製造模製品以供各種應用,例如用於汽車業、軌道車輛、建築業、電氣/電子業和家用電器。藉由改變配方成分數量與類型,可依各種應用要求大範圍修改組成物和製得模製品的熱、流變和機械性質。
就一些應用而言,特別係薄壁部件的例子,含聚碳酸酯組成物的模製品剛度不夠。為增大彈性模量,因而加入強化材料,例如滑石、矽灰石或玻璃纖維。雖然使用滑石基礦物填料往往無法如使用玻璃纖維般顯著提高剛度,但相比之下,其他性質改變程度較小。然即使使用滑石做為填料也常導致韌性性質劣化,添加低玻璃轉化溫度的聚合物摻混配合物做為彈性組分,可至少部分彌補之。
所用耐衝擊改質劑實例為具核殼結構的接枝聚合物,其由含丁二烯的核心與乙烯基(共)聚合物製成的接枝外殼製成,外殼擬確保改質劑與聚碳酸酯和存於混合物的其他聚合物組分的相容性(程度)。
EP 0 315 868 A2描述接枝聚合物的用途,其由粒狀二烯橡膠和聚碳酸酯組成物中的乙烯基單體製成接枝外殼製得。模塑
料具有良好低溫韌性和良好耐石油精的特性。
亦可採用其他不具核殼結構的彈性體組分類型。
WO 2013/045544 A1揭示具良好衝擊強度、流動性和化學抗性的阻燃PC/ABS組成物。組成物含有聚碳酸酯、接枝聚合物和無橡膠之α-烯烴三元共聚物。模塑料特別適合電氣與電子業的薄壁殼體部件。
US 2015/0353732 A1揭示含有聚碳酸酯及/或聚酯、視需要之耐衝擊改質劑和阻燃劑的組成物,還有具馬來酸酐官能化聚烯烴的增容劑。憑藉增容劑可達成改善衝擊強度。
WO 2013/045552 A1揭示由聚碳酸酯和無機填料製成的熱塑性模塑料,其含有0.01至0.5重量份的至少一酸酐改質α-烯烴三元共聚物,並具有高剛度和良好韌性。
US 2014/0329948 A1揭示耐衝擊改質及玻璃纖維強化的聚碳酸酯組成物,其具有高剛度和良好熱與流變性質並結合良好阻燃性。組成物含有聚碳酸酯、阻燃劑、玻璃纖維和酸酐改質α-烯烴三元共聚物。
WO 2015/189761揭示包含聚合物基質、化學反應耐衝擊改質劑和導熱填料的導熱熱塑性組成物。馬來酸酐接枝乙烯共聚物據述做為化學反應耐衝擊改質劑。組成物具有良好導熱性和韌性的特性。
然先前技術所述填料強化組成物和模塑料具有的韌性特性仍然不夠,特別係在拉伸測試的多軸應力、衝擊強度和斷裂伸長率方面。韌性原則上可藉由增加彈性組分比例來加強,但此通常會造成模塑料在如射出成型製程的加工性變差。
因此,期提供礦物強化組成物,其因良好熔體流動性而容易加工,同時還能製造具良好韌性的模製品。
特別係期提供礦物強化組成物,其在穿透測試具有高衝擊強度、高最大力值與總能量、高斷裂伸長率和高MVR值的特性。
現驚人地發現,用於製造熱塑性模塑料的組成物,其中組成物包含下列成分:A)至少一聚合物,選自由芳族聚碳酸酯和芳族聚酯碳酸酯所組成的群組,B)至少一酸酐官能化乙烯-α-烯烴共聚物或乙烯-α-烯烴三元共聚物,在各例中,依高溫凝膠滲透層析測定,使用鄰二氯苯做為溶劑並對照聚苯乙烯標準,具有50000至500000克/莫耳的重量平均分子量Mw,較佳為100000至400000克/莫耳,特佳為150000至350000克/莫耳;及C)至少一滑石基礦物填料,展現有利性質。
組成物較佳包含:40重量%至98.9重量%、更佳50重量%至90重量%、特佳60重量%至85重量%的組分A,0.1重量%至10重量%、更佳0.5重量%至9重量%、特佳1重量%至8重量%的組分B,1重量%至40重量%、較佳5重量%至35重量%、特佳10重量%至25重量%的組分C,及0重量%至20重量%、更佳0.1重量%至15重量%、特佳0.2重量%至10重量%的其他聚合物成分及/或聚合物添加劑做為組分D。
在一較佳具體實例中,組成物在一定程度上由至少90重量%的組分A至D組成。最佳地,組成物只由組分A至D組成。
組分B的馬來酸酐基團可與組分A及/或組成物的其他組分發生化學反應。馬來酸酐基團亦可與水分或其他雜質發生化學反應。
