CN103403079A - 添加剂混合物 - Google Patents
添加剂混合物 Download PDFInfo
- Publication number
- CN103403079A CN103403079A CN2012800110759A CN201280011075A CN103403079A CN 103403079 A CN103403079 A CN 103403079A CN 2012800110759 A CN2012800110759 A CN 2012800110759A CN 201280011075 A CN201280011075 A CN 201280011075A CN 103403079 A CN103403079 A CN 103403079A
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- China
- Prior art keywords
- acid
- component
- butyl
- agent mixture
- additive agent
- Prior art date
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- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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Abstract
一种添加剂混合物,其包含:(A)由组分(A1)和(A2)构成的二元体系,其中:(A1)为至少一种式(I)的有机环状磷酸酯,其中R0为直接键、-S-、C3-C12亚环烷基或基团-C(X1)(X2)-,其中X1和X2彼此独立地为氢、C1-C18烷基或C3-C12环烷基;且基团R1相同且为C1-C18烷基或未被取代或被1、2或3个C1-C4烷基取代的C3-C12环烷基;且(A2)为至少一种未被取代或被-OH取代的饱和或不饱和脂族单或二羧酸的碱金属或碱土金属盐;和(B)二价金属醇盐,其中所述金属为Zn、Ca或Mg。
Description
本发明涉及一种添加剂混合物、包含天然或合成聚合物和所述添加剂混合物的组合物、相应的母料、借助所述添加剂混合物使天然或合成聚合物成核的方法和降低天然或合成聚合物的雾度值的方法。
更详细地,本发明涉及一种添加剂混合物,其包含:
(A)由组分(A1)和(A2)构成的二元体系,其中:
(A1)为至少一种式(I)的有机环状磷酸酯:
其中R0为直接键、-S-、C3-C12亚环烷基或基团-C(X1)(X2)-,其中X1和X2彼此独立地为氢、C1-C18烷基或C3-C12环烷基;且基团R1相同且为C1-C18烷基或未被取代或被1、2或3个C1-C4烷基取代的C3-C12环烷基;且
(A2)为至少一种未被取代或被-OH取代的饱和或不饱和脂族单或二羧酸的碱金属或碱土金属盐;和
(B)二价金属醇盐,其中所述金属为Zn、Ca或Mg。
组分(A1)、(A2)和(B)的化合物是已知的且如果无法商购获得的话,可根据已知方法制备。
组分(A)与组分(B)的二元体系可显示出协同增效效果。
组分(A1):(A2)的摩尔比优选为1:5-5:1,特别为1:2-2:1,例如约1:1。
组分(A):(B)的重量比优选为1:20-20:1,特别为1:5-5:1,例如1:2-2:1。
具有至多18个碳原子的烷基的实例为甲基、乙基、正丙基、1-甲基乙基、正丁基、2-甲基丙基、1-甲基丙基、叔丁基、戊基、1-甲基丁基、2-甲基丁基、3-甲基丁基、1,1-二甲基丙基、1-乙基丙基、叔丁基甲基、己基、1-甲基戊基、庚基、异庚基、1-乙基己基、2-乙基戊基、1-丙基丁基、辛基、壬基、异壬基、新壬基、2,4,4-三甲基戊基、十一烷基、十三烷基、十五烷基、十七烷基和十八烷基。基团R1的优选含义为支化C3-C8烷基,例如C3-C5烷基,特别是叔丁基。
C3-C12环烷基,优选C3-C5环烷基的实例为环己基。
被1、2或3个C1-C4烷基取代的C3-C12环烷基的实例为α-甲基环己基。
组分(A1)优选为式(I-1)或(I-2)的化合物:
R0优选为直接键、-S-、-CH2-或-CH(C1-C18烷基)-;且
基团R1优选为C1-C12烷基、环己基或甲基环己基。
未被取代或被-OH取代的饱和或不饱和脂族单或二羧酸的实例为癸酸、新癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、十九烷酸、花生酸、山萮酸、二十四烷酸、蜡酸、褐煤酸、蜂花酸、4-十碳烯酸、5-十二碳烯酸、粗租酸、棕榈油酸、岩芹酸、油酸、反油酸和11-十八碳烯酸。
优选月桂酸、肉豆蔻酸、硬脂酸、褐煤酸和油酸。
组分(A2)的碱金属或碱土金属阳离子的优选实例为Li+、Na+、K+、Mg+、Ca2+、Ba2+、Al3+和Al(OH)2+。
根据本发明的另一优选实施方案,组分(A2)为C10-C20链烷醇盐,其中阳离子为Li+、Na+、K+、Mg+、Ca2+、Ba2+、Al3+或Al(OH)2+。
根据优选实施方案,(A2)为月桂酸、肉豆蔻酸、硬脂酸、褐煤酸或油酸的Li盐,特别为硬脂酸Li。
根据本发明的优选实施方案,组分(B)为多羟基(C2-C20烷烃)的二价金属醇盐。
所述二价金属醇盐的粒度优选使得80%的颗粒具有不大于100nm的尺寸,根据激光分析测定。
所述二价金属醇盐特别地衍生自多羟基(C2-C10烷烃),例如乙二醇(=1,2-乙烷二醇)或甘油(=1,2,3-丙烷三醇)。
根据特别优选的实施方案,所述二价金属醇盐为甘油锌(CAS登记号87189-25-1)。
特别优选微粉化的甘油锌。
所述二价金属醇盐可为单体、低聚物或聚合物,特别为聚合物。
所述金属醇盐优选为通过例如如US-A-5,475,123(此处通过引用)并入所述的锌化合物与多羟基化合物的反应形成的聚合物物质。
所述醇盐基本上是已知的且可商购获得或者可根据例如US-A-5,475,123或US-A-7,074,949所述的已知方法制备。市售的合适甘油Zn例如为Prifer3881(RTM)甘油Zn或Prifer3888(RTM)纳米尺寸的甘油Zn。
本发明的特别优选的实施方案涉及一种添加剂混合物,其中组分(A1)为式(I-1)或(I-2)的化合物:
组分(A2)为硬脂酸Li;且
组分(B)为甘油Zn。
本发明的另一实施方案为一种组合物,其包含如下组分:
(I)天然或合成有机聚合物,优选合成有机聚合物,特别是聚烯烃;和
(II)如上所定义的添加剂混合物。
组分(I)的实例为:
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基环己烷、聚异戊二烯或聚丁二烯、以及环烯烃的聚合物,例如环戊烯或降冰片烯的聚合物,聚乙烯(其可任选交联),例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、(VLDPE)和(ULDPE)。
聚烯烃,即前段中所例示的单烯烃聚合物(优选聚乙烯和聚丙烯)可通过不同方法,尤其是通过下述方法制备:
a)自由基聚合(通常在高压和升高的温度下)。
b)使用催化剂的催化聚合,所述催化剂通常包含一种或多于一种周期表第IVb、Vb、VIb或VIII族的金属。这些金属通常具有一个或多于一个配体,典型地为氧化物、卤化物、醇盐、酯、醚、胺、烷基、链烯基和/或芳基,其可为π-或σ-共轭的。这些金属配合物可呈游离形式或固定在基体上,典型地固定在活化氯化镁、氯化钛(III)、氧化铝或二氧化硅上。这些催化剂可溶于或不溶于聚合介质中。所述催化剂自身可单独用于聚合反应中或可使用其他活化剂,典型的为烷基金属、金属氢化物、烷基金属卤化物、烷基金属氧化物或烷基金属烷(metal alkyloxane),所述金属为周期表第Ia、IIa和/或IIIa族的元素。活化剂可用其他酯、醚、胺或甲硅烷基醚基团方便地改性。这些催化剂体系通常称为Philips、Standard Oil Indiana、Ziegler(-Natta)、TNZ(DuPont)、茂金属或单中心催化剂(SSC)。
1)中提及的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物、聚丙烯与聚乙烯的混合物(例如PP/HDPE、PP/LDPE)以及不同类型聚乙烯的混合物(例如LDPE/HDPE)。
