TW200837127A - Filled polyolefin compositions - Google Patents
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200837127 九、發明說明: 【發明所屬之技術領域】 本發明係關於含塡料之聚烯烴組成物,具有改良之加 工性能和機械性質之平衡。 特別,雖然顯著且甚至極高量的塡料存在,本發明的 組成物能夠獲得相當高値的熔體流率(下文中簡稱爲M F R ) 連帶的具有非常有利且異常平衡之機械性質。 【先前技術】 ® 爲了增加此種組成物的最後MFR値,該技藝方面己建 議使用用具有高MFR値之丙烯聚合物。特別,根據u.S.專 利No. 49 97 875,改良之熔體流動特性及良好機械性質經由 摻合至多50重量%的纖維強化劑至具有約55至約430g/10 min之MFR値之初聚合丙烯聚合物材料而獲得。 根據U · S ·專利申請案N 〇 · 2 0 〇 6 0 2 6 4 5 5 7,具有良好抗冲 擊性質之強化聚丙烯組成物係經由摻合等高量的有機纖維 及視需要之無機纖維至具有約20至約1 5 00g/l〇min之MFR 之聚丙烯樹脂中而獲得。 實際上,該文獻之實例中所使用之丙烯聚合物的最高 MFR 値是 400-430g/10min。 【發明內容】 現己發現:撓性模數、抗衝擊性、抗拉性質及熱撓曲 溫度(下文中稱爲HDT)等的改良平衡經由摻合塡料與具 有非常高MFR値之丙烯聚合物而實現。 經由本發明組成物所獲得之其他改良性質有尺寸穩定 200837127 性,抗塑性變形性及抗環境應力裂解性。 詳細言之,本發明提供塡充性聚烯烴組成物,包括: A) 20-80重量%的聚丙烯成分; B) 20-80重量%的塡料; 其中‘ A)和B)的百分率係以A)和B)的總和爲基準而A) 係選自下列組成物: a) —種聚丙烯組成物含20-80重量%!的具有500g/10min 或更大之熔體流率(MFR1 )値之聚丙烯分率A1),及20-80 重量%的具有0.1至30g/10min之熔體流率(MFR11)値之 聚丙烯分率A11),A1)和A11)的百分率係以A1)和A11)的總和 爲基準;或 b) —種聚丙烯組成物含15-72重量%的具有500g/10min 或更大之熔體流率(MFR1)値之聚丙烯分率A1),自15-70重 量%的具有〇·1至30g/10min之熔體流率(MFRn)値之聚丙 烯分率A11),及自0.5至15重量%之相容劑Q) ’ A1),A11) 及Q)的百分率係以A1),A11)及Q)的總和爲基準; 該等分率A1)和A11)係獨立選自丙烯同元聚合物及含至多 5莫耳%之乙烯及/或C4-Cio α -烯烴之丙烯的共聚物;所有 熔體流率値係根據IS 〇 1 1 3 3,在2 3 0 °C、2.1 6 k g負載時予以 量測。 本發明的組成物較佳包括相對於A)和B)的總重量’自 20-70重量%,更佳自30-60重量%的A),及自30-80重量 %,更佳自40-70重量%的B)。 200837127 如上文中所界定之分率Α。是具有很高MFR値之丙烯 聚合物或聚合物組成物,即,具有5 00g/10min或更大,較 佳 1200g/10min或更大,尤其自 5 00 - 2 5 0 0 g/1 0mi η或自 1200-2500g/10min· 〇 而且,此等MFR値較佳無任何降解處理而獲得。換言 之,分率A1)較佳係由初聚合之丙烯聚合物所造成,在聚合 後,未歷經能實質上改變MFR値之任何處理。因此,分率 A1)的分子量亦是在使用來製備丙烯聚合物之聚合方法中 大體上直接所獲得者。 或者,但不佳,MFR値係由具有較低MFR値之丙烯聚 合物的降解(減黏)而獲得。 可能存在於分率 A1)中之丙烯共聚物的共單體係選自 乙烯及/或CiCio α -烯烴,舉例而言例如,丁烯-1,戊烯 -1,4-甲基戊烯-1,己烯-1,及辛烯-1。較佳之共單體是乙烯 和丁燒-1。 分率 Α1)的所有丙烯聚合物和共聚物可經由使用 Ziegler-Natta觸媒或以金屬芳香類爲基底之觸媒系統在聚 合方法中予以製備。該等觸媒及聚合方法在該項技藝中係 熟知。 可使用該技藝方面所熟知之習用分子量調節齊,例如 鏈轉移劑(例如氫或ZnEU )。200837127 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin composition containing a coating having a balance of improved processing properties and mechanical properties. In particular, although significant and even very high amounts of dip are present, the compositions of the present invention are capable of achieving a very high melt flow rate (hereinafter abbreviated as M F R ) with very advantageous and exceptionally balanced mechanical properties. [Prior Art] ® In order to increase the final MFR of such a composition, it has been proposed in the art to use a propylene polymer having a high MFR. In particular, according to US Patent No. 49 97 875, improved melt flow characteristics and good mechanical properties are achieved by blending up to 50% by weight of fiber reinforcement to a polymerized propylene polymerization having an MFR of from about 55 to about 430 g/10 min. Obtained from the material. According to U · S · Patent Application N 〇 · 2 0 〇 6 0 2 6 4 5 5 7, reinforced polypropylene composition with good impact resistance is blended with high amounts of organic fibers and optionally inorganic fibers Obtained in a polypropylene resin having an MFR of from about 20 to about 1 500 g/l〇min. In fact, the highest MFR 丙烯 of the propylene polymer used in the examples of this document is 400-430 g/10 min. SUMMARY OF THE INVENTION It has been found that an improved balance of flexibility modulus, impact resistance, tensile properties, and heat deflection temperature (hereinafter referred to as HDT), etc., via blending of tantalum and polymerization of propylene having a very high MFR値Realized by things. Other improved properties obtained by the compositions of the present invention are dimensionally stable 200837127, resistance to plastic deformation and resistance to environmental stress cracking. In particular, the present invention provides a rhodium-containing polyolefin composition comprising: A) 20-80% by weight of a polypropylene component; B) 20-80% by weight of a dike; wherein the percentages of 'A) and B) are Based on the sum of A) and B), A) is selected from the following compositions: a) a polypropylene composition containing 20-80% by weight of a melt flow rate of 500 g/10 min or more (MFR1) The polypropylene fraction A1), and 20-80% by weight of the melt fraction (MFR11) having a melt flow rate of 0.1 to 30 g/10 min (AFR), the percentage of A1) and A11) is A1 And the sum of A11) as a reference; or b) a polypropylene composition containing 15-72% by weight of a polypropylene fraction (AFR) having a melt flow rate (MFR1) of 500 g/10 min or more, from 15-70% by weight of a melt flow rate (MFRn) of 〇·1 to 30 g/10 min, a polypropylene fraction A11), and from 0.5 to 15% by weight of a compatibilizer Q) 'A1), A11) And the percentage of Q) is based on the sum of A1), A11) and Q); the equal parts A1) and A11) are independently selected from the group consisting of propylene homopolymers and containing up to 5 mol% of ethylene and/or Copolymer of C4-Cio α-olefin propylene; all melting The flow rate based IS square Zhi 1133, in 2 3 0 ° C, to be measured when the load g 2.1 6 k. The composition of the invention preferably comprises from 20 to 70% by weight, more preferably from 30 to 60% by weight of A), and from 30 to 80% by weight, more preferably from 40 to 40% by weight relative to the total weight of A) and B). - 70% by weight of B). 200837127 The rate of division as defined above. Is a propylene polymer or polymer composition having a very high MFR, i.e., having 500 g/10 min or more, preferably 1200 g/10 min or more, especially from 5 00 - 2 5 0 0 g / 1 0mi η Or from 1200-2500g/10min·〇, and these MFR値 are preferably obtained without any degradation treatment. In other words, the fraction A1) is preferably caused by the initial polymerization of the propylene polymer, and after the polymerization, does not undergo any treatment which substantially changes the MFR. Therefore, the molecular weight of the fraction A1) is also generally obtained directly in the polymerization method used to prepare the propylene polymer. Alternatively, but not preferred, MFR is obtained by degradation (reduction of viscosity) of a propylene polymer having a lower MFR. The co-single system of the propylene copolymer which may be present in fraction A1) is selected from the group consisting of ethylene and/or CiCio α-olefins, for example, butene-1, pentene-1, 4-methylpentene, for example 1, hexene-1, and octene-1. Preferred comonomers are ethylene and dibutyl-1. Fractions All of the propylene polymers and copolymers of Α1) can be prepared in a polymerization process via a Ziegler-Natta catalyst or a metal aromatic based catalyst system. Such catalysts and polymerization methods are well known in the art. Conventional molecular weight adjustments well known in the art, such as chain transfer agents (e.g., hydrogen or ZnEU), can be used.