反應特別發生在高溫熔體,例如普遍存於熔融化合(如在押出機中)和射出成型期間者。此會降低馬來酸酐基團比例。在本專利申請書內文中,根據本發明的模塑料應理解成亦包括組分
A、B、C和視需要之D物理混合及熔融化合而得者。
在本發明內文中,聚碳酸酯不僅包括均聚碳酸酯,還有共聚碳酸酯及/或聚酯碳酸酯;聚碳酸酯如已知可為直鏈或支鏈。根據本發明,亦可使用聚碳酸酯混合物。
熱塑性聚碳酸酯(包括熱塑性芳族聚酯碳酸酯)的重量平均分子量Mw以GPC(凝膠滲透層析,在二氯甲烷中以聚碳酸酯為標準)測定為15000克/莫耳至50000克/莫耳,較佳為20000克/莫耳至35000克/莫耳,特別係23000克/莫耳至33000克/莫耳。
在根據本發明所用聚碳酸酯中,至多80莫耳%、較佳20莫耳%至50莫耳%的部分碳酸酯基團被芳族二羧酸酯基團取代。此類聚碳酸酯稱作芳族聚酯碳酸酯,其含有羧酸的酸原子團與芳族二羧酸的酸原子團攙入分子鏈。在本發明內文中,其用傘式術語「熱塑性芳族聚碳酸酯」一詞涵蓋。
聚碳酸酯以已知方式由二酚、碳酸衍生物、視需要之鏈終止劑和視需要之分枝劑製造,其中為製造聚酯碳酸酯,乃依據碳酸酯結構單元待被芳族聚碳酸酯中芳族二羧酸酯結構單元取代的程度,讓部分碳酸衍生物被芳族二羧酸或二羧酸衍生物取代。
適於製造聚碳酸酯的二羥基芳基化合物為具式(1)者,HO-Z-OH (1),其中Z係芳族原子團,其具有6至30個碳原子及含有一或更多芳環,可被取代及含有脂族或環脂族原子團或烷基芳基或雜原子做為橋接元素。
式(1)的Z較佳代表式(2)原子團,
其中
R6和R7個別代表H、C1-至C18-烷基、C1-至C18-烷氧基、鹵素(如Cl或Br),或在各例中為視需要之取代芳基或芳烷基,較佳為H或C1-至C12-烷基,更佳為H或C1-至C8-烷基,再佳為H或甲基,及X代表單鍵、-SO2-、-CO-、-O-、-S-、C1-至C6-伸烷基、C2-至C5-烷叉基或C5-至C6-環烷叉基,其可被C1-至C6-烷基取代,較佳為甲基或乙基,或代表C6-至C12-亞芳基且可視需要之融合其他含雜原子的芳環。
X較佳代表單鍵、C1-至C5-伸烷基、C2-至C5-烷叉基、C5-至C6-環烷叉基、-O-、-SO-、-CO-、-S-、-SO2-或式(2a)原子團,
二羥基芳基化合物(二酚)的實例為二羥基苯、二羥基聯苯、雙(羥基苯基)烷烴、雙(羥基苯基)環烷、雙(羥基苯基)芳、雙(羥基苯基)醚、雙(羥基苯基)酮、雙(羥基苯基)硫醚、雙(羥基苯基)碸、雙(羥基苯基)亞碸、1,1’-雙(羥基苯基)二異丙苯和其環烷基化與環鹵化化合物。
適於製造根據本發明所用聚碳酸酯的二酚例如為對苯二酚、間苯二酚、二羥基聯苯、雙(羥基苯基)烷烴、雙(羥基苯基)環烷、雙(羥基苯基)硫醚、雙(羥基苯基)醚、雙(羥基苯基)酮、雙(羥基苯基)碸、雙(羥基苯基)亞碸、α,α’-雙(羥基苯基)二異丙苯和其烷基化、環烷基化和環鹵化化合物。
較佳二酚為4,4’-二羥基聯苯、2,2-雙(4-羥基苯基)-1-苯基丙烷、1,1-雙(4-羥基苯基)苯基乙烷、2,2-雙(4-羥基苯基)丙烷、2,4-雙(4-羥基苯基)-2-甲基丁烷、1,3-雙[2-(4-羥基苯基)-2-丙基]苯(雙酚M)、2,2-雙(3-甲基-4-羥基苯基)丙烷、雙(3,5-二甲基-4-羥基苯基)甲烷、2,2-雙(3,5-二甲基-4-羥基苯基)丙烷、雙(3,5-二甲基-4-羥基苯基)碸、2,4-雙(3,5-二甲基-4-羥基苯基)-2-甲基丁烷、1,3-雙[2-(3,5-二甲基-4-羥基苯基)-2-丙基]苯和1,1-雙(4-羥基苯基)-3,3,5-
三甲基環己烷(雙酚TMC)。
特佳二酚為4,4’-二羥基聯苯、1,1-雙(4-羥基苯基)苯基乙烷、2,2-雙(4-羥基苯基)丙烷(雙酚A)、2,2-雙(3,5-二甲基-4-羥基苯基)丙烷、1,1-雙(4-羥基苯基)環己烷和1,1-雙(4-羥基苯基)-3,3,5-三甲基環己烷(雙酚TMC)。2,2-雙(4-羥基苯基)丙烷(雙酚A)尤佳。