单烯烃和二烯烃彼此之间或与其他乙烯基单体的共聚物,例如乙烯/丙烯共聚物、线性低密度聚乙烯(LLDPE)及其与低密度聚乙烯(LDPE)的混合物、丙烯/丁-1-烯共聚物、丙烯/异丁烯共聚物、乙烯/丁-1-烯共聚物、乙烯/己烯共聚物、乙烯/甲基戊烯共聚物、乙烯/庚烯共聚物、乙烯/辛烯共聚物、乙烯/乙烯基环己烷共聚物、乙烯/环烯烃共聚物(例如乙烯/降冰片烯,例如COC)、乙烯/1-烯烃共聚物(其中1-烯烃原位产生);丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、乙烯/乙烯基环己烯共聚物、乙烯/丙烯酸烷基酯共聚物、乙烯/甲基丙烯酸烷基酯共聚物、乙烯/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物及其盐(离聚物)、以及乙烯与丙烯及二烯(例如己二烯、二环戊二烯或亚乙基降冰片烯)的三元共聚物;和这些共聚物彼此之间的混合物以及与上述1)中提及的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA和交替或无规聚亚烷基(polyalkylene)/一氧化碳共聚物及其与其他聚合物(如聚酰胺)的混合物。
4.烃树脂(例如C5-C9),包括其氢化改性产物(例如增粘剂)及聚亚烷基和淀粉的混合物。
1.)-4.)的均聚物及共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
5.聚苯乙烯、聚对甲基苯乙烯、聚α-甲基苯乙烯。
6.衍生自乙烯基芳族单体的芳族均聚物和共聚物,所述单体包括苯乙烯、α-甲基苯乙烯、乙烯基甲苯的所有异构体,尤其是对乙烯基甲苯,乙基苯乙烯的所有异构体、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽及其混合物。均聚物和共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
6a.包括上述乙烯基芳族单体及选自下述共聚单体的共聚物:乙烯、丙烯、二烯、腈、酸、马来酸酐类、马来酰亚胺类、乙酸乙烯酯和氯乙烯或丙烯酸系衍生物及其混合物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(共聚物)、苯乙烯/甲基丙烯酸烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸烷基酯、苯乙烯/马来酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;苯乙烯共聚物与其他聚合物(例如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物)的高抗冲混合物;以及苯乙烯的嵌段共聚物如苯乙烯/丁二烯/苯乙烯、苯乙烯/异戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b.由上述6.)中提及的聚合物氢化衍生的氢化芳族聚合物,尤其是包括由无规聚苯乙烯氢化制得的聚环己基乙烯(PCHE),通常称为聚乙烯基环己烷(PVCH)。
6c.由上述6a.)中提及的聚合物氢化衍生的氢化芳族聚合物。
均聚物和共聚物可具有任何立体结构,包括间规、等规、半等规或无规;其中优选无规聚合物。也包括立体嵌段聚合物。
7.乙烯基芳族单体(如苯乙烯或α-甲基苯乙烯)的接枝共聚物,例如苯乙烯接枝的聚丁二烯、苯乙烯接枝的聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物;苯乙烯和丙烯腈(或甲基丙烯腈)接枝的聚丁二烯;苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝的聚丁二烯;苯乙烯和马来酸酐接枝的聚丁二烯;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝的聚丁二烯;苯乙烯和马来酰亚胺接枝的聚丁二烯;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝的聚丁二烯;苯乙烯和丙烯腈接枝的乙烯/丙烯/二烯三元共聚物;苯乙烯和丙烯腈接枝的聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯;苯乙烯和丙烯腈接枝的丙烯酸酯/丁二烯共聚物、及其与6)中所列共聚物的混合物,例如称为ABS、MBS、ASA或AES聚合物的共聚物的混合物。
8.含卤素的聚合物,例如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化或溴化共聚物(卤丁橡胶)、氯化或氯磺化聚乙烯、乙烯和氯化乙烯的共聚物、表氯醇均聚物及共聚物,尤其是含卤素的乙烯基化合物的聚合物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯;及其共聚物如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。
9.衍生自α,β-不饱和酸及其衍生物的聚合物,例如聚丙烯酸酯和聚甲基丙烯酸酯;聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈,其用丙烯酸丁酯进行抗冲击改性。
10.9.)中所提及的单体彼此之间的共聚物或与其他不饱和单体的共聚物,例如丙烯腈/丁二烯共聚物、丙烯腈/丙烯酸烷基酯共聚物、丙烯腈/丙烯酸烷氧基烷基酯或丙烯腈/乙烯基卤共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.衍生自不饱和醇及胺或其酰基衍生物或缩醛的聚合物,例如聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙基酯或聚烯丙基三聚氰胺;及其与上述1.)中所提及的烯烃的共聚物。
12.环醚的均聚物和共聚物,例如聚亚烷基二醇、聚氧化乙烯、聚氧化丙烯或其与二缩水甘油基醚的共聚物。
13.聚缩醛如聚甲醛和含有氧化乙烯作为共聚单体的那些聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
14.聚苯醚和聚苯硫醚、以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15.聚氨酯,其一方面衍生自羟基封端的聚醚、聚酯或聚丁二烯,另一方面衍生自脂族或芳族多异氰酸酯及其前体。
16.聚酰胺和共聚酰胺,其衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺,例如聚酰胺4、聚酰胺6、聚酰胺6/6、6/10、6/9、6/12、4/6、12/12、聚酰胺11、聚酰胺12、由间二甲苯二胺和己二酸获得的芳族聚酰胺;在存在或不存在作为改性剂的弹性体下由六亚甲基二胺与间苯二甲酸和/或对苯二甲酸制备的聚酰胺,例如聚-2,4,4-三甲基六亚甲基对苯二甲酰胺或聚间亚苯基间苯二甲酰胺;以及上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键合或接枝的弹性体的嵌段共聚物;或与聚醚,例如与聚乙二醇、聚丙二醇或聚四亚甲基二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;以及在加工过程中缩合的聚酰胺(RIM聚酰胺体系)。
17.聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑。
18.聚酯,其衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应的内酯或交酯,例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、聚萘二甲酸亚烷基酯和聚羟基苯甲酸酯以及衍生自羟基封端聚醚的共聚醚酯;以及用聚碳酸酯或MBS改性的聚酯。共聚酯可包括,例如(但不限于):聚琥珀酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸丁二醇酯/对苯二甲酸丁二醇酯、聚己二酸四亚甲基酯/对苯二甲酸四亚甲基酯、聚琥珀酸丁二醇酯/己二酸丁二醇酯、聚琥珀酸丁二醇酯/碳酸丁二醇酯、聚-3-羟基丁酸酯/3-羟基辛酸酯共聚物、聚-3-羟基丁酸酯/3-羟基己酸酯/3-羟基癸酸酯三元共聚物。此外,脂族聚酯可包括,例如(但不限于):聚(羟基链烷酸酯)类,特别为聚丙内酯、聚丁内酯、聚新戊内酯、聚戊内酯和聚己内酯、聚琥珀酸乙二醇酯、聚琥珀酸丙二醇酯、聚琥珀酸丁二醇酯、聚琥珀酸六亚甲基酯、聚己二酸乙二醇酯、聚己二酸丙二醇酯、聚己二酸丁二醇酯、聚己二酸六亚甲基酯、聚草酸乙二醇酯、聚草酸丙二醇酯、聚草酸丁二醇酯、聚草酸六亚甲基酯、聚癸二酸乙二醇酯、聚癸二酸丙二醇酯、聚癸二酸丁二醇酯和聚乳酸(PLA)以及用聚碳酸酯或MBS改性的相应聚酯。术语“聚乳酸(PLA)”表示优选为聚-L-丙交酯的均聚物及其与其他聚合物的任何共混物或合金;乳酸或丙交酯与其他单体的共聚物,所述其他单体例如羟基羧酸如乙醇酸、3-羟基丁酸、4-羟基丁酸、4-羟基戊酸、5-羟基戊酸、6-羟基己酸及其环状形式;术语“乳酸”或“丙交酯”包括L-乳酸、D-乳酸、其混合物及二聚物,即L-丙交酯、D-丙交酯、内消旋丙交酯及其任何混合物。