Ziegler-Natta觸媒的較佳實例是受載之觸媒系統其中 包括三烷基鋁化合物,視需要,一種電子予體,及固體觸 200837127 媒成分包括Ti的鹵化物或鹵素-醇化物及視需要,受載在 無水氯化鎂上之電子予體化合物。具有上述特性之觸媒在 專利文獻中係眾所周知;特別有利者是U S P 4,3 9 9,0 5 4及 EP-A-45 977中所述之觸媒。其他實例可在USP 4,472,524 中見到。 特定Ziegler-NatU觸媒及適合於製備分率A1)的丙烯聚 合物之聚合方法掲示於EP06223 80中。 較佳’當分率A1)的丙烯聚合物使用Ziegler-Natta觸媒 予以製備時,彼等具有,在範圍自600至lOOOg/lOmin之 MFR 時、自 1 00,000-60,000 之 Mw 値,及在高於 1000g/10min 之MFR時、具有高於或等於1 40,000之Mz値,如ΕΡ06223 80 中所揭示。 使用ZUgler-Natta觸媒所製備之丙烯聚合物之其他較 佳特徵是: 自 2.5-2.8 之 Mz/Mw 値 以在室溫(25 °C )時,以不溶於二甲苯中之重量分率 計,高於或等於95 %之等規度指數,更佳高於或等於97 %。 更佳分.率A1)的丙烯聚合物係在以金屬芳香類爲基底 之觸媒系統存在時,於聚合中直接獲得。 就大體而言,此等聚合條件不須與使用Ziegler-Natta 觸媒所使用之那些聚合條件不同。 較佳之以金環屬芳香類爲基底之觸媒系統係由 a)式(I)的金屬芳香類化合物: 200837127A preferred example of a Ziegler-Natta catalyst is a supported catalyst system comprising a trialkylaluminum compound, optionally, an electron acceptor, and a solid touch 200837127 media component comprising a halide or halogen-alcohol of Ti and It is required to be supported by an electron donor compound supported on anhydrous magnesium chloride. Catalysts having the above characteristics are well known in the patent literature; particularly preferred are the catalysts described in U S P 4, 39,058 and EP-A-45 977. Other examples are found in USP 4,472,524. A specific Ziegler-NatU catalyst and a polymerization process suitable for the preparation of the propylene polymer of fraction A1) are shown in EP06223 80. Preferably, when the propylene polymer of the 'partition ratio A1' is prepared using a Ziegler-Natta catalyst, they have a Mw of from 00,000 to 60,000 at a MFR ranging from 600 to 1000 g/lOmin, and at a high At a MFR of 1000 g/10 min, there is an Mz 高于 higher than or equal to 1 40,000, as disclosed in ΕΡ06223 80. Other preferred features of the propylene polymer prepared using the ZUgler-Natta catalyst are: Mz/Mw from 2.5 to 2.8 at a room temperature (25 ° C), in a weight fraction insoluble in xylene , above or equal to 95% of the iso-index, more preferably higher than or equal to 97%. More preferably, the propylene polymer of the ratio A1) is obtained directly in the polymerization in the presence of a catalyst system based on a metal aromatic. In general, these polymerization conditions do not have to be different from those used in the Ziegler-Natta catalyst. Preferably, the catalyst system based on the genus of the genus Golden Ring is a) the metal aryl compound of the formula (I): 200837127
(I) 其中: • 、 M是屬於元素周期表中第3,4,5,6族或鑭系或锕系之過 渡金屬,較佳Μ是鈦、或鈴;X,相同或不同,是氫原子、 «素原子或 R、OR、OS〇2CF3、OCOR、sR、NR2 或 pR2 基其 中R是線性或分枝、環狀或無環之Cl_c4。烷基、C2_C4q矯 基、C2-C4。炔基、C6-C4。芳基、C7-C4〇烷芳基或C7-C4()芳烷 基;視需要,含屬於元素周期表1 3 -17族之雜原子;R較佳 疋線性或分枝C 1 - C 2 0院基,或視需要,兩個X可形成取代 或未取代之丁二烯基或〇R’〇基其中R’是選自Cl-C4()亞院 _ 基、C6-C40亞芳基、C7-C4D亞烷芳基及C7-C40亞芳烷基之二 價基;X較佳是氫原子、鹵素原子或R,更佳X是氯或Cl_Ci。 烷基,例如甲基或乙基; L是二價Ci-Cw烴基,視需要,含屬於元素周期表的 0-17族之雜原子或含至多5個矽原子之二價之亞甲矽烷 基;L較佳是二價橋連基’係条自Ci-C4。亞院基、C3-C4◦亞 環烷基、C6-C40亞芳基、C7-C4。亞烷芳基或C7-C4。亞芳烷基, 視需要,含元素周期表中1 3 -1 7族之雜原子及含至多5個 -10- 200837127 矽原子之亞甲矽烷基例如:SiMe2、SiPh2 ; L較佳是(Z (R”)2) n 其中Z是碳或矽原子,n是1或2而R”是Ci-Cao烴基,視 需要,含屬於元素周期表中13-17族之雜原子;R”較佳是 線性或分枝,環狀或無環之C^C^o烷基、C2-C2〇烯基、C2-C2。 炔基、C6-C2〇芳基、c7-C2〇烷芳基或C7-C2〇芳烷基,視需要, 含屬於元素周期表中13-17族之雜原子;更佳,(Z (R”)2) n 基是 Si( CH3) 2、SiPh2、SiPhMe、SiMe( SiMes)、CH2、(CH2) 2 及 C ( CH3 ) 2,甚至更佳(Z (R”)2) n 是 Si ( CH3 ) 2。 R1是C^-Ce烴基,視需要,含屬於元素周期表中13-17 族之雜原子;較佳R1是線性或分枝,環狀或無環之ChC^。 烷基、C2-C4。烯基、C2-C4。炔基、C6-C4D芳基、C7-C40烷芳 基或C7-C4 0芳烷基;視需要,含屬於元素周期表中13-17 族之雜原子,更佳R1是線性或分枝,飽和或不飽和之C i - C 2。 烷基。 R2、R3、R4與R5相同或相互不同,是氫原子或ChC4。 φ 烴基,視需要,含屬於元素周期表中13-17族之雜原子, 或在R2、R3、R4和R5中,兩R形成C4-C7環,其可能是不 飽和或飽和,視需要,含屬於元素周期表中1 4 -1 6族之雜 原子;所形成之環可帶有Ci-C2。烴取代基。 b)至少一種鋁腭烷或能形成烷基金屬芳香類陽離子之 化合物。 金屬芳香類化合物a)的特定實例是消旋-二甲基甲矽 烷基雙(2-甲基-4,5-苯并-印基)锆二氯化物。 -11 - 200837127 將鋁噚烷考慮爲含至少〜組的下面型式之線性、分枝 或環狀化合物:(I) where: • M is a transition metal belonging to Groups 3, 4, 5, 6 or a lanthanide or lanthanide series of the Periodic Table of the Elements, preferably 钛 or Ti; X, the same or different, is hydrogen Atom, a prime atom or a R, OR, OS〇2CF3, OCOR, sR, NR2 or pR2 group wherein R is linear or branched, cyclic or acyclic Cl_c4. Alkyl, C2_C4q, and C2-C4. Alkynyl, C6-C4. Aryl, C7-C4 nonane aryl or C7-C4() aralkyl; optionally containing a hetero atom belonging to Groups 1 3 -17 of the Periodic Table of the Elements; R preferably 疋 linear or branched C 1 - C 2 0, or optionally, two X may form a substituted or unsubstituted butadienyl or fluorene R' fluorenyl group, wherein R' is selected from the group consisting of Cl-C4(), phenyl, and C6-C40 arylene And a divalent group of a C7-C4D alkylene aryl group and a C7-C40 aralkylene group; X is preferably a hydrogen atom, a halogen atom or R, and more preferably X is chlorine or Cl_Ci. An alkyl group such as a methyl group or an ethyl group; L is a divalent Ci-Cw hydrocarbon group, optionally containing a hetero atom of Groups 0-17 belonging to the Periodic Table of the Elements or a divalent methymethylene group having up to 5 ruthenium atoms, if necessary ; L is preferably a divalent bridging group's strip from Ci-C4. Affiliation, C3-C4 ◦ cycloalkyl, C6-C40 arylene, C7-C4. Alkylene aryl or C7-C4. An aralkylene group, if necessary, a hetero atom having a group of 1 3 -1 7 of the periodic table and a methylene group containing at most 5 -10 - 10,37,37,127 atom: for example, SiMe2, SiPh2; L is preferably (Z) (R") 2) n wherein Z is a carbon or germanium atom, n is 1 or 2 and R" is a Ci-Cao hydrocarbon group, optionally containing a hetero atom belonging to Groups 13-17 of the periodic table; R" is preferred. Is linear or branched, cyclic or acyclic C^C^o alkyl, C2-C2 nonenyl, C2-C2. alkynyl, C6-C2 aryl, c7-C2 decane aryl or C7 -C2 aralkyl, optionally containing a hetero atom belonging to Groups 13-17 of the Periodic Table of the Elements; more preferably, (Z(R")2) n is Si(CH3) 2, SiPh2, SiPhMe, SiMe ( SiMes), CH2, (CH2) 2 and C(CH3) 2, even better (Z (R") 2) n is Si (CH3) 2. R1 is a C^-Ce hydrocarbon group, and if necessary, belongs to the elemental period a hetero atom of the group 13-17; preferably R1 is a linear or branched, cyclic or acyclic ChC^ alkyl, C2-C4, alkenyl, C2-C4, alkynyl, C6-C4D aryl , a C7-C40 alkaryl group or a C7-C4 0 aralkyl group; if necessary, a hetero atom belonging to Groups 13-17 of the periodic table, more preferably R1 is Sexually or branched, saturated or unsaturated C i - C 2 . Alkyl. R 2 , R 3 , R 4 and R 5 are the same or different from each other and are a hydrogen atom or a ChC 4 . φ hydrocarbon group, as required, containing 13 of the periodic table. a hetero atom of group -17, or in R2, R3, R4 and R5, two R form a C4-C7 ring which may be unsaturated or saturated, and if desired, is a group belonging to the group 14-14 of the periodic table. a hetero atom; the ring formed may carry a Ci-C2. a hydrocarbon substituent. b) at least one aluminoxane or a compound capable of forming an alkyl metal aromatic cation. A specific example of the metal aromatic compound a) is racemic- Dimethylmethane alkyl bis(2-methyl-4,5-benzo-indene) zirconium dichloride. -11 - 200837127 Considering aluminoxane as a linear, branched group containing at least a group of the following types Or cyclic compound:
其中,取代基u’相同或不同是氫原子、鹵素原子、 Cl-C2D院基、C3_C2〇fe院基、C6-C2。芳基、C7-C2。院芳基或 C 7 - C 2。芳院基’視需要’含砂或鍺原子,附有條件爲:至少 一個U與氫不同。 特別可使用下式的鋁噚烷:Among them, the substituents u' are the same or different and are a hydrogen atom, a halogen atom, a Cl-C2D yard group, a C3_C2〇fe yard group, and a C6-C2 group. Aryl, C7-C2. Courtyard aryl or C 7 - C 2 . Fangyuan base 'as needed' contains sand or helium atoms, with the condition that at least one U is different from hydrogen. In particular, aluminoxane of the formula:
i—0—(A1一0)n -A1I-0-(A1_0)n -A1
U 在線性化合物的情況中’其中n 1是〇或1- 4 0之整數而取代 基U如上文中所界定;或可使用下式的鋁噚烷··U is in the case of a linear compound wherein n 1 is an integer of 〇 or 1 - 40 and the substituent U is as defined above; or an aluminoxane of the following formula may be used
-12- 200837127 在環狀化合物的情況中,其中η2是自2-40之整數而取 代基U係如上文中所界定。 適當鋁噚烷的實例是甲基鋁噚烷(ΜΑΟ)、四(異丁基) 鋁噚烷(ΤΊΒΑΟ )、四-(2,4,4-三甲基-戊基))鋁噚烷 (ΤΙΟΑΟ)、四-(2,3-二甲基丁基)鋁曙院(TDMBAO)及四 -(2,3,3-三甲基丁基)鋁噚烷h(TTMBAO)。 能形成烷基金屬芳香類陽離子之化合物的實例是D + E-式之化合物,其中D +是布忍士特酸,能給出一個質子並與 ^ 式(I)的金屬芳香類之取代基X不可逆的反應及Ε·是可相 容之陰離子,其能將源自兩化合物的反應之活性觸媒物種 穩定化,且是充分不穩定,經由烯屬單體予以移除。陰離 子Ε_較佳包括一或多個硼原子。更佳,陰離子Ε·是ΒΑγΛ」 式的陰籬子,其中可能相同或不同之取代基Ar是芳基。例 如:苯基、五氟苯基或雙(三氟甲基)苯基。硼酸肆-五氟 苯酯是特佳化合物,例如:W09 1/02012中所述。而且,BAn φ 式之化合物可便利的使用,舉例而言,此型化合物記述於 國際專利申請案W092/003 33中。能形成烷基金屬芳香陽離 子之化合物的其他實例是BAi^P其中P是取代或未經取代 之吡咯基。此等化合物記述於WO 01/62764中。含硼原子 之所有此等化合物可以硼與金屬芳香類之金屬間之莫耳比 使用,包括約1 : 1至約1 〇 : 1之間,較佳1 : 1至2 : 1, 更佳約1 : 1。 使用金屬芳香類爲基底之觸媒系統所製備之丙烯聚合 -13 - 200837127 物的其他較佳特徵是: 分子量Mw/Mn的分布小於4,更佳小於3,最佳小於 2.7 ; 使用13C-NMR所量測之等規度五價物高於 90%,更佳高於92% ; 2 5 °C時,二甲苯中可溶物少於2重量%,更佳少於1 .6 重量% ; 藉DSC所量測之熔點高於143°C。 • 聚丙烯分率A11)可能是任何丙烯同元聚合物或具有 Q.l-30g/10min之MFR値之共聚物。因此,可將該分率a11) 以習用之聚合方法,使用習用觸媒(Ziegler-Natta或 以金屬芳香類爲基底者)予以製備。 聚丙烯分率Απ)之較佳特徵是: 自 0.5-20g/10min 之 MFR 値; 以在室溫下(約25 °C )不溶於二甲苯中之重量分率計, φ 等規度指數高於或等於92%,更佳高於或等於95% ; 共單體的數量,至多9莫耳%,更佳至多5莫耳% ; Mw/Mn大於4,更佳Mw/Mn大於7,最佳Mw/Mn大於 10 ; 在230 °C時所量計之熔體強度大於1,50 cN,尤其在 1.6 0至12.00cN之範圍內,更佳1.60至8.00cN; 可存在於A11)中之共單體的實例與上文中關於聚丙烯 分率A1)所界定者相同。 -14- 200837127 使用作爲分率 An)之特佳者是下列組成物,其中含 3 0-70重量%,較佳自40-60重量%之分率士具有以Mw/Mn 比計4-9之分子量分布及3 0_70重量%,較佳40-6 0重量% 的分率ii)具有以Mw/Mn比計大於10之分子量分布,分率 i)和ii)係獨立選自丙烯同元聚合物及含至多5莫耳%的乙 烯及/或α ·烯烴之丙烯的無規共聚物,i)和il:)的百分 率皆以i)和ii)的總和爲基準。亦可使用餾分ii)作爲分率 Απ)。 爲了獲得丙燃同兀聚合物及具有10或更大Mw/Mn値 之共聚物,可能使用不同數量之分子量調節劑(尤其是 氫),在兩或多階段中進行聚合方法。此方法的實例揭示於 EP0573 8 62中,其較佳在氣相中進行。亦可能(且較佳)使 用至少兩個互連之聚合區中所進彳了之氣相聚合方法來製備 同元聚合物和共聚物。此聚合方法記述於歐洲專利案 EP7 8 25 87及國際專利申請案WO 00/02929中。 此方法係在第一和第二互連之聚合區中進行,在觸媒 系統存在時,將丙烯和乙烯或丙烯和α -烯烴進給入該等聚 合區中,並自其中卸出所產生之聚合物。生長之聚合物粒 子在快速流體化條件下流經第一聚合區(上升管),離開第 一聚合區後,進入第二聚合區(降液管),通過此區彼等在 重力的作用下,以稠化形式流動,離開第二聚合區並再引 入第一聚合區中’如此建立聚合物在兩聚合區之間之循 環。通常,第一聚合區中快速流體化的狀況係經由進給單 -15- .200837127 體氣體混合物在生長聚合物的再引入點下面而進入第一聚 合區中。進入第一聚合區中的輸送氣體速度高於操作條件 下之輸送速度,通常是2-15 m/s之間。在第二聚合區中, 聚合物在其中受重力的作用下,以稠化形式流動,達到固 體密度的高値,其接近聚合物之體密度,因此壓力的正增 益可沿著流動的方向而獲得,以致不須機械工具的協助, 可將聚合物再引入第一反應區中。以此方式建立“環路” 循環,其經由兩聚合區間之壓力平衡及經由引入系統中之 ® 高差損失所限定。視需要,將一或數種惰性氣體,例如氮 或脂肪族烴維持在各聚合區中,其數量係使惰性氣體分壓 之總和較佳在5-80%的氣體總壓力之間。操作參數,舉例 而言例如:溫度是汽相烯烴聚合方法中通常使用者,舉例 而言:50°C -120°C,較佳 70°C -9 0°C。該方法可在 0.5-lOMPa 的操作壓力下進行,較佳在1.5-6MPa。將不同觸媒成分較 佳進給至第一聚合區,在該第一聚合區的任何位置。然而, φ 亦可將彼等進給至第二聚合區的任何位置。 提供設備在聚合方法中,此設備能完全或部分地防止 存在於上升管中之氣體及/或液體混合物進入降流管中,並 將存在於上升管中之具有與氣體混合物不同組成之氣體及 /或液體混合物引入降流管中。根據較佳實例,通過一或多 個引入管路,將具有與存在於上升管中之氣體混合物不同 組成之氣體及/或液體混合物引入降流管中,在防止後者混 合物進入降流管方面係有效。可將被運送至降流管之不同 -16 - 200837127 組成的氣體及/或液體混合物視需要,以部分或完全液化形 式予以運送。 生長聚合物的分子量分布可經由國際專利申請案wo 0 0 / 0 2 9 2 9的第4圖中圖解所tjk之反應器中及經由獨立計量 共單體和習用之分子量調節劑,特別是氫,以不同比例進 入至少一個聚合區中,較佳進入上升管中進行聚合方法而 便利的特製。 使用於本發明組成物中之塡料成分B )可能是有機或 無機。 較佳者是有機及無機纖維及其他無機塡料(與纖維不 同),例如金屬片、玻璃片、硏磨之玻璃、玻璃球及礦物塡 料。例如:滑石、碳酸鈣、雲母、矽灰石、或矽酸鹽,就 大體而論,高嶺土,硫酸鋇,金屬氧化物和氫氧化物。 另外適當塡料是木屑。 適合本發明之適當纖維包括由玻璃、金屬、陶瓷、石 墨所造成之纖維,以及有機聚合物例如:聚酯和尼龍,例 如··長絲形式的芳族聚醯胺,所有此等物件商業上可供應。 以玻璃纖維較佳。 玻璃纖辉可能是切斷玻璃纖維或長玻璃纖維’或可能 是呈連續長絲纖維的形式,唯優先給予使用玻璃纖維’亦 稱爲短纖維或切斷纖維。 就大體而論,玻璃纖維可具有自1至50mm長度。使 用於本發明組成物中之切斷或短玻璃纖維具有idmm長 -17- .200837127 ► — 'Wa- 度,更佳3-4.5mm及l〇-20um之直徑,更佳12-14um。 如先前所述,本發明之聚丙烯組成物亦可包括相容劑 Q) 0 可使用之一種型式是具有反應性極性基團之低分子量 化合物,其功能是使塡料較少親水性而因此與聚合物更可 相容。舉例而言,適當化合物是矽烷,例如··胺基矽烷, 環氧矽烷,醯胺矽烷,或丙烯矽烷。 然而’相容劑較佳包含改質(功能化)聚合物及視需 ® 要,具有反應性極性基之低分子量化合物。以改質之烯烴 聚合物,尤其丙烯同元聚合物和共聚物,例如··乙烯和丙 烯相互或與其他α 烯烴的共聚物爲最佳,因爲彼等與本發 明組成物的成分Α)可高度相容。同樣可使用改質之聚乙烯。 以結構計,改質聚合物較佳選自接枝或嵌段共聚物。 關於這一點,優先給予含自極性化合物衍生之基團之 改質聚合物,尤其選自酸酐,羧酸,羧酸衍生物,一級胺 ^ 和二級胺,經基化合物,曙哩啉和環氧化物及離子化合物。 極性化合物的特定實例是不飽和之環酐及其脂肪族二 酯,及二酸衍生物。尤其,可使用馬來酐及選自下列之化 合物:-12- 200837127 In the case of a cyclic compound, wherein η2 is an integer from 2 to 40 and the substituent U is as defined above. Examples of suitable aluminoxanes are methylalumoxane, tetrakis(isobutyl)aluminoxane (ΤΊΒΑΟ), tetrakis-(2,4,4-trimethyl-pentyl)aluminoxane ( ΤΙΟΑΟ), tetrakis-(2,3-dimethylbutyl)aluminum brothel (TDMBAO) and tetrakis-(2,3,3-trimethylbutyl)aluminoxane h (TTMBAO). An example of a compound capable of forming an alkyl metal aromatic cation is a compound of the formula D + E-, wherein D + is a succinic acid which gives a proton and a substituent X of the metal aryl group of the formula (I) The irreversible reaction and oxime is a compatible anion which stabilizes the active catalytic species derived from the reaction of the two compounds and is sufficiently unstable to be removed via the olefinic monomer. The anion Ε_ preferably includes one or more boron atoms. More preferably, the anion Ε· is a yttrium of the formula ,, wherein the substituents Ar which may be the same or different are aryl groups. For example: phenyl, pentafluorophenyl or bis(trifluoromethyl)phenyl. Barium borate-pentafluorophenyl ester is a particularly preferred compound, for example, as described in W09 1/02012. Further, a compound of the formula BAn φ can be conveniently used. For example, this type of compound is described in International Patent Application No. WO 92/003. Other examples of compounds capable of forming an alkyl metal aromatic cation are BAi^P wherein P is a substituted or unsubstituted pyrrolyl group. These compounds are described in WO 01/62764. All such compounds containing boron atoms may be used in molar ratios between boron and metal aromatic metals, including between about 1:1 and about 1 〇: 1, preferably between 1:1 and 2: 1, more preferably 1 : 1. Other preferred features of the propylene polymerization-13 - 200837127 prepared using a metal aromatic base-based catalyst system are: a molecular weight Mw/Mn distribution of less than 4, more preferably less than 3, most preferably less than 2.7; using 13C-NMR The measured isotactic pentads are higher than 90%, more preferably higher than 92%; at 25 ° C, the soluble matter in xylene is less than 2% by weight, more preferably less than 1.6% by weight; The melting point measured by DSC is higher than 143 °C. • Polypropylene fraction A11) may be any propylene homopolymer or a copolymer having an MFR of Q.l-30g/10min. Therefore, the fraction a11) can be prepared by a conventional polymerization method using a conventional catalyst (Ziegler-Natta or a metal aromatic substrate). The preferred characteristics of the polypropylene fraction Απ) are: MFR 自 from 0.5-20 g/10 min; φ isotactic index is high in the weight fraction which is insoluble in xylene at room temperature (about 25 ° C) Or equal to 92%, more preferably higher than or equal to 95%; the number of comonomers, up to 9 