上述和其他適合二酚例如描述於US 2 999 835 A、3 148 172 A、2 991 273 A、3 271 367 A、4 982 014 A與2 999 846 A、德國公開說明書1 570 703 A、2 063 050 A、2 036 052 A、2 211 956 A與3 832 396 A、法國專利說明書1 561 518 A1、專題論文”H.Schnell,Chemistry and Physics of Polycarbonates,Interscience Publishers,New York 1964,p.28 ff.;p.102 ff.”和”D.G.Legrand,J.T.Bendler,Handbook of Polycarbonate Science and Technology,Marcel Dekker New York 2000,p.72ff.”。
在均聚碳酸酯例子中,只使用一種二酚;在共聚碳酸酯例子中,使用二或更多種二酚。所用二酚和所有其他加入合成的化學品與助劑可能遭出自其本身合成、搬運及儲存的污染物污染。然期使用盡量最高純度的原料。
分子量調節所需單官能基鏈終止劑(如酚或烷基酚,特別係苯酚、對叔丁基酚、異辛基酚、異丙苯基酚、其氯碳酸酯或單羧酸醯氯或鏈終止劑混合物)乃供應以與雙酚鹽反應或於任何時間加入合成,前提係光氣或氯碳酸端基仍存於反應混合物,或在醯氯與氯碳酸酯做為鏈終止劑的情況下,只要所得聚合物有足夠的酚端基即可。然鏈終止劑較佳係在光氣化程序後於不再存有光氣、但催化劑尚未加入所在或時刻加入,或在催化劑前或與催化劑一起或並行加入。
所用任何分枝劑或分枝劑混合物以相同方式加入合成,但通常係在鏈終止劑前。一般使用化合物為三酚、四酚、或三或四羧酸醯氯化物、或多酚或醯氯化物混合物。
可做為分枝劑並具三或超過三個酚羥基的一些化合
物例如為間苯三酚、4,6-二甲基-2,4,6-三(4-羥基苯基)庚-2-烯、4,6-二甲基-2,4,6-三(4-羥基苯基)庚烷、1,3,5-三(4-羥基苯基)苯、1,1,1-三(4-羥基苯基)乙烷、三(4-羥基苯基)苯基甲烷、2,2-雙[4,4-雙(4-羥基苯基)環己基]丙烷、2,4-雙(4-羥基苯基異丙基)苯酚、四(4-羥基苯基)甲烷。
一些其他三官能基化合物為2,4-二羥基苯甲酸、對稱苯三甲酸、氰尿醯氯和3,3-雙(3-甲基-4-羥基苯基)-2-側氧-2,3-二氫吲哚。
較佳分枝劑為3,3-雙(3-甲基-4-羥基苯基)-2-側氧-2,3-二氫吲哚和1,1,1-三(4-羥基苯基)乙烷。
視需要之使用的分枝劑量按各例所用二酚莫耳計為0.05莫耳%至2莫耳%。
分枝劑可先和二酚與鏈終止劑一起加進鹼性水相或在光氣化前加入溶於有機溶劑。
所有聚碳酸酯製造手段為熟諳此技術者所知悉。
適於製造聚酯碳酸酯的芳族二羧酸例如為鄰苯二甲酸、對苯二甲酸、間苯二甲酸、叔丁基間苯二甲酸、3,3’-二苯基二羧酸、4,4’-二苯基二羧酸、4,4-二苯酮二羧酸、3,4’-二苯酮二羧酸、4,4’-二苯基醚二羧酸、4,4’-二苯基碸二羧酸、2,2-雙(4-羧基苯基)丙烷、三甲基-3-苯基茚烷-4,5’-二羧酸。
在芳族二羧酸中,特佳使用對苯二甲酸及/或間苯二甲酸。
二羧酸衍生物包括二羰基二鹵化物和二烷基二羧酸酯,特別係二羰基二氯化物和二甲基二羧酸酯。
以芳族二羧酸酯基團取代碳酸酯基團本質上係按化學計量及定量進行,故反應配合物的莫耳比亦反映在最終聚酯碳酸酯。芳族二羧酸酯基團可無規或嵌段攙入。
根據本發明所用聚碳酸酯(包括聚酯碳酸酯)的較佳製造模式為已知界面法和已知熔體交酯化法(參見如WO
2004/063249 A1、WO 2001/05866 A1、WO 2000/105867、US 5,340,905 A、US 5,097,002 A、US-A 5,717,057 A)。