19.聚碳酸酯和聚酯碳酸酯。
20.聚酮。
21.聚砜、聚醚砜和聚醚酮。
22.交联聚合物,其一方面衍生自醛,另一方面衍生自酚类、脲类和三聚氰胺类,例如苯酚/甲醛树脂、尿素/甲醛树脂及三聚氰胺/甲醛树脂。
23.干性和非干性醇酸树脂。
24.不饱和聚酯树脂,其衍生自饱和和不饱和二羧酸与多元醇以及作为交联剂的乙烯基化合物的共聚酯,及其低可燃性的含卤改性产物。
25.可交联丙烯酸系树脂,其衍生自取代的丙烯酸酯,例如丙烯酸环氧酯、氨基甲酸酯丙烯酸酯或聚酯丙烯酸酯。
26.用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸酯树脂。
27.交联环氧树脂,其衍生自脂族、脂环族、杂环族或芳族缩水甘油基化合物,例如双酚A及双酚F的二缩水甘油醚的产物,其在存在或不存在促进剂下使用常规硬化剂如酸酐或胺交联。
28.天然聚合物例如纤维素、橡胶、明胶及其化学改性的同系衍生物,例如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚,例如甲基纤维素;以及松香及其衍生物。
29.上述聚合物的共混物(聚合物共混物),例如PP/EPDM、聚酰胺/EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/PBT、PVC/CPE、PVC/丙烯酸酯、POM/热塑性PUR、PC/热塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA6,6及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
30.天然和合成的有机材料,其为纯单体化合物或这些化合物的混合物,例如矿物油、动物和植物脂肪、油和蜡,或基于合成酯(例如邻苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)的油、脂肪和蜡,以及合成酯与矿物油的任意重量比的混合物,典型地为用作纺丝组合物的那些,以及这些材料的含水乳液。
31.天然或合成橡胶的含水乳液,例如天然胶乳或羧化苯乙烯/丁二烯共聚物的胶乳。
组分(I)的优选合成聚合物列于上述项目1-3下。
所述合成聚合物的特别优选的实例为聚丙烯均聚物、无规共聚物、交替或多嵌段共聚物、嵌段共聚物或聚丙烯与其他合成聚合物的共混物。
最优选聚丙烯无规共聚物和均聚物作为组分(I)。
丙烯/乙烯共聚物包含例如50-99.9重量%,优选80-99.9重量%,特别是90-99.9重量%的丙烯。
其中共聚单体为C9-C20α-烯烃如1-壬烯、1-癸烯、1-十一碳烯、1-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯或1-二十碳烯,C9-C20链烷二烯、C9-C12环烷烃二烯或降冰片烯衍生物如5-亚乙基-2-降冰片烯(ENB)或亚甲基-domethylene-六氢萘(MEN)的丙烯共聚物优选包含大于90mol%,特别是90-99.9mol%或90-99mol%的丙烯。
其中共聚单体为C4-C8α-烯烃如1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯或4-甲基-1-戊烯,乙烯基环己烷、乙烯基环己烯、C4-C8链烷二烯或C5-C8环烷二烯的丙烯共聚物优选包含大于80mol%,特别是80-99.9mol%或80-99mol%的丙烯。
组分(I)的其他实例为丙烯/异丁烯共聚物、丙烯/丁二烯共聚物、丙烯/环烯烃共聚物,丙烯与乙烯和二烯如己二烯、二环戊二烯或亚乙基降冰片烯的三元共聚物;丙烯/1-烯烃共聚物,其中1-烯烃原位产生;和丙烯/一氧化碳共聚物。
组分(I)的其他实例为聚丙烯与丙烯/乙烯共聚物、丙烯/丁烯共聚物、聚乙烯如HDPE或LDPE、聚丁烯、聚异丁烯、聚-4-甲基戊烯或交替或无规聚亚烷基/一氧化碳共聚物的共混物。这些共混物优选包含至少50重量%的聚丙烯,相对于总共混物的重量。
组分(II)的添加剂混合物优选以0.0001-5%,例如0.001-5%,0.001-2%,0.005-1%,0.01-1%或0.01-0.5%的量存在,相对于组分(I)的重量。
本发明的另一优选实施方案涉及一种组合物,其包含相对于组分(I)的重量例如为0.001-5%,优选0.01-5%的一种或多种常规成核剂作为其他组分(III-1)。
常规成核剂的实例为:
1)芳族二缩醛,例如:
●1,3:2,4-双(亚苄基)山梨糖醇,以Irgaclear D(RTM)、Millad3905(RTM)和Gel All D(RTM)商购获得。
●1,3:2,4-双(4-甲基亚苄基)山梨糖醇,以Irgaclear DM(RTM)、Millad3940(RTM)、NC-6(Mitsui(RTM))和Gel All MD(RTM)商购获得。
●1,3:2,4-双(3,4-二甲基亚苄基)山梨糖醇,以Millad3988(RTM)商购获得。
●1,3:2,4-双(4-乙基亚苄基)山梨糖醇,以NC-4(Mitsui(RTM))商购获得。
●1,2,3-三脱氧-4,6:5,7-双-O-[(4-丙基苯基)亚甲基]nonitol,以MilladNX8000(RTM)商购获得。
2)基于羧酸的盐,如苯甲酸钠的成核剂。
3)基于羧基氢氧化铝的成核剂,例如双[4-(叔丁基)苯甲酸]氢氧化铝,以Sandostab4030(RTM)商购获得。
4)分别基于松香、松香酸的盐的成核剂,例如:
●Pinecrystal KM-1300(RTM),
●Pinecrystal KM-1600(RTM)。
5)顺式内型双环(2.2.1)庚烷2,3-二甲酸的二钠盐(=化学文摘登记号351870-33-2),以Hyperform HPN-68(RTM)商购获得,和六氢邻苯二甲酸的钙盐,以Hyperform HPN-20E(RTM)商购获得。
本发明的组合物具有优异的结晶性、高透射率、高透明度、低雾度和/或改善的热稳定性。
因此,本发明的另一实施方案为一种降低天然或合成有机聚合物的雾度值的方法,其包括向其中引入如上所定义的添加剂混合物。
本发明的又一实施方案涉及一种提高天然或合成有机聚合物的结晶温度的方法,其包括向所述合成聚合物中引入如上所定义的添加剂混合物。结晶温度可例如提高超过3℃,特别是超过5℃。尤其优选结晶温度提高4-30℃,例如4-25℃或4-20℃。
雾度可根据ASTM D1003测定。雾度定义为与入射光线偏离平均超过2.5°的透过试样(板)的透射光百分比。透明度以小于2.5°的角度评价。所述试样应具有基本面平行且不含灰尘、油脂、划痕和污点的表面,且应不含明显的内部孔洞和颗粒。
本发明的另一实施方案涉及一种改善天然或合成有机聚合物的机械性能的方法,例如却贝冲击强度或弯曲模量,其包括向其中引入如上所定义的添加剂混合物。
本发明的组合物可通过本领域技术人员公知的复合的标准程序制备,例如将指定的组分在常规混合器中混合并用单或双螺杆挤出机将所述混合物熔融并捏合等。
可通过使用本领域已知的任何技术将本发明的添加剂混合物例如以包含浓度例如为0.5-50重量%或1-50重量%,特别是0.5-10重量%或1-10重量%的粉末、颗粒、浓缩物、喷雾涂料或母料形式,以纯净形式或者与其他共添加剂和任选的根据公知和常规的技术的合适载体材料一起添加至所述天然或合成有机聚合物中。
因此,本发明的一个实施方案为母料,其包含天然或合成聚合物和相对于所述天然或合成聚合物的重量优选为0.5-10%,特别为0.5-5%的本发明的添加剂混合物。
可任选向本发明的组合物中添加浓度为不负面影响本发明有益效果的其他材料,例如相容性聚合物、改性剂或添加剂。优选相对于待稳定的材料为0.001-10%,特别是0.001-1%的浓度。这些添加剂可包括稳定剂、抗氧化剂、抗菌剂、紫外吸收剂、热稳定剂、光稳定剂、中和剂、抗静电剂、抗粘连剂、重金属减活剂、阻燃剂、过氧化物、水滑石、发泡剂、弹性体、其他成核剂等及其混合物。
这些常规添加剂的更详细的实例列于下文中。
1.抗氧化剂