mol%, more preferably up to 5 mol%; Mw/Mn is greater than 4, more preferably Mw/Mn is greater than 7, most Good Mw / Mn is greater than 10; the melt strength measured at 230 ° C is greater than 1,50 cN, especially in the range of 1.6 0 to 12.00 cN, more preferably 1.60 to 8.00 cN; may be present in A11) Examples of co-monomers are the same as those defined above for the polypropylene fraction A1). -14- 200837127 The most preferred component used as the fraction An) is the following composition, which contains 30-70% by weight, preferably from 40-60% by weight, with a Mw/Mn ratio of 4-9. The molecular weight distribution and the fraction of 30 to 70% by weight, preferably 40 to 60% by weight ii) have a molecular weight distribution greater than 10 in terms of Mw/Mn ratio, and the fractions i) and ii) are independently selected from the group consisting of propylene homopolymerization. And random copolymers of propylene containing up to 5 mole % of ethylene and/or alpha olefins, i) and il:) are based on the sum of i) and ii). Fraction ii) can also be used as the fraction Απ). In order to obtain a fluorinated homofluorene polymer and a copolymer having 10 or more Mw/Mn?, it is possible to carry out the polymerization method in two or more stages using different amounts of molecular weight regulators (especially hydrogen). An example of such a process is disclosed in EP0573 8 62, which is preferably carried out in the gas phase. It is also possible (and preferred) to use a gas phase polymerization process carried out in at least two interconnected polymerization zones to prepare the homopolymers and copolymers. This polymerization method is described in European Patent No. EP 7 8 25 87 and International Patent Application WO 00/02929. The process is carried out in a polymerization zone of the first and second interconnects, in the presence of a catalyst system, feeding propylene and ethylene or propylene and alpha-olefin into the polymerization zone and discharging therefrom polymer. The grown polymer particles flow through the first polymerization zone (rising tube) under rapid fluidization conditions, and after leaving the first polymerization zone, enter the second polymerization zone (downcomer), through which the gravity is under the action of Flowing in a thickened form, leaving the second polymerization zone and reintroducing into the first polymerization zone' thus establishing a cycle of polymer between the two polymerization zones. Typically, the condition of rapid fluidization in the first polymerization zone enters the first polymerization zone via a feed mono-15-200837127 body gas mixture below the reintroduction point of the growing polymer. The velocity of the transport gas entering the first polymerization zone is higher than the transport velocity under operating conditions, typically between 2-15 m/s. In the second polymerization zone, the polymer flows in a thickened form under the action of gravity to reach a high density of solid density, which is close to the bulk density of the polymer, so that the positive gain of the pressure can be obtained along the direction of the flow. The polymer can be reintroduced into the first reaction zone without the assistance of a mechanical tool. In this way a "loop" cycle is established which is defined by the pressure equalization of the two polymerization zones and by the ® height difference loss introduced into the system. If desired, one or more inert gases, such as nitrogen or aliphatic hydrocarbons, are maintained in each polymerization zone in an amount such that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total gas pressure. Operating parameters, for example, temperature are typical users of vapor phase olefin polymerization processes, for example: 50 ° C - 120 ° C, preferably 70 ° C - 9 0 ° C. The process can be carried out at an operating pressure of from 0.5 to 10 MPa, preferably from 1.5 to 6 MPa. Preferably, different catalyst components are fed to the first polymerization zone at any location in the first polymerization zone. However, φ can also feed them to any location in the second polymerization zone. Providing a device in a polymerization process that completely or partially prevents a gas and/or liquid mixture present in the riser from entering the downcomer and will present a gas of a different composition than the gas mixture present in the riser and / or a liquid mixture is introduced into the downcomer. According to a preferred embodiment, a gas and/or liquid mixture having a different composition than the gas mixture present in the riser is introduced into the downcomer through one or more inlet lines to prevent the latter mixture from entering the downcomer. effective. The gas and/or liquid mixture consisting of -16 - 200837127, which is transported to the downcomer, can be transported in partial or complete liquefaction as needed. The molecular weight distribution of the growing polymer can be illustrated in the reactor of tjk illustrated in Figure 4 of the International Patent Application WO 0 0 / 0 2 9 2 9 and via separate metered comonomers and conventional molecular weight regulators, in particular hydrogen It is convenient to enter the at least one polymerization zone in different proportions, preferably into the riser tube for the polymerization method. The tanning component B) used in the composition of the present invention may be organic or inorganic. Preferred are organic and inorganic fibers and other inorganic materials (as opposed to fibers) such as metal flakes, glass flakes, honed glass, glass spheres and mineral coatings. For example: talc, calcium carbonate, mica, ash, or strontium, in general, kaolin, barium sulfate, metal oxides and hydroxides. Another suitable material is wood chips. Suitable fibers suitable for the present invention include fibers derived from glass, metals, ceramics, graphite, and organic polymers such as polyesters and nylons, such as aromatic polyamines in the form of filaments, all of which are commercially available. Available. It is preferred to use glass fibers. The glass fiber may be in the form of cut glass fibers or long glass fibers or may be in the form of continuous filament fibers, with the exception of the use of glass fibers, also referred to as staple fibers or staple fibers. In general, glass fibers can have a length of from 1 to 50 mm. The cut or short glass fibers used in the composition of the present invention have an idmm length of -17-.200837127 ► - 'Wa-degree, more preferably 3-4.5 mm and a diameter of l〇-20 um, more preferably 12-14 um. As described previously, the polypropylene composition of the present invention may also include a compatibilizing agent Q). One type that can be used is a low molecular weight compound having a reactive polar group, the function of which is to make the tanning less hydrophilic and thus More compatible with polymers. For example, suitable compounds are decane, such as amino decane, epoxy decane, decyl decane, or propylene decane. However, the compatibilizer preferably comprises