在前者情況下,所用酸衍生物較佳為光氣和視需要之二羰基二氯化物;在後者情況下,較佳為二苯基碳酸酯和視需要之二羧酸二酯。在兩種情況下,用於聚碳酸酯製造/聚酯碳酸酯製造的催化劑、溶劑、後續處理、反應條件等已充分描述及知悉。
在一較佳具體實例中,只使用芳族聚碳酸酯做為組分A,最佳包含雙酚A做為二酚單元的芳族聚碳酸酯。
用作組分B的是具接枝酸酐基團的乙烯-α-烯烴共聚物或三元共聚物。在本專利申請書內文中,組分B亦稱作用酸酐基團官能化的乙烯-α-烯烴共聚物或三元共聚物。
酸酐較佳選自包含馬來酸酐、酞酐、富馬酸酐、伊康酸酐和其混合物的群組。特佳酸酐為馬來酸酐。
除了乙烯,共聚物或三元共聚物較佳還包含共單體(α-烯烴)1-丙烯、1-丁烯、1-異丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十一烯、1-十二烯、1-十三烯、1-十四烯、1-十八烯、1-十九烯或其混合物。特佳採用乙烯與1-辛烯共聚物。
烯烴共聚物可依US 5272236 A和US 5278272 A所述製造。用酸酐基團接枝例如描述於US 323691 A。α-烯烴共單體含量在各例中按乙烯與一或更多共單體的總和計較佳為2-40莫耳%,更佳為5-35莫耳%,特佳為10-25莫耳%。
所述乙烯-α-烯烴共聚物或三元共聚物較佳為無規共聚物。
具接枝酸酐基團的共聚物或三元共聚物可如WO 98/02489所述經初始交聯,以最佳化彈性性質。
乙烯與共單體的比例可利用1H和13C NMR光譜及以三氯乙烷做為溶劑測定。
酸酐改質聚合物較佳具有下列組成:
B(1):90.0重量%至99.99重量%、更佳97.0重量%至99.9重量%、再佳98.0重量%至99.7重量%、極佳99.0重量%至99.5重量%的共聚物或三元共聚物,B(2):0.01重量%至10.0重量%、更佳0.1重量%至3.0重量%、再佳0.3重量%至2.0重量%、極佳0.5重量%至1.0重量%的酸酐。
在另一較佳具體實例中,組分B的主鏈由乙烯與1-辛烯單元的無規共聚物組成。
酸酐改質共聚物或三元共聚物的重量平均分子量Mw在各例中以HT-GPC(高溫凝膠滲透層析)及使用鄰二氯苯做為溶劑並對照聚苯乙烯標準測定為超過50000至500000克/莫耳,較佳為100000至400000克/莫耳,特佳為150000至350000克/莫耳。
較佳產物的玻璃轉化溫度不超過-50℃。玻璃轉化溫度係依據DIN EN 61006(2004年版),由示差掃描卡計(DSC)以10K/分鐘的加熱速率測定,並定義Tg為中點溫度(切線法)。
組成物含有至少一滑石基礦物填料做為組分C。
在本發明內文中,適合做為滑石基礦物填料的是熟諳滑石或皂石相關領域者所知任何粒狀填料。適合的還有所有市售粒狀填料,其產品性狀含有滑石或皂石等術語為特性化特徵。
較佳為礦物填料,依據DIN 55920,滑石含量按填料總質量計為超過50重量%,較佳為超過80重量%,特佳為超過95重量%,極佳為超過98重量%。
滑石應理解為意指天然或人造滑石。
純滑石的化學組成為3MgO.4SiO2.H2O,是以MgO含量為31.9重量%,SiO2含量為63.4重量%,化學鍵結水含量為4.8重量%。其係具有層狀結構的矽酸鹽。
天然滑石材料通常不具上述理想組成,因其會因為如其他元素部分取代鎂、鋁部分取代矽及/或與其他礦物(如白雲石、菱鎂礦和綠泥石)交生而受到污染。
有利的是在根據本發明組成物中,組分E含有或由滑石(E2)組成,其中滑石的MgO含量為28重量%至35重量%,特別係30.5重量%至32重量%,SiO2含量為55重量%至65重量%,Al2O3含量為小於1重量%。在包含組分E的組成物中,發現尤其係加工引起的聚碳酸酯降解反應僅以輕微限度發生。
亦有利又較佳的特別係使用根據本發明的細磨等級型滑石,其平均粒徑d50為0.1-20微米(μm),較佳為0.2-10μm,更佳為0.3-5μm,再佳為0.3-2.5μm,特佳為0.4-1.0μm。