1.1烷基化单酚,例如2,6-二叔丁基-4-甲基苯酚、2-叔丁基-4,6-二甲基苯酚、2,6-二叔丁基-4-乙基苯酚、2,6-二叔丁基-4-正丁基苯酚、2,6-二叔丁基-4-异丁基苯酚、2,6-二环戊基-4-甲基苯酚、2-(α-甲基环己基)-4,6-二甲基苯酚、2,6-二(十八烷基)-4-甲基苯酚、2,4,6-三环己基苯酚、2,6-二叔丁基-4-甲氧基甲基苯酚,侧链为线性或支化的壬基酚例如2,6-二壬基-4-甲基苯酚、2,4-二甲基-6-(1'-甲基十一烷-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十七烷-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十三烷-1'-基)苯酚及其混合物。
1.2.烷硫基甲基苯酚,例如2,4-二辛硫基甲基-6-叔丁基苯酚、2,4-二辛硫基甲基-6-甲基苯酚、2,4-二辛硫基甲基-6-乙基苯酚、2,6-二(十二烷硫基甲基)-4-壬基苯酚。
1.3.氢醌类和烷基化氢醌类,例如2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸3,5-二叔丁基-4-羟基苯酯、己二酸双(3,5-二叔丁基-4-羟基苯基)酯。
1.4.生育酚类,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(维生素E)。
1.5.羟基化硫代二苯醚,例如2,2'-硫代双(6-叔丁基-4-甲基苯酚)、2,2'-硫代双(4-辛基苯酚)、4,4'-硫代双(6-叔丁基-3-甲基苯酚)、4,4'-硫代双(6-叔丁基-2-甲基苯酚)、4,4'-硫代双(3,6-二仲戊基苯酚)、4,4'-双(2,6-二甲基-4-羟基苯基)二硫醚。
1.6.亚烷基双酚,例如2,2'-亚甲基双(6-叔丁基-4-甲基苯酚)、2,2'-亚甲基双(6-叔丁基-4-乙基苯酚)、2,2'-亚甲基双[4-甲基-6-(α-甲基环己基)苯酚]、2,2'-亚甲基双(4-甲基-6-环己基苯酚)、2,2'-亚甲基双(6-壬基-4-甲基苯酚)、2,2'-亚甲基双(4,6-二叔丁基苯酚)、2,2'-亚乙基双(4,6-二叔丁基苯酚)、2,2'-亚乙基双(6-叔丁基-4-异丁基苯酚)、2,2'-亚甲基双[6-(α-甲基苄基)-4-壬基酚]、2,2'-亚甲基双[6-(α,α-二甲基苄基)-4-壬基酚]、4,4'-亚甲基双(2,6-二叔丁基苯酚)、4,4'-亚甲基双(6-叔丁基-2-甲基苯酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟基苄基)-4-甲基苯酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-正十二烷基巯基丁烷、乙二醇双[3,3-双(3'-叔丁基-4'-羟基苯基)丁酸酯]、双(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯、双[2-(3'-叔丁基-2'-羟基-5'-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双(3,5-二甲基-2-羟基苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟基苯基)丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-正十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷。
1.7.O-、N-和S-苄基化合物,例如3,5,3',5'-四叔丁基-4,4'-二羟基二苄基醚、4-羟基-3,5-二甲基苄基巯基乙酸十八烷基酯、4-羟基-3,5-二叔丁基苄基巯基乙酸十三烷基酯、三(3,5-二叔丁基-4-羟基苄基)胺、双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯、双(3,5-二叔丁基-4-羟基苄基)硫醚、3,5-二叔丁基-4-羟基苄基巯基乙酸异辛基酯。
1.8.羟基苄基化丙二酸酯,例如2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸二(十八烷基)酯、2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二(十八烷基)酯、2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸二(十二烷基巯基乙基)酯、双[4-(1,1,3,3-四甲基丁基)苯基]-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯。
1.9.芳族羟基苄基化合物,例如1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟基苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯酚。
1.10.三嗪类化合物,例如2,4-双(辛基巯基)-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟基苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟基苯基丙酰基)-六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟基苄基)异氰脲酸酯。
1.11.苄基膦酸酯类,例如2,5-二叔丁基-4-羟基苄基膦酸二甲酯、3,5-二叔丁基-4-羟基苄基膦酸二乙酯、3,5-二叔丁基-4-羟基苄基膦酸二(十八烷基)酯、5-叔丁基-4-羟基-3-甲基苄基膦酸二(十八烷基)酯、3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐。
1.12.酰氨基苯酚类,例如4-羟基月桂酰替苯胺、4-羟基硬脂酰替苯胺、N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.13.β-(3,5-二叔丁基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.14.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷、3,9-双[2-{3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷的酯。
1.15.β-(3,5-二环己基-4-羟基苯基)丙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.16.3,5-二叔丁基-4-羟基苯基乙酸与如下一元醇或多元醇的酯:例如与甲醇、乙醇、辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫二甘醇、二甘醇、三甘醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟基甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯。
1.17.β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺,例如N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二胺、N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰基)三亚甲基二胺、N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰基)肼、N,N'-双[2-(3-[3,5-二叔丁基-4-羟基苯基]丙酰氧基)乙基]草酰胺(XL-1,由Uniroyal提供)。
1.18.抗坏血酸(维生素C)。
1.19.胺类抗氧化剂,例如N,N'-二异丙基对苯二胺、N,N'-二仲丁基对苯二胺、N,N'-双(1,4-二甲基戊基)对苯二胺、N,N'-双(1-乙基-3-甲基戊基)对苯二胺、N,N'-双(1-甲基庚基)对苯二胺、N,N'-二环己基对苯二胺、N,N'-二苯基对苯二胺、N,N'-双(2-萘基)对苯二胺、N-异丙基-N'-苯基对苯二胺、N-(1,3-二甲基丁基)-N'-苯基对苯二胺、N-(1-甲基庚基)-N'-苯基对苯二胺、N-环己基-N'-苯基对苯二胺、4-(对甲苯胺磺酰基)二苯胺、N,N'-二甲基-N,N'-二仲丁基对苯二胺、二苯胺、N-烯丙基二苯胺、4-异丙氧基二苯胺、N-苯基-1-萘基胺、N-(4-叔辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化二苯胺如p,p'-二叔辛基二苯胺、4-正丁基氨基苯酚、4-丁酰基氨基苯酚、4-壬酰基氨基苯酚、4-十二烷酰基氨基苯酚、4-十八烷酰基氨基苯酚、双(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲基氨基甲基苯酚、2,4'-二氨基二苯基甲烷、4,4'-二氨基二苯基甲烷、N,N,N',N'-四甲基-4,4'-二氨基二苯基甲烷、1,2-双[(2-甲基苯基)氨基]乙烷、1,2-双(苯基氨基)丙烷、邻甲苯基双胍、双[4-(1',3'-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘基胺、单-和二-烷基化叔丁基二苯胺/叔辛基二苯胺的混合物、单-和二-烷基化壬基二苯胺的混合物、单-和二-烷基化十二烷基二苯胺的混合物、单-和二-烷基化异丙基二苯胺/异己基二苯胺的混合物、单-和二-烷基化叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单-和二-烷基化叔丁基吩噻嗪/叔辛基吩噻嗪的混合物、单-和二-烷基化叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N',N'-四苯基-1,4-二氨基丁-2-烯。
2.UV吸收剂和光稳定剂
2.1.2-(2'-羟基苯基)苯并三唑类,例如2-(2'-羟基-5'-甲基苯基)苯并三唑、2-(3',5'-二叔丁基-2'-羟基苯基)苯并三唑、2-(5'-叔丁基-2'-羟基苯基)苯并三唑、2-(2'-羟基-5'-(1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(3',5'-二叔丁基-2'-羟基苯基)-5-氯苯并三唑、2-(3'-叔丁基-2'-羟基-5'-甲基苯基)-5-氯苯并三唑、2-(3'-仲丁基-5'-叔丁基-2'-羟基苯基)苯并三唑、2-(2'-羟基-4'-辛氧基苯基)苯并三唑、2-(3',5'-二叔戊基-2'-羟基苯基)苯并三唑、2-(3',5'-双(α,α-二甲基苄基)-2'-羟基苯基)苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-辛氧基羰基乙基)苯基)-5-氯苯并三唑、2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羟基苯基)-5-氯苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)苯基)-5-氯苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-甲氧羰基乙基)苯基)苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-辛氧基羰基乙基)苯基)苯并三唑、2-(3'-叔丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羟基苯基)苯并三唑、2-(3'-十二烷基-2'-羟基-5'-甲基苯基)苯并三唑、2-(3'-叔丁基-2'-羟基-5'-(2-异辛氧基羰基乙基)苯基苯并三唑、2,2'-亚甲基双[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3'-叔丁基-5'-(2-甲氧基羰基乙基)-2'-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;,其中R=3'-叔丁基-4'-羟基-5'-2H-苯并三唑-2-基苯基、2-[2'-羟基-3'-(α,α-二甲基苄基)-5'-(1,1,3,3-四甲基丁基)苯基]苯并三唑;2-[2'-羟基-3'-(1,1,3,3-四甲基丁基)-5'-(α,α-二甲基苄基)苯基]苯并三唑。
2.2.2-羟基二苯甲酮类,例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2',4'-三羟基和2'-羟基-4,4'-二甲氧基衍生物。
2.3.取代和未取代苯甲酸的酯,例如水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰间苯二酚、双(4-叔丁基苯甲酰)间苯二酚、苯甲酰间苯二酚、3,5-二叔丁基-4-羟基苯甲酸2,4-二叔丁基苯酯、3,5-二叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二叔丁基-4-羟基苯甲酸2-甲基-4,6-二叔丁基苯酯。
2.4.丙烯酸酯类,例如α-氰基-β,β-二苯基丙烯酸乙酯、α-氰基-β,β-二苯基丙烯酸异辛酯、α-甲酯基肉桂酸甲酯、α-氰基-β-甲基对甲氧基肉桂酸甲酯、α-氰基-β-甲基对甲氧基肉桂酸丁酯、α-甲酯基对甲氧基肉桂酸甲酯、N-(β-甲酯基-β-氰基乙烯基)-2-甲基二氢吲哚、四(α-氰基-β,β-二苯基丙烯酸新戊基酯。
2.5.镍化合物,例如2,2'-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,例如1:1或1:2配合物,其具有或不具有其他配体如正丁胺、三乙醇胺或N-环己基二乙醇胺,二丁基二硫代氨基甲酸镍,4-羟基-3,5-二叔丁基苄基膦酸的单烷基酯如甲酯或乙酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物,其具有或不具有其他配体。
2.6.位阻胺,例如双(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)碳酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合物、N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、1,1'-(1,2-亚乙基)-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰基-2,2,6,6-四甲基哌啶、4-硬脂氧基-2,2,6,6-四甲基哌啶、双(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸-2,4-二酮、双(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、双(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N'-双-(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合物、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮、4-十六烷氧基-和4-硬脂氧基-2,2,6,6-四甲基哌啶的混合物、N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合物、1,2-双(3-氨基丙基氨基)乙烷与2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[136504-96-6]);1,6-己二胺与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记号[192268-64-7]);N-(2,2,6,6-四甲基-4-哌啶基)正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)正十二烷基琥珀酰亚胺、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷、7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧代螺[4,5]癸烷与表氯醇的反应产物、1,1-双(1,2,2,6,6-五甲基-4-哌啶基氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N'-双甲酰基-N,N'-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺、4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷、马来酸酐-α-烯烃共聚物与2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物、2,4-双[N-(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)-N-丁基氨基]-6-(2-羟乙基)氨基-1,3,5-三嗪、1-(2-羟基-2-甲基丙氧基)-4-十八烷酰氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、Sanduvor(Clariant;CAS登记号[106917-31-1])、5-(2-乙基己酰基)氧基甲基-3,3,5-三甲基-2-吗啉酮、2,4-双[(1-环己氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N'-双(3-氨基丙基)乙二胺)的反应产物、1,3,5-三(N-环己基-N-(2,2,6,6-四甲基哌嗪-3-酮-4-基)氨基)-s-三嗪、1,3,5-三(N-环己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)氨基)-s-三嗪。