a modified (functionalized) polymer and, if desired, a low molecular weight compound having a reactive polar group. Modified olefin polymers, especially propylene homopolymers and copolymers, such as copolymers of ethylene and propylene with each other or with other alpha olefins, because they are compatible with the composition of the present invention. Highly compatible. It is also possible to use modified polyethylene. The modified polymer is preferably selected from the group consisting of graft or block copolymers by structure. In this connection, preference is given to modifying polymers comprising groups derived from polar compounds, in particular selected from the group consisting of anhydrides, carboxylic acids, carboxylic acid derivatives, primary amines and secondary amines, via compounds, porphyrins and rings. Oxides and ionic compounds. Specific examples of polar compounds are unsaturated cyclic anhydrides and their aliphatic diesters, and diacid derivatives. In particular, maleic anhydride and a compound selected from the group consisting of:
Ci-Ci。線性和分枝之馬來酸二烷酯、匕-Cm線性和分枝 之富馬酸二烷酯、衣康酸酐、C! - C !。線性和分枝之衣康酸二 烷酯、馬來酸、富馬酸、衣康酸及其混合物。特佳爲使用 以馬來酐所接枝之丙烯聚合物作爲改質聚合物者。 -18- 200837127 低分子量化合物用來偶合塡料至改質聚合物而因此牢 固的黏合它至丙烯聚合物成分A)。通常,此等是雙官能化 合物,在此情況中,一個官能基可進入與塡料成爲結合相 互作用。而第二官能基可進入與改質聚合物成爲結合相互 作用。低分子量化合物較佳是胺基或環氧矽院,更佳是胺 基矽烷。 當塡料B)包括玻璃纖維時,具有矽烷羥基之胺基矽烷 鍵結合至玻璃纖維,同時胺基,舉例而言與以馬來酐所接 枝之聚丙烯形成一穩定醯胺鍵。 將彼等倂合入組成物中之前,施加低分子量化合物至 玻璃纖維是特別有利。 改質聚合物可以簡單方式,係經由在自由基產生劑(例 如··有機過氧化物)存在時,聚合物與例如馬來酐的反應 性擠壓而製造,例如:EP05 7 2028中所揭示。 改質聚合物中自極性化合物衍生之基團的較佳量是自 〇·5至3重量%。 改質聚合物之MFR的較佳値是50-400g/10min.。 亦可能使用母料其包括呈預混合形式之塡料和相容 劑。 根據本發明之聚烯烴組成物係由熔化和混合各成分可 獲得’混合可在混合裝置於通常爲180°C -310°C之溫度有效 進行,較佳爲 190°C-28(TC,更佳爲 20(TC-25(TC。 爲了此目的,可使用任何熟知之裝置。 -19- .200837127 關於這一點,有用之混合裝置特別是擠壓機或捏揉 機,特佳爲雙螺桿擠壓機。亦可能在室溫時,於混合裝置 中預混合各成分。 爲了減少混合裝置中之磨耗及纖維斷裂(當使用纖維 作塡料時)較佳初始熔化成分A),及視需要,成分Q),隨 後將成分B)與熔體混合。 在製備本發明的聚丙烯組成物期間,除去兩主要成分 A)和B)及可能某些相容劑Q)以外,可能引入該技藝中一般 ® 所使用之添加劑,例如··穩定劑(對抗熱、光、U.V.)塑 化劑,抗靜電劑及拒水劑。 本發明組成物之特佳特徵是: 密度:自 1.1 至 4kg/dm3,更佳 1.1 至 1.8kg/dm3; 撓曲模數:自 2500至 1 9000MPa,更佳 5000至 17000MPa ; 抗拉模數:2500-20000MPa,更佳 5,000- 1 8,000MPa; φ 23°C時,查皮(查皮)無缺口:自 30-200kJ/m2,更 佳 35-65 kJ/m2 ; -30°C時,查皮無缺口:自 30-150 U/m2,更佳 40-70 kJ/m2 ; 23°C 時,查皮缺口 :自 5-200 kJ/m2,更佳自 10-20kJ/m2; 30 °C時,查皮缺口 :自 50- 1 50 kJ/m2,更佳自 10-25kJ/m2 ; 斷裂時抗拉強度:自50-150 MPa,更佳自80-140 MPa; -20- 200837127 斷裂伸長率:自1 -200%,特別自1·5 % ; HDT 1.8MPa:自 60- 1 55 °C,更佳自 1 3 5 - 1 5 5 °C。 由於其各種性質的有利平衡,可使用本發明組成物在 許多應用方面,例如:射出成型製品,尤其是汽車組件, 電氣用具,傢具,或就大體而言,成形之製品,特別是片 板,電氣用具組件,傢倶,家用器具,或作爲超塡充之母 料。 特別,當成分B)的量是特別高時,相對於A)和B)之總 重量,指示自50-80重量%,藉由與額外之聚合物摻合, 本發明組成物亦可有利地使用作爲濃縮物,導引塡料入聚 合組成物中,特別是導入聚烯烴組成物中。 爲了舉例說明,示出下列實例但是無限制之目的。 使用下列分析方法進行測定,敘述中及實例中所記述 之各種性質。 溶體流率(MFR ) : IS01133,在 230°C 時,負載 2.16kg; • 極限黏度:在135°C時,於四氫化萘中所量測; 密度:IS01 183 ; 燒曲模數(正割):IS0178在80xl〇x4mm長方形樣品 上,自T-桿IS0527-1 1A型量測; 抗拉模數(正割):IS0527/-1、-2在1 A型之樣品上具 有lmm/min之速度,50mm之跨距; 查皮無缺口 = ISO 179 ( 1型,沿邊),在80x10x4mm長 方形樣品上,自T-杆,IS0 527-1 1A型; -21- 200837127 查皮無缺口: ISO 179( 1型,沿邊,缺口 A )在80x1 0x4mm 長方形樣品上,自T-杆,IS0527-1 1A型; 斷裂時抗拉強度:IS0527/-1、-2,在1A型樣品上,具 有5 0mm/ min之速度,50mm之跨距; 斷_裂俥長率:IS〇5 27/- 1、-2,在1 A型樣品上,具有50mm/ min之速度,50mm之跨距; HDT ( 1.80MPa):(熱撓曲溫度)IS〇7 5 A -1、- 2在樣品 clause6 上。 • T-杆製備(射出成型) 試驗樣品係根據ISO 1 87 3 -2試驗方法(1 989 )予以射 出成型。 篕規度指數的測定(在室溫下,於二甲苦中之溶解度,以 重量%計) 將2.5g聚合物及250cm3之二甲苯引入配置有冷凍機和 磁性攬拌器之玻璃燒瓶中。於3 0分鐘內,將溫度上昇直至 • 溶劑的沸點。將如此獲得之透明溶液保持在回流下,並攪 拌歷另外30分鐘。然後將封閉之燒瓶保持在冰和水的恆溫 水浴中歷3 0分鐘。及同樣保持在2 5 °C之恒溫水浴中歷3 0 分鐘。將如此形成之固體在快速濾紙上過濾。將丨〇〇cm3經 過濾之液體倒入先前稱重之鋁容器中,將其在氮氣流動 下’在加熱板上加熱以便經由蒸發移除容劑。然後將容器 保持在真空下之80°C烘箱中直至獲得恆定重量。然後計算 在室溫時可溶於二甲苯中之聚合物的重量%。 -22- 200837127 將在室溫時不溶於二甲苯中之聚合物的重量%作爲聚 合物之等規度指數。此數値大體上相當於經由沸騰之正庚 烷萃取所測定之等規度指數,按照定義,其構成聚丙烯的 等規度指數。 MWD測定Ci-Ci. Linear and branched dialkyl maleate, 匕-Cm linear and branched dialkyl fumarate, itaconic anhydride, C! - C!. Linear and branched diacontanates, maleic acid, fumaric acid, itaconic acid, and mixtures thereof. It is particularly preferred to use a propylene polymer grafted with maleic anhydride as a modified polymer. -18- 200837127 Low molecular weight compounds are used to couple the dip to the modified polymer and thus firmly bond it to the propylene polymer component A). Typically, these are difunctional compounds, in which case one functional group can enter into a binding interaction with the dip. The second functional group can enter into a binding interaction with the modified polymer. The low molecular weight compound is preferably an amine group or an epoxy broth, more preferably an amino decane. When the bake material B) comprises glass fibers, the amine decane having a decane hydroxy group is bonded to the glass fibers, while the amine group, for example, forms a stable amide bond with the polypropylene grafted with maleic anhydride. It is particularly advantageous to apply a low molecular weight compound to the glass fibers prior to their incorporation into the composition. The modified polymer can be produced in a simple manner by reactive extrusion of the polymer with, for example, maleic anhydride in the presence of a free radical generator (for example, an organic peroxide), as disclosed in, for example, EP 05 7 2028 . The preferred amount of the group derived from the polar compound in the modified polymer is from 5 to 3% by weight. A preferred enthalpy of the MFR of the modified polymer is 50-400 g/10 min. It is also possible to use a masterbatch which comprises a premixed form of the dip and compatibilizer. The polyolefin composition according to the present invention can be obtained by melting and mixing the components. The mixing can be carried out efficiently at a temperature of usually from 180 ° C to 310 ° C in a mixing apparatus, preferably from 190 ° C to 28 ° C (TC, more Good for 20 (TC-25 (TC. For this purpose, any well-known device can be used. -19-.200837127) In this regard, useful mixing devices, especially extruders or kneading machines, especially for twin-screw extrusion It is also possible to premix the ingredients in the mixing device at room temperature. In order to reduce the abrasion and fiber breakage in the mixing device (when using fiber as a material), the preferred initial melting component A), and, if desired, the composition Q), component B) is subsequently mixed with the melt. In addition to the two main components A) and B) and possibly some compatibilizers Q) during the preparation of the polypropylene composition of the present invention, it is possible to introduce additives which are generally used in the art, such as stabilizers. Heat, light, UV) plasticizer, antistatic agent and water repellent. Particularly preferred features of the composition of the invention are: Density: from 1.1 to 4 kg/dm3, more preferably from 1.1 to 1.8 kg/dm3; flexural modulus: from 2500 to 1 9000 MPa, more preferably from 5,000 to 17,000 MPa; tensile modulus: 2500-20000MPa, better 5,000-1 8,000MPa; φ 23°C, no inspection of the skin (chapi): from 30-200kJ/m2, better 35-65 kJ/m2; at -30°C, check No gap in the skin: from 30-150 U/m2, better 40-70 kJ/m2; at 23 °C, the inspection gap: from 5-200 kJ/m2, more preferably from 10-20kJ/m2; 30 °C When, the inspection gap: from 50 - 1 50 kJ / m2, better from 10-25kJ / m2; tensile strength at break: from 50-150 MPa, more preferably from 80-140 MPa; -20- 200837127 elongation at break Rate: from 1 - 200%, especially from 1 / 5 %; HDT 1.8MPa: from 60 - 1 55 ° C, more preferably from 1 3 5 - 1 5 5 °C. Due to the advantageous balance of its various properties, the compositions of the invention can be used in a number of applications, for example, injection molded articles, especially automotive components, electrical appliances, furniture, or, in general, shaped articles, particularly sheets, Electrical appliance components, furniture, household appliances, or as a masterbatch for super-filling. In particular, when the amount of component B) is particularly high, the composition of the invention may advantageously be blended with from 50 to 80% by weight, based on the total weight of A) and B), by blending with additional polymer. Used as a concentrate to direct the feed into the polymeric composition, especially into the polyolefin composition. For purposes of illustration, the following examples are shown but are not limiting. The following analytical methods were used to determine the various properties described in the examples and in the examples. Solution flow rate (MFR): IS01133, load 2.16 kg at 230 ° C; • ultimate viscosity: measured in tetralin at 135 ° C; density: IS01 183; calcined modulus (positive Cut): IS0178 on 80xl〇x4mm rectangular sample, measured from T-rod IS0527-1 1A type; tensile modulus (cutting): IS0527/-1, -2 has lmm/ on sample of type A Min speed, 50mm span; no skin gap = ISO 179 (type 1, edge), on 80x10x4mm rectangular sample, from T-bar, IS0 527-1 1A; -21- 200837127 No skin: ISO 179 (type 1, edge, notch A) on 80x1 0x4mm rectangular specimen, from T-bar, IS0527-1 1A; tensile strength at break: IS0527/-1, -2, on type 1A, with Speed of 50 mm/min, span of 50 mm; length of splitting_breaking: IS〇5 27/- 1, 2, with a speed of 50 mm/min and a span of 50 mm on a type A sample; HDT ( 1.80 MPa): (heat deflection temperature) IS〇7 5 A -1, -2 on sample Clause6. • T-rod preparation (injection molding) The test sample is injection molded according to the ISO 1 87 3 -2 test method (1 989). Determination of the 篕 degree index (solubility in dimethyl bitterness at room temperature, in % by weight) 2.5 g of the polymer and 250 cm 3 of xylene were introduced into a glass flask equipped with a freezer and a magnetic stirrer. Within 30 minutes, the temperature is raised until the boiling point of the solvent. The clear solution thus obtained was kept under reflux and stirred for another 30 minutes. The closed flask was then kept in a constant temperature water bath of ice and water for 30 minutes. And keep it in a constant temperature water bath at 25 ° C for 30 minutes. The solid thus formed was filtered on a fast filter paper. The 丨〇〇cm3 filtered liquid was poured into a previously weighed aluminum container, which was heated under a nitrogen flow to remove the solvent via evaporation. The vessel was then held in an 80 ° C oven under vacuum until a constant weight was obtained. The weight % of the polymer soluble in xylene at room temperature is then calculated. -22- 200837127 The weight % of the polymer insoluble in xylene at room temperature is taken as the isotactic index of the polymer. This number is substantially equivalent to the isocratic index determined by boiling n-heptane extraction, which by definition constitutes the isotactic index of polypropylene. MWD measurement
Mn/Mw値係經由在145°C時之凝膠透過層析法(GPC) 予以量測。使用具有1 3um粒子大小之配置三個混合床管柱 TosoHaasTSK GMHXL-HT 之 Alliance GPCV2000 儀器 I ( Waters )進行。管柱的尺寸是300x7.8mm。所使用之移動 相是真空蒸餾之1,2,4-三氯苯(TCB )並將流速保持在 1 .Oml/min。樣品溶液經由在攪拌下,在145乞時於TCB中 加熱樣品歷二小時予以製備。濃度是lmg/ml。爲了防止降 解,添加0.1 g/Ι的2,6-二第三丁基-對-甲酚。將3 26.5从L 之溶液注射入管柱組中。使用具有分子量在自5 80至 7,50〇,〇〇〇範圍內之10個聚苯乙烯標準樣品(由Polymer 0 Laboratories製造之EasiCal kit)獲得校正曲線;來自相同 製造商之具有11,600,000至13,200,000的尖峰分子量之另 外兩其他標準品亦包括在內。假定Mark-Houwink關係式的 K値是: · 對聚苯乙烯標準品K = 1.21xl(T4dL/g及α = 0.706。 對聚丙烯樣品 K = 1.90xl(T4dL/g 及 α = 0.7 25。 對丙烯共聚物樣品K = 1.93xl0_4dL/g及α = 0.7 25。 使用第三階多項式於配合用以內插實驗數據並獲得校 -23- 200837127 正曲線》數據獲得和處理係經由使用 Waters公司之具有 G P C V選擇之E m ρ 〇 w e r 1.0予以完成。 熔體溫度 係根據IS03 146,使用20K/min的加熱速率進行,以 DSC予以測定。 13C-NMR (對金屬芳香類產牛▲之丙烯聚合物) NMR分析PP的"C-NMR光譜在120°C以Fourier轉換 模式,在100.61MHz時操作之DPX-400/分光計上獲得。使 ^ 用mmmm五價物碳分別在21.8ppm和29.9ppm的尖峰作爲 內參考。將樣品溶入120°C之1,1,2,2,-四氯乙烷-d2中,在 5mm管中具有8% wt/v濃度。各光譜係使用90°脈衝而獲 得,脈衝間有12秒之延遲及CPD( WALTZ 16 )來移除1H-13C 耦合。使用6000Hz的譜窗,將約2500暫態存儲在32K數 據點中。 PP 光譜的鑑定係根據 “Selectivity in Propylene • Polymerization with Metallocene Catalysts ,L.Resconi, L.Cavallo,A. Fait, F. Piemontesi, Chem.Rev, 1 00, 1 253, (2000 )) mmmm含量使用鏡像位置模型,模擬實驗五價物 分布而獲得。具有2,1(E)和1,3(H)誤差的高含量之PP 的 mmmm 含量獲得爲〔mmmm〕= 100( Σ〔 CH3〕·5〔 mrrm〕 -5〔E〕-5〔H〕)/ ( Σ 〔CH3〕)其中 Σ 〔CH3〕是 CH3 基的 總和。 2,1和3,1誤差的含量獲得爲: -24- 200837127 [E]= 100 ( Ε9/Σ [CH2]) [Η] = 100 ( 0.5Π2/ Σ [CH2]) 其中E9是在42.14ppm的尖峰,H2是在30.82ppm的尖 峰及Σ [CH2]是所有CH2的總和。 熔體強度 所使用之裝置是具有用於數據處理之電子計算機 Toyo-Sieki Seisakusho有限公司製造之熔體張力試驗機。該 方法在於量測以特定伸展速度所伸展之熔融聚合物單紗的 ® 抗拉強度。特別,將被試驗之聚合物在2 3 0 °C時,以 0.2mm/min通過具有8mm長和1mm直徑之毛細孔的模子予 以擠壓,然後將出口之單紗經由使用牽引滑輪的系統,以 0.000 6m/sec2固定加速度予以拉伸,量測張力直至斷點。該 裝置記綠單紗的張力値作拉伸的函數。該熔體強度相當於 聚合物斷裂時之熔體張力。 實例1至15及比較性竇例1辛3 φ 使用下列材料作爲成分A),B)和Q)。 成分 A) PP-1 :丙烯同元聚合物,具有2300g/10min的MFR,2.6 之Mw/Mn及在室溫下,於二甲苯中,98.5%的等規度指數 (等規五價物(mmmm)高於92%),146 °C之DSC熔化溫 度,0.47 dl/g之固有黏度,呈九粒的形式。 PP-2:丙烯同元聚合物,具有Ug/lOmin的MFR,5.4 之Mw/Mn及96.7%的等規度指數,呈九粒的形式。 -25- 200837127 PP-3 :含 1.6重量%的乙烯之丙烯共聚物,3g/10min 之MFR,19.2之Mw/Mn及9 6%的等規度指數,呈九粒的形 式。 PP-4:丙嫌同元聚合物,具有550g/10min之MFR,2,3 之M w/Mn及98.7%的在室溫下,於二甲苯中的等規度指數 (等規五價物(mmmm)高於92% ),145.3°C之DSC熔化 溫度,0.69 dl/g之固有黏度,呈九粒的形式。 PP-5:丙烯同元聚合物,具有2.5g/10min之MFR,8.4 之Mw/Mn及6.74cN的熔體強度,呈九粒的形式。 PP-1係經由使用消旋-二甲基甲矽烷基雙(2-甲基-4, 5-苯并-印基)銷二氯化物,使用如PCT/EP2004/007061形 式中所述之觸媒系統而獲得。 將如PCT/EP2004/00706 1形式中所述,獲得之形式爲觸 媒泥漿之觸媒系統進給入預接觸容器中,在其中,將它用 約5 ( Kg/h )之丙烷稀釋。自預接觸容器,將該觸媒系統進 φ 給至預聚合環路,同時將丙烯進給入其中。預聚溫度是45 °C。觸媒在預聚合環路中之滯留時間是8分鐘。然後將預 聚合環路中所獲得之經預聚觸媒連續進給入環路反應器 中,將丙烯以340Kg/h之速率進給入其中。聚合溫度是70 °C。將聚合物自環路反應器中卸出,與未反應之單體分離 並予以乾燥。產物的MFR由進給氫予以控制,調節進給量 而得到聚合物所需要之MFR。在PP-1的情況中,氫濃度是 1080ppm 〇 -26- 200837127 pp_4係以與ΡΡ-l之相同方式予以製備’其差別是將丙 烯以329Kg/h之速率進給,氫進料是550ppm° 成分B): GF :玻璃纖維,白ECS 03T 480 (日本電氣玻璃有限公 司)具有3mm之纖維長度及13//m之直徑。 成分 Q): PP-MA :使用馬來酐(MA)接枝之丙烯同元聚合物, 具有115g/10min之MFR及1重量%之MA含量(由Chemtura ^ 公司所售之Polybond 3200)。 成分A)亦含約0.3重量%的習用之抗氧化劑添加劑。 實例 13中,其亦含以重量計 300ppm之酞花青藍 (PV-Echtblau 2GLSP,Clariant)。實例 14 中,其亦含 0.18 %的Mi llad 3988 3,4-二甲基亞苯甲基花楸醇。 該組成物係由使用雙螺桿擠壓機,Werner& Pfleiderer ZSK40SC型進行擠壓予以製備。此線具有大槪43L/D的加 φ 工處理長度並具有重量進料器。經由施力側進料,將成分 A)和Q)進給入第一筒管中,及將成分B)進給入第五筒管 中〇 使用具有冷却浴和單紗切刀Scheer SGS100之單紗模 板來形成九粒;亦施加真空除氣(筒管Νο·8 )來萃取^氣 和分解產物。 