根據本發明使用的滑石基礦物填料較佳具有小於10μm、更佳小於7μm、特佳小於6μm、極佳小於4.5μm的上粒徑或粒度d95。填料的d95和d50值係依據ISO 13317-3,利用SEDIGRAPH D 5 000沉降分析測定。滑石基礦物填料可視需要之表面處理,以達成更好地耦接至聚合物基質。其例如可配有以官能化矽烷為基料的黏著促進劑系統。
滑石基礦物填料的平均高寬比(直徑對厚度)由超薄成品切片電子顯微圖測定及代表性填料顆粒量(約50)測量較佳為1-100,更佳為2-25,特佳為5-25。
由於加工提供模塑料/模製品,模塑料/模製品中的滑石基礦物填料具有比最初使用填料小的d95/d50。
組成物可含有一或更多其他添加劑做為組分D,較佳選自由阻燃劑(如有機磷或鹵素化合物,特別係雙酚-A系寡聚磷酸鹽)、防滴劑(如出自氟化聚烯烴、矽酮和聚芳醯胺纖維物類的化合物)、阻燃增效劑(如奈米級金屬氧化物)、煙霧抑制劑(如硼酸鋅)、潤滑劑與脫模劑(如季戊四醇四硬脂酸酯)、成核劑、抗靜電劑、導電添加劑、穩定劑(如水解、熱老化與UV穩定劑,還有交酯化抑制劑及酸/鹼猝熄劑)、流動性促進劑、增容劑、其他聚合物成分(如聚酯、乙烯基(共)聚合物或功能性摻混配合物)、填料與強化劑(如碳纖、玻璃纖維、雲母、高嶺土、CaCO3)、及染料與顏料(如二氧
化鈦或氧化鐵)所組成的群組。
在一較佳具體實例中,組成物不含阻燃劑、防滴劑、阻燃增效劑和煙霧抑制劑。
在一較佳具體實例中,組成物含有選自由潤滑劑與脫模劑、穩定劑、流動性促進劑、增容劑、其他聚合物成分和染料與顏料所組成群組的至少一聚合物添加劑。
在一較佳具體實例中,組成物含有季戊四醇四硬脂酸酯做為脫模劑。
在一較佳具體實例中,組成物含有選自由立體障礙酚、有機亞磷酸鹽、硫系共安定劑和有機與無機布氏酸(Brønsted acid)所組成群組的至少一代表物做為穩定劑。所用布氏酸較佳為檸檬酸。
在一特佳具體實例中,組成物含有選自由十八基-3-(3,5-二叔丁基-4-羥基苯基)丙酸鹽和三(2,4-二叔丁基苯基)亞磷酸鹽所組成群組的至少一代表物做為穩定劑。
在一極佳具體實例中,組成物含有十八基-3-(3,5-二叔丁基-4-羥基苯基)丙酸鹽與三(2,4-二叔丁基苯基)亞磷酸鹽組合物做為穩定劑。
特佳組成物含有季戊四醇四硬脂酸酯做為脫模劑,選自由十八基-3-(3,5-二叔丁基-4-羥基苯基)丙酸鹽和三(2,4-二叔丁基苯基)亞磷酸鹽與檸檬酸所組成群組的至少一代表物做為穩定劑。
根據本發明的組成物可用於製造熱塑性模塑料。
根據本發明,熱塑性模塑料例如可藉由混合組成物的各成分及熔融化合,並在較佳200℃至320℃、更佳240℃至300℃的溫度下,在習用設備中,例如內部捏合機、押出機和雙軸螺桿系統,以已知方式熔融押出所得混合物而製造。在本申請案內文中,此過程通稱化合。在此方法中,至少使組分A熔融,並使組成物的所有成分分散及/或互溶,在進一步步驟中,藉由冷卻,使所得熔體重新
固化,及視需要之造粒。固化及造粒步驟可以任一預定彼此相關順序進行。故「模塑料」一詞應理解為意指組成物的成分經熔融化合及熔體押出而得的產物。
組成物的個別成分可以已知方式在約20℃(室溫)或更高溫度下相繼或同時混合。故例如,一些成分可由押出機的主要入口加入,其餘成分隨後由輔助入口供給化合過程,例如利用輔助押出機。
本發明亦提供製造根據本發明模塑料的方法。
方法較佳為聚碳酸酯熔體和添加劑由雙螺桿押出機的主要入口加入,滑石基礦物填料由輔助入口加至熔融區域下游的區域。為確保聚碳酸酯有最佳可行穩定性和加工性,填料應於化合時的最遲應許時刻添加,但不會因停留時間及混合效果不足而阻礙填料充分分散。
根據本發明的模塑料可用於製造任何類型的模製品。其例如可利用射出成型、押出和吹塑成型方法製造。另一加工形式為由預製片或膜抽製成型來製造模製品。組成物的成分亦可計量加入射出成型機或押出單元,及直接加工成模製品。