2.7.草酰胺类,例如4,4'-二辛氧基草酰替苯胺、2,2'-二乙氧基草酰替苯胺、2,2'-二辛氧基-5,5'-二叔丁基草酰替苯胺、2,2'-二(十二烷氧基)-5,5'-二叔丁基草酰替苯胺、2-乙氧基-2'-乙基草酰替苯胺、N,N'-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2'-乙基草酰替苯胺及其与2-乙氧基-2'-乙基-5,4'-二叔丁基草酰替苯胺的混合物、邻-和对-甲氧基二取代草酰替苯胺的混合物以及邻-和对-乙氧基二取代草酰替苯胺的混合物。
2.8.2-(2-羟基苯基)-1,3,5-三嗪类,例如2,4,6-三(2-羟基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2-羟基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-辛氧基苯基)-4,6-双(4-甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十二烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-十三烷氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-丁氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-辛氧基丙氧基)苯基]-4,6-双(2,4-二甲基)-1,3,5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羟基丙氧基)-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羟基-4-(2-羟基-3-十二烷氧基丙氧基)苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1,3,5-三嗪、2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪、2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(4-[2-乙基己氧基]-2-羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪。
3.金属减活剂,例如N,N'-二苯基草酰胺、N-水杨醛-N'-水杨酰肼、N,N'-双(水杨酰)肼、N,N'-双(3,5-二叔丁基-4-羟基苯基丙酰)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰二肼、草酰替苯胺、间苯二甲酰二肼、癸二酰双苯基肼、N,N'-二乙酰己二酰二肼、N,N'-双(水杨酰)草酰二肼、N,N'-双(水杨酰)硫代丙酰二肼。
4.亚磷酸酯和亚膦酸酯,例如亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂基酯、亚磷酸三(十八烷基)酯、二硬脂基季戊四醇二亚磷酸酯、亚磷酸三(2,4-二叔丁基苯基)酯、二异癸基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、二异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、4,4'-亚联苯基二亚膦酸四(2,4-二叔丁基苯基)酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂磷杂八环、亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙酯、6-氟-2,4,8,10-四叔丁基-12-甲基二苯并[d,g]-1,3,2-二氧杂磷杂八环、2,2',2''-次氮基[三乙基三(3,3',5,5'-四叔丁基-1,1'-联苯-2,2'-二基)亚磷酸酯]、(3,3',5,5'-四叔丁基-1,1'-联苯-2,2'-二基)亚磷酸2-乙基己酯、5-丁基-5-乙基-2-(2,4,6-三叔丁基苯氧基)-1,3,2-二氧杂磷杂环丙烷(dioxaphosphirane)。尤其优选如下亚磷酸酯:
亚磷酸三(2,4-二叔丁基苯基)酯(168,Ciba Specialty ChemicalsInc.)、亚磷酸三(壬基苯基)酯,
5.羟胺类,例如N,N-二苄基羟胺、N,N-二乙基羟胺、N,N-二辛基羟胺、N,N-二月桂基羟胺、N,N-二(十四烷基)羟胺、N,N-二(十六烷基)羟胺、N,N-二(十八烷基)羟胺、N-十六烷基-N-十八烷基羟胺、N-十七烷基-N-十八烷基羟胺、衍生自氢化牛油脂肪胺的N,N-二烷基羟胺。
6.硝酮类,例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、衍生自N,N-二烷基羟胺(其衍生自氢化牛油脂肪胺)的硝酮。
7.硫代协合剂,例如硫代二丙酸二月桂基酯、硫代二丙酸二肉豆蔻基酯、硫代二丙酸二硬脂基酯或二硬脂基二硫醚。
8.过氧化物清除剂,例如β-硫代二丙酸的酯,例如月桂基酯、硬脂基酯、肉豆蔻基酯或十三烷基酯、巯基苯并咪唑或2-巯基苯并咪唑的锌盐、二丁基二硫代氨基甲酸锌、二(十八烷基)二硫醚、季戊四醇四(β-十二烷基巯基)丙酸酯。
9.聚酰胺稳定剂,例如与碘和/或磷化合物组合的铜盐和二价锰盐。
10.碱性助稳定剂,例如三聚氰胺、聚乙烯吡咯烷酮、双氰胺、氰脲酸三烯丙基酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙、硬脂酸锌、山萮酸镁、硬脂酸镁、蓖麻醇酸钠和棕榈酸钾、焦儿茶酸锑或焦儿茶酸锌。
11.成核剂,例如无机物质如滑石,金属氧化物如二氧化钛或氧化镁,优选碱土金属的磷酸盐、碳酸盐或硫酸盐;有机化合物如单-或聚羧酸及其盐,例如4-叔丁基苯甲酸、己二酸、二苯基乙酸、琥珀酸钠或苯甲酸钠;聚合化合物如离子共聚物(离聚物)。尤其优选为1,3:2,4-双(3',4'-二甲基亚苄基)山梨糖醇、1,3:2,4-二(对甲基二亚苄基)山梨糖醇和1,3:2,4-二(亚苄基)山梨糖醇。特别感兴趣的是对组分C-1)所列的那些。
12.填料和增强剂,例如碳酸钙、硅酸盐、表面处理的二氧化硅(例如如US-A-2007/60,697和US-A-2009/111,918所述)、玻璃纤维、玻璃珠、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和氢氧化物、炭黑、石墨、木粉和其他天然产物的粉或纤维、合成纤维。
13.其他添加剂,例如增塑剂、颜料、催化剂、荧光增白剂、阻燃剂、抗静电剂和发泡剂。
14.苯并呋喃酮类和吲哚满酮类,例如US4,325,863、US4,338,244、US5,175,312、US5,216,052、US5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839、EP-A-0591102、EP-A-1291384中所公开的那些,或3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基苯并呋喃-2-酮、5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]苯并呋喃-2-酮、3,3’-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二叔丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2-乙酰基-5-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
本发明的优选实施方案涉及一种组合物,其包含(III-2)一种或多种位阻胺化合物作为其他组分。