操作條件: 螺桿速率:200rpm· -27-Mn/Mw lanthanum was measured by gel permeation chromatography (GPC) at 145 °C. The Alliance GPCV2000 Instrument I (Waters) with three mixed bed columns TosoHaasTSK GMHXL-HT with a particle size of 13 μm was used. The size of the string is 300x7.8mm. The mobile phase used was vacuum distilled 1,2,4-trichlorobenzene (TCB) and the flow rate was maintained at 1.0 ml/min. The sample solution was prepared by heating the sample in TCB for two hours at 145 Torr with stirring. The concentration is 1 mg/ml. To prevent degradation, 0.1 g/Ι of 2,6-di-t-butyl-p-cresol was added. A solution of 3 26.5 from L was injected into the column set. A calibration curve was obtained using 10 polystyrene standards (EasiCal kit manufactured by Polymer 0 Laboratories) having a molecular weight in the range of 580 to 7,50 Å, ;; from the same manufacturer having 11,600,000 to Two other standards for the peak molecular weight of 13,200,000 are also included. Assuming the K値 of the Mark-Houwink relationship is: • For polystyrene standards K = 1.21xl (T4dL/g and α = 0.706. For polypropylene samples K = 1.90xl (T4dL/g and α = 0.7 25. The propylene copolymer sample K = 1.93xl0_4dL/g and α = 0.7 25. The third-order polynomial was used to interpolate the experimental data and obtain the -23-200837127 positive curve. The data was obtained and processed by using Waters' GPCV. The selected E m ρ 〇wer 1.0 was completed. The melt temperature was measured according to IS03 146 using a heating rate of 20 K/min and determined by DSC. 13 C-NMR (for propylene polymers of metal aromatics ▲) NMR The "C-NMR spectrum of the analysis PP was obtained on a DPX-400/spectrometer operating at 100.61 MHz in a Fourier conversion mode at 120 ° C. The peak of 21.8 ppm and 29.9 ppm was used as the peak of the mmmm pentad carbon Internal reference. The sample was dissolved in 1,1,2,2,-tetrachloroethane-d2 at 120 ° C and had a concentration of 8% wt/v in a 5 mm tube. Each spectrum was obtained using a 90° pulse. There is a 12 second delay between pulses and CPD (WALTZ 16) to remove 1H-13C coupling. Use 6000Hz spectrum , about 2500 transients are stored in 32K data points. The identification of PP spectra is based on "Selectivity in Propylene • Polymerization with Metallocene Catalysts, L. Resconi, L. Cavallo, A. Fait, F. Piemontesi, Chem. Rev, 1 00, 1 253, (2000)) The mmmm content was obtained by simulating the experimental pentads distribution using the mirror position model. The mmmm content of the high content PP with 2,1 (E) and 1,3 (H) errors was obtained as [mmmm] = 100 (Σ[CH3]·5[ mrrm] -5[E]-5[H])/ ( Σ [CH3]) wherein Σ [CH3] is the sum of CH3 groups. 2, 1 and 3, 1 The error content is obtained as: -24- 200837127 [E]= 100 ( Ε9/Σ [CH2]) [Η] = 100 (0.5Π2/ Σ [CH2]) where E9 is the peak at 42.14ppm and H2 is at The peak of 30.82 ppm and Σ [CH2] is the sum of all CH2. The device used for melt strength is a melt tension tester manufactured by Toyo-Sieki Seisakusho Co., Ltd., an electronic computer for data processing. The method consists in measuring the tensile strength of the molten polymer single yarn stretched at a specific stretching speed. Specifically, the polymer to be tested was extruded at 0.2 mm/min through a mold having pores of 8 mm in length and 1 mm in diameter at 0.2 mm/min, and then the single yarn of the outlet was passed through a system using a traction sheave. Stretch at a fixed acceleration of 0.000 6 m/sec 2 and measure the tension until the break point. The device records the tension of the green single yarn as a function of stretching. The melt strength corresponds to the melt tension at which the polymer breaks. Examples 1 to 15 and Comparative Sinus Case 1 辛 3 φ The following materials were used as the components A), B) and Q). Ingredient A) PP-1: propylene homopolymer having an MFR of 2300 g/10 min, Mw/Mn of 2.6 and an isotactic index of 98.5% in xylene at room temperature (isotactic pentad ( Mmmm) is higher than 92%), DSC melting temperature at 146 °C, intrinsic viscosity of 0.47 dl/g, in the form of nine particles. PP-2: a propylene homopolymer having an MFR of Ug/lOmin, an Mw/Mn of 5.4, and an isotactic index of 96.7% in the form of nine particles. -25- 200837127 PP-3: a propylene copolymer containing 1.6% by weight of ethylene, an MFR of 3g/10min, an Mw/Mn of 19.2 and an isotactic index of 96%, in the form of nine particles. PP-4: a generic polymer of propylene, having an MFR of 550 g/10 min, an M w/Mn of 2,3, and an isotactic index (isotactic pentads) in xylene at room temperature at 98.7%. (mmmm) higher than 92%), 145.3 ° C DSC melting temperature, 0.69 dl / g of intrinsic viscosity, in the form of nine. PP-5: a propylene homopolymer having an MFR of 2.5 g/10 min, a Mw/Mn of 8.4, and a melt strength of 6.74 cN in the form of nine particles. PP-1 is via the use of racemic-dimethylformamidinium bis(2-methyl-4,5-benzo-indene) pin dichloride, using the touch as described in PCT/EP2004/007061 Obtained by the media system. The catalyst system obtained in the form of a catalyst slurry is fed into a precontacted vessel as described in the form of PCT/EP2004/00706 1 in which it is diluted with about 5 (Kg/h) of propane. From the precontacted vessel, the catalyst system is fed φ to the prepolymerization loop while propylene is fed therein. The prepolymerization temperature is 45 °C. The residence time of the catalyst in the prepolymerization loop is 8 minutes. The prepolymerized catalyst obtained in the prepolymerization loop was then continuously fed into the loop reactor, and propylene was fed therein at a rate of 340 Kg/h. The polymerization temperature was 70 °C. The polymer is discharged from the loop reactor, separated from the unreacted monomer and dried. The MFR of the product is controlled by the feed hydrogen, and the feed rate is adjusted to obtain the MFR required for the polymer. In the case of PP-1, the hydrogen concentration was 1080 ppm. 〇-26-200837127 pp_4 was prepared in the same manner as ΡΡ-1. The difference was that propylene was fed at a rate of 329 Kg/h, and the hydrogen feed was 550 ppm. Ingredient B): GF: Glass fiber, white ECS 03T 480 (Japan Electric Glass Co., Ltd.) has a fiber length of 3 mm and a diameter of 13//m. Ingredient Q): PP-MA: a propylene homopolymer polymer grafted with maleic anhydride (MA) having an MFR of 115 g/10 min and an MA content of 1 wt% (Polybond 3200 sold by Chemtura Company). Ingredient A) also contains about 0.3% by weight of a conventional antioxidant additive. In Example 13, it also contained 300 ppm by weight of phthalocyanine blue (PV-Echtblau 2GLSP, Clariant). In Example 14, it also contained 0.18 % of Mi llad 3988 3,4-dimethylbenzylidenesterol. The composition was prepared by extrusion using a twin-screw extruder, Werner & Pfleiderer ZSK40SC. This line has a length of 43L/D plus φ processing length and has a weight feeder. The components A) and Q) are fed into the first bobbin via the force-feeding side, and the component B) is fed into the fifth bobbin, using a single bath with a cooling bath and a single yarn cutter Scheer SGS100 The yarn template is used to form nine particles; vacuum degassing (bobbin Νο·8) is also applied to extract gas and decomposition products. Operating conditions: Screw speed: 200rpm· -27-
.200837127 容量:5 0 筒管溫度 * 將如此獲 列於表I至V 60kg/h. :200-220〇C . 得之組成物的最後性質連同相對數量的成分 中。.200837127 Capacity: 5 0 Bobbin temperature * This will be listed in Tables I to V 60 kg / h. : 200-220 ° C. The final properties of the resulting composition together with the relative amount of ingredients.