可由根據本發明組成物和模塑料製造的模製品實例為膜、型材、任何類型的外殼零件,例如用於家用電器(如榨汁機、咖啡機、混合器)、用於事務性機器(如監視器、平面螢幕、筆記型電腦、印表機、影印機)、用於建築業的片材、管道、電氣安裝管路、窗、門與其他型材(內部裝配和外部應用),還有電氣與電子部件,例如開關、插頭和插座,及用於營業車輛的零組件,特別係用於汽車業。根據本發明組成物和模塑料亦適於製造下列模製品或塑模:軌道車輛、船舶、飛機、巴士和其他機動車輛的內部裝配零件、機動車輛的車身部件、含小型變壓器的電氣裝備外殼、處理及傳輸資訊的裝備外殼、醫療裝備的外殼與包層、按摩設備及其外殼、兒童玩具車、片狀壁件、安全裝備外殼、隔熱運輸容器、衛浴設備的模製零件、通風口的防護格柵和花園設備外殼。
本發明的其他具體實例1至28描述如下。
1.一種組成物,用於製造熱塑性模塑料,其中組成物含有或由下列成分組成:A)至少一聚合物,選自由芳族聚碳酸酯、芳族聚酯碳酸酯和聚酯所組成的群組,B)至少一酸酐官能化乙烯-α-烯烴共聚物或乙烯-α-烯烴三元共聚物,依高溫凝膠滲透層析測定,使用鄰二氯苯做為溶劑並對照聚苯乙烯標準,具有50000至500000克/莫耳的重量平均分子量Mw,C)滑石基礦物填料。
2.根據具體實例1之組成物,其中組分B按α-烯烴與乙烯的總和計包含2-40莫耳%的α-烯烴單元和60-98莫耳%的乙烯單元。
3.根據具體實例1之組成物,其中組分B按α-烯烴與乙烯的總和計包含5-35莫耳%的α-烯烴單元和65-95莫耳%的乙烯單元。
4.根據具體實例1之組成物,其中組分B按α-烯烴與乙烯的總和計包含10-25莫耳%的α-烯烴單元和75-90莫耳%的乙烯單元。
5.根據任一前述具體實例之組成物,其中組分B具有0.01重量%至10.0重量%的酸酐含量。
6.根據任一前述具體實例之組成物,其中組分B具有0.1重量%至3.0重量%的酸酐含量。
7.根據任一前述具體實例之組成物,其中組分B具有0.3重量%至2.0重量%的酸酐含量。
8.根據任一前述具體實例之組成物,其中組分B具有0.5重量%至1.0重量%的酸酐含量。
9.根據任一前述具體實例之組成物,其中組分B係馬來酸酐官能化的乙烯與1-辛烯共聚物。
10.根據任一前述具體實例之組成物,其中組分B具
有100000至400000克/莫耳的重量平均分子量Mw。
11.根據任一前述具體實例之組成物,其中組分B具有150000至350000克/莫耳的重量平均分子量Mw。
12.根據任一前述具體實例之組成物,其中組分A僅由芳族聚碳酸酯組成。
13.根據任一前述具體實例之組成物,其中滑石用作組分C。
14.根據具體實例13之組成物,其中滑石的平均粒徑d50為0.3-5μm。
15.根據具體實例14之組成物,其中滑石的平均粒徑d50為0.3-2.5μm。
16.根據具體實例14之組成物,其中滑石的平均粒徑d50為0.4-1.0μm。
17.根據任一前述具體實例之組成物,含有或由以下組成:40重量%至98.9重量%的組分A,0.1重量%至10重量%的組分B,1重量%至40重量%的組分C,0重量%至20重量%的其他聚合物成分及/或聚合物添加劑做為組分D。
18.根據任一前述具體實例之組成物,含有或由以下組成:50重量%至90重量%的組分A,0.5重量%至9重量%的組分B,5重量%至35重量%的組分C,0.1重量%至15重量%的其他聚合物成分及/或聚合物添加劑做為組分D。
19.根據任一前述具體實例之組成物,含有或由以下組成:
60重量%至85重量%的組分A,1重量%至8重量%的組分B,10重量%至25重量%的組分C,0.2重量%至10重量%的其他聚合物成分及/或聚合物添加劑做為組分D。
20.根據任一前述具體實例之組成物,其中組分D包含選自由酚系抗氧化劑、亞磷酸鹽和布氏酸所組成群組的至少一穩定劑。