这些位阻胺化合物的优选实例为在上文项目2.6下所列的那些。组分(II)和(III-2)的组合使用甚至可导致进一步降低可结晶合成聚合物的雾度的效果。组分(III-2)优选以相对于组分(II)的重量为5-70%,更优选10-30%,最优选15-25%的量使用。
本发明组合物的加工实例为:注吹模塑、挤出、吹塑、滚塑、模内装饰(反注法)、搪塑、注射模塑、共注射模塑、成型、压缩模塑、压制、薄膜挤出(流延膜;吹塑膜)、纤维纺丝(纺织的、无纺的)、拉伸(单轴、双轴)、退火、深拉、砑光、机械转化(mechanical transformation)、烧结、共挤出、涂覆、层压、交联(辐射、过氧化物、硅烷)、气相沉积、焊接、胶接、硫化、热成型、管挤出、型材挤出、板材挤出、板材流延、旋涂、带捆扎(strapping)、发泡、回收/再加工、挤出涂覆、减粘裂化(过氧化物、热)、纤维熔融吹塑、纺粘、表面处理(电晕放电、火焰、等离子体)、消毒(通过γ射线、电子束)、凝胶涂覆、带挤出、SMC加工或增塑溶胶。
本发明组合物可有利地用于制备各种成型制品。实例为:
I-1)漂浮装置、航海用具、浮筒、浮标、甲板用塑料木材、防波堤、船、皮艇、桨和海滩加固物。
I-2)汽车用具,特别是保险杠、仪表板、电池、后和前衬板、在引擎盖下的模制品部分、帽架、车厢衬板、车内衬板、气囊包、配件(照明)用的电子模制品、仪表板用的窗格、头灯玻璃、仪器板、车外衬板、车内装饰、汽车照明、头灯、边灯、尾灯、停车灯、车内外装饰;门板;油箱;前侧装配玻璃;后车窗;椅背、外板、电线绝缘物、密封用轮廓挤出物、覆盖层、支柱机盖、底盘零件、排气系统、燃料过滤器/填料、燃油泵、燃料箱、车身模制品、可折叠顶盖、车外后视镜、外部装饰、固着/固定装置、前端模件、玻璃、铰链、车锁系统、行李/车顶架、冲压/模压部件、密封物、防侧撞梁、隔音装置/隔热装置和天窗。
I-3)道路交通装置,特别是信号标识杆、路标、车辆配件、警告三角架、急救箱、安全帽、轮胎。
I-4)飞机、铁道、机动车(汽车、摩托车)用装置,包括装备。
I-5)太空应用的装置,特别是火箭和卫星,例如重返防护罩。
I-6)建筑与设计用装置、采矿用具、静音体系、街道安全岛和庇护所。
II-1)在常规电器/电子设备(个人电脑、电话、移动式电话、打印机、电视机、影音装置)中的器具、箱子和罩盖、花盆、卫星TV碗和面板装置。
II-2)用于其它材料如钢或织物的护套。
II-3)电子工业用装置,特别是插头用绝缘材料,尤其是电脑插头、电和电子零件用的箱子、印制板和用于电子数据储存的材料如晶片、提款卡或信用卡。
II-4)电器用具,特别是洗衣机、滚筒、烘箱(微波炉)、洗碗机、混合器和熨斗。
II-5)灯(例如街灯、台灯)罩。
II-6)在电线和电缆中的应用(半导体、绝缘体和电缆护套)。
II-7)用于冷凝器、冰箱、加热装置、空气调节机、电子封装、半导体、咖啡机和真空清洁器的箔片。
III-1)科技物品,例如嵌齿轮(齿轮)、滑动配件、垫片、螺丝、螺栓、把手和按钮。
III-2)旋转叶片、通风机和风车轮叶、太阳能装置、游泳池、游泳池盖、泳池衬里、水池衬里、壁橱、衣柜、隔墙板、墙板、折叠墙、屋顶、百叶窗(例如卷帘)、配件、管子之间的连接机构、套管和输送带。
III-3)卫生制品,特别是淋浴隔间、马桶坐圈、马桶盖和水槽。
III-4)卫生用品,特别是尿布(婴儿、成人失禁用)、女性卫生制品、浴帘、浴刷、浴毡、浴盆、移动厕所、牙刷和便盆。
III-5)水、废水和化学品用管道(交叉结合或未交叉结合)、电线与电缆保护用管道、气体、油和污水用管道、排水沟、下流管和排水系统。
III-6)任何几何(窗格)和板壁的型材。
III-7)玻璃代用品,特别是挤出板材、用于建筑物(整体、双壁或多壁)、飞机、学校的装配玻璃、用于建筑装配玻璃、火车、运输、卫生物品和温室的窗膜。
III-8)板(墙壁、砧板)、挤出涂层(相纸、利乐包和管道涂层)、筒仓、木材代替物、塑料木材、木材复合物、墙壁、表面、家具、装潢箔、地板覆盖材料(内用和外用)、地板、沟槽板道和瓷砖。
III-9)进口和出口支管。
III-10)水泥-、混凝土-、复合物应用和盖、板壁和覆盖层、扶手、栏杆、厨房工作台、屋顶、屋面薄面板、瓷砖和防水布。
IV-1)板(墙壁和砧板)、盘子、人工草皮、阿斯特罗特夫尼龙草皮、用于体育馆圆形场地(运动)的人工覆盖物、用于体育馆圆形场地(运动)的人工地板和胶带。
IV-2)织物连续和定长纤维(地毯/卫生用品/土工织物/单丝;过滤器;纸巾/帘(遮光物)/医学应用)、散纤维(应用如睡衣/保护服装)、网、粗绳、电缆、绳、粗线、线、安全带、服装、内衣、手套;长靴;雨靴、贴身内衣、衣服、泳衣、运动装、伞(阳伞、遮阳伞)、降落伞、飞行伞、帆、“气球-丝”、露营用品、帐篷、空气床、日光床、太空包和袋。
IV-3)用于屋顶、隧道、垃圾场、池塘、垃圾场、墙壁屋顶薄膜、土工膜、游泳池、窗帘(遮光物)/太阳防护罩、遮阳篷、遮篷、壁纸、食物包装和包封(柔韧和坚固的)、医用包装(柔性和坚固的)、安全气囊/安全带、臂-和头靠、地毯、中心控制台、仪表板、座舱、门、头顶控制台组件、车门板、汽车顶蓬、内部照明、内部后视镜、包裹架、后行李盖、座位、转向柱、方向盘、纺织物和车厢装饰。
V)薄膜(包装膜、垃圾膜、层压膜、农业和园艺用膜、温室膜、护根膜、隧道膜、青贮膜)、打包包装纸、游泳池用膜、垃圾袋、壁纸、拉伸薄膜、酒椰纤维、脱盐膜、电池和连接器用膜。
VI-1)食物包装和包装材料(柔韧和坚固型)、BOPP、BOPET、瓶。
VI-2)存储体系如箱(板条箱)、皮箱、盒、家用箱、垫板、架子、轨道、螺丝盒、包装和罐子。
VI-3)药筒、注射器、医疗器具、用于任何运输的容器、垃圾篮和垃圾箱、垃圾袋、箱、垃圾箱、箱衬里、轮箱、常规容器、用于水/用后水/化学/气体/油/汽油/柴油的罐;槽衬层、箱、板条箱、电池箱、水槽、医学装置如活塞、眼科用具、诊断装置和药剂泡罩包装。
VII-1)挤出涂层(相纸、利乐包、管面涂层)、任何种类的家庭用品(例如用具、热水瓶/衣架)、紧固系统如插头、电线和电线夹、拉链、密封盒、锁和按扣密封盒。
VII-2)支撑装置,休闲用品如运动和健身装置、体操垫、滑雪靴、直排轮鞋、滑雪板、大脚、运动表面(例如网球场地);用于瓶子和罐子的螺旋盖、盖和木塞。
VII-3)常规家具,泡沫制品(垫子、吸震器)、泡沫体、海绵、抹布、垫、花园椅、体育馆座位、桌子、长椅、玩具、建筑套具(板/外形/球)、剧场、滑梯和游戏车辆。
VII-4)用于光学和磁数据存储的材料。
VII-5)厨房用具(吃、喝、烹饪、储存)。
VII-6)用于CD、卡带和录影带的盒子;DVD电子物件、任何种类的办公用品(圆珠笔、图章和印泥、鼠标、架子、轨道)、任何体积和含量的瓶子(饮料、洗涤剂、包括香水的化妆品)和胶带。
VII-7)鞋类(鞋/鞋底)、鞋垫、护脚、粘合剂、结构粘着剂、食物(水果、蔬菜、肉、鱼)盒、合成纸、瓶用标签、长椅、人造关节(人类)、印刷版(苯胺印刷)、印刷电路板和显示技术。
VII-8)填充聚合物(滑石、粉笔、陶土(高岭土)、硅酸钙岩矿、颜料、炭黑、TiO2、云母、纳米复合材料、白云石、硅酸盐、玻璃、石棉)的装置。
因此,本发明的另一优选实施方案涉及一种可由上述组合物获得的成型制品,特别是膜、纤维、型材、管、瓶、槽或容器。
优选为模制品。模塑特别通过注射、吹塑、压缩、滚塑、搪塑或挤出进行。
本发明的另一优选实施方案涉及一种可由上述组合物获得的单轴取向膜或双轴取向膜。
本发明进一步涉及一种多层体系,其中一个或多个层包含上述组合物。
本发明的又一实施方案涉及一种母料,其优选通过高剪切熔体加工获得,其包含天然或合成聚合物,优选聚烯烃,和相对于所述天然或合成聚合物的重量为0.5-5%的如权利要求1所定义的组分(A1)和(A2),其特征在于组分(A1):(A2)的摩尔比为1:5-5:1,优选为1:2-2:1,例如约1:1;条件是所述母料不含颜料。
本发明的又一优选实施方案涉及一种制备含添加剂的天然或合成聚合物的方法,其包括向其中引入1-50%的如上所定义的母料。
下文实施例更详细地描述本发明。除非另有说明,所有份和百分数均以重量给出。
在下述实施例中使用下述测试方法:
实验室级复合和注射模塑:
将Borealis供应的粉末状丙烯无规共聚物“PP raco”(市售型RD-204CF,230℃和2.16kg下的熔体流动速率=8dg/分钟)与添加剂混合物以本文表中所给的浓度预混。然后在恒定的氮气吹扫下,将所述混合物在下文实施例中所给的温度(210℃或240℃)下使用同向旋转实验室双螺杆挤出机,如DSM Xplore(RTM)的15cm3Micro-Compounder在100rpm的螺杆速率下充分熔融复合3分钟。
出于成型目的,随后将所述均质熔体转移至10cm3Micro-Injector(DSM Xplore(RTM))中,其中将所述熔体以约8巴的压力和50℃的模具温度注射至抛光的模具中。所得试样的直径为40mm,厚度为1mm。