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表I 樣本編號 1 2 3 4 組成成份(重量%) PP4 17.6 23.75 23,75 15.9 PP-2 17.6 23.75 擊 15.8 PP-3 17.6 - 23.75 15.8 GF 45 50 50 50 PP-MA 2.2 2.5 2.5 2.5 A) 55 50 50 50 B) . 45 50 50 50 A丨) 32 47.5 47.5 31.8 A11) 64 47.5 47.5 63.2 Q) 4 5 5 5 i) 50 100 • 50 ϋ) 50 - 100 50 性質 密度(kg/dm3) 1.275 1.334 1.333 1.330 MFR(dg/min) 5.3 14.6 6 6.5 撓曲模數(MPa) 10090 11630 11370 11470 抗拉模數(MPa) 10440 12010 12100 12110 23°C查皮無缺口 (k〗/m2) 61.2 51 63.8 56.4 -30°C 查皮無缺口(kJ/m2) 67.5 52 68.9 61 23°C 查皮缺 口(1^/1112) 13 13.7 13.8 13 -30°C 查皮缺 口(1^/1112) 16.8 18,1 17.9 19 斷裂拉伸強度(MPa) 121.1 127 130 129 斷裂伸長率(%) 2.5 1.8 2.4 1.9 HDT 1.82N(〇C) 150 148 146 149 -29- 200837127Table I Sample No. 1 2 3 4 Composition (% by weight) PP4 17.6 23.75 23,75 15.9 PP-2 17.6 23.75 Shot 15.8 PP-3 17.6 - 23.75 15.8 GF 45 50 50 50 PP-MA 2.2 2.5 2.5 2.5 A) 55 50 50 50 B) . 45 50 50 50 A丨) 32 47.5 47.5 31.8 A11) 64 47.5 47.5 63.2 Q) 4 5 5 5 i) 50 100 • 50 ϋ) 50 - 100 50 Nature density (kg/dm3) 1.275 1.334 1.333 1.330 MFR(dg/min) 5.3 14.6 6 6.5 Flexural modulus (MPa) 10090 11630 11370 11470 Tensile modulus (MPa) 10440 12010 12100 12110 23°C inspection without gap (k〗/m2) 61.2 51 63.8 56.4 -30°C No peeling of skin (kJ/m2) 67.5 52 68.9 61 23°C Inspection gap (1^/1112) 13 13.7 13.8 13 -30°C Inspection gap (1^/1112) 16.8 18, 1 17.9 19 Tensile strength at break (MPa) 121.1 127 130 129 Elongation at break (%) 2.5 1.8 2.4 1.9 HDT 1.82N (〇C) 150 148 146 149 -29- 200837127
表II 樣本編號 5 6 7 組成成份(重量%) PP-1 14 14.1 12.34 PP-2 15.8 14.1 12.33 PP-3 17.7 14.1 12.33 GF 50 55 60 PP-MA 2.5 2.7 3 A) 50 45 40 B) 50 55 60 A丨) 28 31.3 30.8 A11) 67 62.7 61.7 Q) 5 6 7.5 i) 47.2 50 50 ii) 52.8 50 50 性質 密度(kg/dm3) 1.335 1.404 1.453 MFR(dg/min) 5.9 4.7 3,4 撓曲模數(MPa) 11360 12500 14080 抗拉模數(MPa) 12150 12960 14250 23°C查皮無缺口 (kJ/m2) 57.2 49.4 46 -30°C 查皮無缺口 (ld/m2) 61 57 49 23°C 查皮缺口 (kJ/m2) 13.1 12.7 12.2 -30°C 查皮缺口(U/m2) 19.3 19 18.5 斷裂拉伸強度(MPa) 126.6 126.3 122 斷裂伸長率(%) 2.2 1.7 1.7 HDT 1·82ΝΓ〇 148 149.2 148 -30- 200837127Table II Sample No. 5 6 7 Composition (% by weight) PP-1 14 14.1 12.34 PP-2 15.8 14.1 12.33 PP-3 17.7 14.1 12.33 GF 50 55 60 PP-MA 2.5 2.7 3 A) 50 45 40 B) 50 55 60 A丨) 28 31.3 30.8 A11) 67 62.7 61.7 Q) 5 6 7.5 i) 47.2 50 50 ii) 52.8 50 50 Properties Density (kg/dm3) 1.335 1.404 1.453 MFR(dg/min) 5.9 4.7 3,4 Deflection Modulus (MPa) 11360 12500 14080 Tensile modulus (MPa) 12150 12960 14250 23°C no-notch (kJ/m2) 57.2 49.4 46 -30°C No-notch (ld/m2) 61 57 49 23 °C Inspection gap (kJ/m2) 13.1 12.7 12.2 -30°C Inspection gap (U/m2) 19.3 19 18.5 Tensile strength at break (MPa) 126.6 126.3 122 Elongation at break (%) 2.2 1.7 1.7 HDT 1· 82ΝΓ〇148 149.2 148 -30- 200837127
表III 樣本編號 8 9 10 11 組成成份(重量%) PP4 35.5 12.8 18,5 PP-4 18.5 PP-3 12 34.2 18.5 PP-5 - - 18.5 GF 50 50 60 60 PP-MA 2.5 3 3 3 A) 50 50 40 40 B) 50 50 60 60 A1) 71 25.6 46.25 46.25 A11) 24 68.4 46.25 46.25 Q) 5 6 7.5 7.5 性質 密度(kg/dm3) 1.330 1.331 1.469 1.476 MFR(dg/min) 6.2 1.3 4.6 10.2 撓曲模數(MPa) 11250 11130 14350 13770 抗拉模數(MPa) 12020 11800 14570 13890 23°C查皮無缺口(k]/m2) 59 62 52 55 -30°C 查皮無缺口(kJ/m2) 61 65 54 52 23°C查皮缺口汰1/1112) 13.8 13.7 13.4 13.6 -3CTC 查皮缺口 (kJ/m2) 17.4 18.1 21 20 斷裂拉伸強度(MPa) 129 127 131 120 斷裂伸長率(%) 2.2 2.5 2 1.2 HDT 1.82N(〇C) 146 147 150 148 -31- 200837127Table III Sample No. 8 9 10 11 Composition (% by weight) PP4 35.5 12.8 18,5 PP-4 18.5 PP-3 12 34.2 18.5 PP-5 - - 18.5 GF 50 50 60 60 PP-MA 2.5 3 3 3 A) 50 50 40 40 B) 50 50 60 60 A1) 71 25.6 46.25 46.25 A11) 24 68.4 46.25 46.25 Q) 5 6 7.5 7.5 Property density (kg/dm3) 1.330 1.331 1.469 1.476 MFR(dg/min) 6.2 1.3 4.6 10.2 Variance (MPa) 11250 11130 14350 13770 Tensile modulus (MPa) 12020 11800 14570 13890 23°C no gap (k]/m2) 59 62 52 55 -30°C No gap (kJ/m2) 61 65 54 52 23°C inspection snips 1/1112) 13.8 13.7 13.4 13.6 -3CTC inspection gap (kJ/m2) 17.4 18.1 21 20 tensile strength at break (MPa) 129 127 131 120 elongation at break (%) ) 2.2 2.5 2 1.2 HDT 1.82N (〇C) 146 147 150 148 -31- 200837127
表IV 樣本編號 12 13 14 15 組成成份(重量%) PP-1 18.5 18.5 18.5 15.85 PP-2 18.5 - • 養 PP-3 - 18.5 18.5 15.85 GF 60 60 60 65 PP-MA 3 3 3 3.3 A) 40 40 40 35 B) 60 60 60 65 A1) 46.25 46.25 46.25 45.29 A11) 46.25 46.25 46.25 45.29 Q) 7.5 7.5 7.5 9.42 性質 密度(kg/dm3) 1.470 1.476 1.475 1.557 MFR(dg/min) 9.9 5.9 6.8 3.8 撓曲模數(MPa) 14110 14420 14350 15050 抗拉模數(MPa) 14200 14630 14750 16060 23DC查皮無缺口(kJ/m2) 43 45 44 40 -30°C 查皮無缺口(kJ/m2) 46 47 47 41 23°C 查皮缺口(kJ/m2) 13,1 12.7 13,7 12.4 -30°C查皮缺口(k】/m2) 21 22 21 21.5 斷裂拉伸強度(MPa) 121 127 130 121 斷裂伸長率(%) 1.7 2.2 2 L6 HDT 1.82N(〇C) 150 148 148 150 -32- 200837127Table IV Sample No. 12 13 14 15 Composition (% by weight) PP-1 18.5 18.5 18.5 15.85 PP-2 18.5 - • Nutrient PP-3 - 18.5 18.5 15.85 GF 60 60 60 65 PP-MA 3 3 3 3.3 A) 40 40 40 35 B) 60 60 60 65 A1) 46.25 46.25 46.25 45.29 A11) 46.25 46.25 46.25 45.29 Q) 7.5 7.5 7.5 9.42 Property density (kg/dm3) 1.470 1.476 1.475 1.557 MFR(dg/min) 9.9 5.9 6.8 3.8 Flexing Modulus (MPa) 14110 14420 14350 15050 Tensile modulus (MPa) 14200 14630 14750 16060 23DC uncovered (kJ/m2) 43 45 44 40 -30°C No gap (kJ/m2) 46 47 47 41 23°C Chapi gap (kJ/m2) 13,1 12.7 13,7 12.4 -30°C inspection gap (k)/m2) 21 22 21 21.5 Tensile strength at break (MPa) 121 127 130 121 Elongation at break Rate (%) 1.7 2.2 2 L6 HDT 1.82N (〇C) 150 148 148 150 -32- 200837127
表V •30°C 查皮缺口(kJ/m2)Table V • 30°C inspection gap (kJ/m2)
HDT 1.82N(〇C) 根據下列astm方法,亦量測某些上述材料上HDT 1.82N (〇C) is also measured on some of the above materials according to the following ast method
撓性, 抗衝擊,和抗拉等性質。 撓曲 ( MPa ) : ASTM D790 ; 撓曲 ( MPa) : ASTM D790 ; 23 °C 時一,艾氏缺口 ( J/m ) ·· ASTM D256A ; -30〇C 篆,1 庄.缺口( J/m) : ASTM D25 6A ; -33- 200837127 抗拉強度(MPa ) : ASTM D63 8 ; 斷裂伸長率(% ) : ASTM D63 8. 結果列於表VI中,其中所試驗之材料經由參照先前所 述之實例予以鑑別。 樣本編號 2 3 4 7 15 性質 撓曲模數(MPa) 8480 11310 11420 14100 15450 撓曲強度(MPa) 168 192 177 165 183 23°C 艾氏缺□(kJ/m2) 98.5 129 130 116 107 -30°C 艾氏缺 口(1^/1112) 125 139 144 140 134 抗拉強度(MPa) 116 115 123 118 98 斷裂伸長率(%) 2.8 1.5 2 1.6 1.5Flexibility, impact resistance, and tensile properties. Flexing ( MPa ) : ASTM D790 ; Flexing ( MPa ) : ASTM D790 ; 23 ° C , Ehrlich notch ( J / m ) · · ASTM D256A ; -30 〇 C 篆 , 1 Zhuang . Gap ( J / m) : ASTM D25 6A ; -33- 200837127 Tensile strength (MPa ) : ASTM D63 8 ; Elongation at break (%) : ASTM D63 8. The results are shown in Table VI, where the materials tested were referred to by reference Examples are identified. Sample No. 2 3 4 7 15 Property Flexural Modulus (MPa) 8480 11310 11420 14100 15450 Flexural Strength (MPa) 168 192 177 165 183 23°C Ehrlich Defect (kJ/m2) 98.5 129 130 116 107 -30 °C Ehrlich notch (1^/1112) 125 139 144 140 134 Tensile strength (MPa) 116 115 123 118 98 Elongation at break (%) 2.8 1.5 2 1.6 1.5
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