21.一種製造模塑料的方法,含有步驟(i)、(ii)和視需要之(iii),其中在第一步驟(i)中,引入熱及/或機械能來加熱如具體實例1-18中任一者之組成物,從而至少使組分A熔融,並使所有採用組分分散及/或互溶,及在進一步步驟(ii)中,藉由冷卻,使方法步驟(i)產生的熔體重新固化(ii),及視需要之造粒(iii),其中方法步驟(ii)、(iii)可以任一預定彼此相關順序進行。
22.根據具體實例21之方法,其中步驟(i)係在200℃至320℃的溫度下進行。
23.根據具體實例21之方法,其中步驟(i)係在240℃至300℃的溫度下進行。
24.根據具體實例21-23中任一者之方法,其中方法係用混練單元(compounding unit)進行,組分C係與其他組分分開加入。
25.根據具體實例24之方法,其中所用混練單元係雙螺桿押出機,組分C由輔助入口加至其他組分用熔融區域下游的區域。
26.一種模塑料,獲自或可得自根據具體實例21-25中任一者之方法。
27.一種根據具體實例1-20中任一者之組成物或根據具體實例26之模塑料的用途,用於製造模製品。
28.一種模製品,可得自根據具體實例1-20中任一者之組成物或根據具體實例26之模塑料。
A1:雙酚A系直鏈聚碳酸酯,利用凝膠滲透層析,在二氯甲烷中以聚碳酸酯為標準測定重量平均分子量Mw為28000克/莫耳。
B1:馬來酸酐(MAH)官能化乙烯-1-辛烯共聚物,MAH含量為0.8重量%,乙烯與1-辛烯比為87莫耳%對13莫耳%,重量平均分子量Mw為200000克/莫耳(取自Dow Chemical的ParaloidTM EXL 3815)。
B2:馬來酸酐(MAH)官能化乙烯-1-辛烯共聚物,MAH含量為0.4重量%,乙烯與1-辛烯比為83莫耳%對17莫耳%,重量平均分子量Mw為322000克/莫耳(取自Dow Chemical的ParaloidTM EXL 3815)。
B3(對照組):乙烯-丙烯-辛烯-馬來酸酐共聚物,乙烯:丙烯:辛烯比按重量%計為87:6:7(按莫耳%計,相當於94:4:2),CAS編號:31069-12-2,以GPC及聚苯乙烯標準測定分子量Mw為5000克/莫耳,馬來酸酐比例為4.4重量%,HiWaxTM 1105 A(取自Mitsui Chemicals)。
B4(對照組):Kane ACETM M732,具核殼結構和丁二烯橡膠核心的耐衝擊改質劑(取自Kaneka)。
滑石:取自Imi Fabi的HTP UltraTM,MgO含量為31.0重量%,SiO2含量為61.5重量%,Al2O3含量為0.4重量%,平均粒徑d50=0.65μm。
D1:熱穩定劑,IrganoxTM B900(IrganoxTM B900(80% IrgafosTM 168(三(2,4-二叔丁基苯基)亞磷酸鹽)與20% IrganoxTM 1076(2,6-二叔丁基-4-(十八烷氧基羰基乙基)苯酚)的混合物);BASF(Ludwigshafen,德國)。
D2:脫模劑,季戊四醇四硬脂酸酯。
D3:檸檬酸,純度99.5%,取自Acros Organics(Geel,比利時)。
在Leistritz ZSE-27Maxx雙螺桿押出機中,在熔融溫度260℃下混合組分。在實驗5、6、V7、V8中,由輔助入口將滑石加至其他組分用熔融區域下游的區域。在Arburg 270E射出成型機中,在300℃的熔融溫度及80℃的模具溫度下製造模製品。
MVR係依據ISO 1133(2012年版),在300℃及1.2公斤負載下測定,熔融時間為5分鐘。
夏氏(Charpy)衝擊強度係依據ISO 179/1eU,在各例中,在23℃及-30℃下測定10個測試試樣,試樣尺寸為80毫米(mm)×10mm×4mm。
斷裂伸長率和標稱斷裂伸長率係依據ISO 527(1996年版),在室溫下測定。
在實作相關衝擊/撞擊測試中用作進一步測量延展性的是多軸穿透測試行為表現。穿透測試係基於ISO 6603-2(2000年版;「基於」意指不進行目視檢查測試試樣),在23℃下進行並使用尺寸為60mm×60mm×2mm的試樣。