使用这些圆盘表征所述成核聚合物的性能,通常通过用DSC测量结晶温度或定量测量光学性能,如根据ASTM D-1003在1mm下测量雾度。
中试级复合和注射模塑:
将全部呈粉末形式的添加剂与450g Borealis供应的粉末状丙烯无规共聚物“PP raco”(市售型RD-204CF,230℃和2.16kg下的熔体流动速率=8dg/分钟)在旋转混合装置上干混。通过使用两个独立的重力喂料机(一个用于所述粉状混合物,一个用于所述粒料),将所得干混物与剩余的粒状RD-204CF一起引入双螺杆挤出机(TSE,Werner&Pfleiderer,同向旋转螺杆,直径25mm,L/D44)。温度区域设定为区域1:50℃,区域2:190℃,和区域3-11:200℃,从而获得195℃的熔体温度。所述TSE在氮气流下运行。由于RD-204CF被供应商稳定化且由于据认为TSE几乎无氧,在这些系列中不使用其他加工稳定剂或抗酸剂。
注射模塑步骤用获自TSE的粒料在Arburg370S注塑机上进行,从而获得厚度为1mm和2mm的板以用于测量雾度和结晶温度,并获得ISO-1A哑铃形试样(厚度4mm)以用于测试却贝冲击强度和弯曲模量(刚性)。熔体温度为200℃,模具温度设定为40℃。注射压力为820巴左右。
在使用前,将所述ISO-1A试样切割,从而使得仅保留减小至厚度为4mm,宽度为10mm且长度为80mm的条的中心部分以用于测定机械性能(根据ISO179在缺口试样上测定却贝冲击强度(摆锤0.5J)和根据ISO178以2mm/分钟在64mm的支撑距离下测定弯曲模量)。
差示扫描量热法(DSC):
根据下述严格计算机控制的程序,使用在干燥氮气气氛下运行的型号为DSC820的Mettler-Toledo(RTM)仪器分析各测试试样和参照材料的结晶行为:
将5-10mg试样精确称量入铝坩埚中;然后用4次折叠的打孔盖密封。以10℃/分钟的恒定加热或冷却速率,运行如下温度程序两次(首次运行仅仅是用于消除热历史):由30℃至240℃,在240℃下保持3分钟,随后冷却至30℃。结晶温度“TC[℃]”表示第二次冷却循环过程中的DSC放热的峰值温度。峰值温度之差“ΔTc[℃]”,即含有添加剂的聚合物的峰值温度减去空白聚合物的峰值温度,列于下文表中。这些值越高越好。
光学表征(雾度):
雾度值按照ASTM D-1003在室温下在厚度为1mm或2mm的试样上使用Haze-Gard Plus仪器(BYK Gardner(RTM),照明CIE-C)测定。所有雾度值均在试样注射模塑之后至少24小时后测定,即所述“PP raco”在环境条件下平衡至少1天之后。本文的雾度数据分别在厚度为1mm的盘上(对实验室级加工而言)、在厚度为1mm和2mm的板上(对由中试级加工获得的试样而言)测定。所得结果涉及由5个试样获得的平均值。
结果汇总于下表中。低雾度和高结晶温度值以及高机械性能是所需的。
在下文实施例中使用下述式(I)化合物:
化合物(I-1):
化合物(I-2):
实施例1:
根据上文所述的“实验室级复合和注射模塑”方法进行复合和注射模塑,其中复合温度为240℃。
表A-1:用所示添加剂混合物成核且在240℃下加工的注射模塑“PP raco”的雾度值
“%”意指相对于“PP raco”的“重量%”。
化合物(I-1)和硬脂酸Li以1:1的摩尔比使用。
实施例2:
根据上文所述的“实验室级复合和注射模塑”方法进行复合和注射模塑,其中复合温度为210℃。
表A-2:用所示添加剂混合物成核且在210℃下加工的注射模塑“PP raco”的雾度值
“%”意指相对于“PP raco”的“重量%”。
化合物(I-1)和硬脂酸Li以1:1的摩尔比使用。
实施例3:
根据上文所述的“实验室级复合和注射模塑”方法进行复合和注射模塑,其中复合温度为210℃。
表A-3:用所示添加剂混合物成核且在210℃下加工的注射模塑“PP raco”的雾度值
“%”意指相对于“PP raco”的“重量%”。
化合物(I-2)和硬脂酸Li以1:1的摩尔比使用。
实施例4:
根据上文所述的“实验室级复合和注射模塑”方法进行复合和注射模塑,其中复合温度为210℃。
表A-4:用所示添加剂混合物成核且在210℃下加工的注射模塑“PP raco”的雾度值
“%”意指相对于“PP raco”的“重量%”。
化合物(I-1)和硬脂酸Li以1:1的摩尔比使用。
实施例5:
根据上文所述的“中试级复合和注射模塑”方法进行复合和注射模塑,其中挤出温度为195℃且注射模塑温度为200℃。
表A-5:用所示添加剂混合物成核且在195℃下挤出的注射模塑“PP raco”的雾度值
“%”意指相对于“PP raco”的“重量%”。
化合物(I-1)和硬脂酸Li以1:1的摩尔比使用。
Claims (15)
2.根据权利要求1的添加剂混合物,其中R0为直接键、-S-、-CH2-或-CH(C1-C18烷基)-;且基团R1为C1-C12烷基、环己基或甲基环己基。
4.根据权利要求1-3中任一项的添加剂混合物,其中组分(A2)的碱金属或碱土金属阳离子为Li+、Na+、K+、Mg+、Ca2+、Ba2+、Al3+或Al(OH)2+。
5.根据权利要求1-4中任一项的添加剂混合物,其中组分(A2)为C10-C20链烷醇盐,其中阳离子为Li+、Na+、K+、Mg+、Ca2+、Ba2+、Al3+或Al(OH)2+。
6.根据权利要求1-5中任一项的添加剂混合物,其中组分(A2)为硬脂酸Li。
7.根据权利要求1-6中任一项的添加剂混合物,其中组分(B)为多羟基(C2-C20烷烃)的二价金属醇盐。
8.根据权利要求1-7中任一项的添加剂混合物,其中组分(B)为乙二醇(=1,2-乙烷二醇)或甘油(=1,2,3-丙烷三醇)的二价金属醇盐。
9.根据权利要求1-8中任一项的添加剂混合物,其中组分(B)为甘油锌。
11.一种组合物,其包含如下组分:
(I)天然或合成有机聚合物,和
(II)如权利要求1所定义的添加剂混合物。
12.根据权利要求11的组合物,其中组分(I)为聚烯烃。
13.一种降低天然或合成有机聚合物的雾度值和/或提高其结晶温度Tc的方法,其包括向其中引入如权利要求1所定义的添加剂混合物。
14.一种母料,其优选通过高剪切熔体加工获得,其包含天然或合成聚合物和相对于所述天然或合成聚合物的重量为0.5-5%的如权利要求1所定义的组分(A1)和(A2),其特征在于组分(A1):(A2)的摩尔比为1:5-5:1;条件是所述母料不含颜料。
15.一种制备含添加剂的天然或合成聚合物的方法,其包括向其中引入1-50%的如权利要求14所定义的母料。
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WO2012000992A1 (en) | 2010-06-29 | 2012-01-05 | Basf Se | Process for improving the flow properties of polymer melts |
WO2014139808A1 (en) | 2013-03-13 | 2014-09-18 | Wintershall Holding GmbH | Process for the preparation of substituted tris(2-hydroxyphenyl)methane |
IN2013DE02999A (zh) * | 2013-10-08 | 2015-04-10 | NIIT Technologies Ltd | |
BR112017002836A2 (pt) * | 2014-08-14 | 2017-12-19 | Basell Poliolefine Italia Srl | composições de terpolímero com clareza e brilho aprimorados |
CN108384053A (zh) * | 2018-02-13 | 2018-08-10 | 株式会社Adeka | 成核剂、使用其的聚烯烃系树脂组合物及其成型品 |
CN112449647A (zh) * | 2018-07-27 | 2021-03-05 | 株式会社Adeka | 添加剂组合物、含有其的聚烯烃系树脂组合物、聚烯烃系树脂组合物的制造方法和其成型品 |
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WO2010038907A1 (en) * | 2008-10-01 | 2010-04-08 | Fujifilm Corporation | Film and method for producing film |
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