表1的資料顯示,根據本發明含有組分B1與B2的組成物1、2、5、6可用於製造具良好熔體流動性(相較於V4,MVR值未受損)的模塑料和在衝擊測試、穿透測試和拉伸測試方面有良好韌性的模製品。以具核殼結構的接枝聚合物(B4)替代本發明組分B1/B2時,衝擊強度和穿透測試的最大力值與總能量將降低。使用彈性組分B3時,衝擊強度類似用B1或B2所得者,但穿透測試的韌性明顯受損。又特別有利的是,使用組分B1能顯著改善斷裂伸長率和標稱斷裂伸長率。另外,實施例5、6顯示,由輔助入口添加滑石基礦物填料為本發明組成物的斷裂伸長率和標稱斷裂伸長率帶來顯著改善。儘管比較實施例V7、V8亦顯示由輔助入口添加的好處,但斷裂伸長率和標稱斷裂伸長率增進明顯較不顯著。
Claims (15)
- 一種組成物,用於製造熱塑性模塑料,其中該組成物含有或由下列成分組成:A)至少一聚合物,選自由芳族聚碳酸酯、芳族聚酯碳酸酯和聚酯所組成的群組;B)至少一酸酐官能化乙烯-α-烯烴共聚物或乙烯-α-烯烴三元共聚物,依高溫凝膠滲透層析測定,使用鄰二氯苯做為溶劑並對照聚苯乙烯標準,具有50000至500000克/莫耳的一重量平均分子量Mw;及C)一滑石基礦物填料。
- 根據申請專利範圍第1項之組成物,其中該組分B按α-烯烴與乙烯的總和計包含2至40莫耳%的α-烯烴單元和60至98莫耳%的乙烯單元。
- 根據前述申請專利範圍中任一項之組成物,其中該組分B具有0.1重量%至3.0重量%的酸酐含量。
- 根據前述申請專利範圍中任一項之組成物,其中該組分B係馬來酸酐官能化的乙烯與1-辛烯共聚物。
- 根據前述申請專利範圍中任一項之組成物,其中該組分B按1-辛烯與乙烯的總和計包含10至25莫耳%的1-辛烯單元和75至90莫耳%的乙烯單元。
- 根據前述申請專利範圍中任一項之組成物,其中該組分A僅由芳族聚碳酸酯組成。
- 根據前述申請專利範圍中任一項之組成物,其中使用滑石作為該組分C。
- 根據前述申請專利範圍中任一項之組成物,含有或由以下組成:40重量%至98.9重量%的該組分A;0.1重量%至10重量%的該組分B;1重量%至40重量%的該組分C;及0重量%至20重量%的其他聚合物成分及/或聚合物添加劑做為一 組分D。
- 根據前述申請專利範圍中任一項之組成物,其中該組分D包含選自由酚系抗氧化劑、亞磷酸鹽和布氏酸所組成群組的至少一穩定劑。
- 一種製造模塑料的方法,含有步驟(i)、(ii)和視需要之(iii),其中在一第一步驟(i)中,引入熱及/或機械能來加熱如申請專利範圍第1至9項中任一項之組成物,從而至少使該組分A熔融,並使所有採用的組分分散及/或互溶;及在一進一步步驟(ii)中,藉由冷卻,使該方法步驟(i)產生的熔體重新固化(ii),及(iii)視需要地進行造粒,其中該等方法步驟(ii)、(iii)可以任何預定之彼此相對順序進行。
- 根據申請專利範圍第10項之方法,其中該方法係用一混練單元進行,該組分C係與該等其他組分分開加入。
- 根據申請專利範圍第11項之方法,其中所用該混練單元係一雙螺桿押出機,該組分C由一輔助入口加至該等其他組分用熔融區域下游的一區域。
- 一種模塑料,其係獲自或可得自如申請專利範圍第10至12項中任一項之方法。
- 一種如申請專利範圍第1至9項中任一項之組成物或如申請專利範圍第13項之模塑料的用途,其係用於製造模製品。
- 一種模製品,其係可得自如申請專利範圍第1至9項中任一項之組成物或如申請專利範圍第13項之模塑料。
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US20200332113A1 (en) | 2020-10-22 |
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