CN117222700A - 稳定剂组合物用于稳定有机材料的用途,稳定剂组合物、母料、组合物、用于模制部件的模塑料,用于热塑性塑料的氧化稳定、热稳定、光化稳定的方法以及组合物的用途 - Google Patents
稳定剂组合物用于稳定有机材料的用途,稳定剂组合物、母料、组合物、用于模制部件的模塑料,用于热塑性塑料的氧化稳定、热稳定、光化稳定的方法以及组合物的用途 Download PDFInfo
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- CN117222700A CN117222700A CN202280030618.5A CN202280030618A CN117222700A CN 117222700 A CN117222700 A CN 117222700A CN 202280030618 A CN202280030618 A CN 202280030618A CN 117222700 A CN117222700 A CN 117222700A
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- agents
- styrene
- sulfite
- tert
- metal
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Classifications
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明涉及亚硫酸盐和/或至少一种硫代硫酸盐与聚合或低聚受阻胺的组合使用,其用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解。本发明还涉及相应生产的组合物、可由其生产的模制部件、用于稳定有机材料的方法以及经稳定的有机材料的可能用途。
Description
本发明涉及亚硫酸盐和/或至少一种硫代硫酸盐以及聚合或低聚受阻胺的组合使用,其用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解。此外,本发明涉及相应制备的组合物、可由其生产的模制部件、用于稳定有机材料的方法以及经稳定的有机材料的可能用途。
有机材料如塑料受老化过程的影响,最终导致所需性质如机械特性值的损失。这一过程称为自氧化,导致聚合物链的变化,如分子量的变化或新化学基团的形成,这是由氧存在下的机械化学过程或UV辐射引起的自由基链断裂引发的。因此,稳定剂用于防止或至少延缓这种老化。稳定剂的重要代表是抗氧化剂,其干扰自氧化过程中形成的自由基,从而中断降解过程。通常在初级抗氧化剂和次要抗氧化剂之间进行区分,初级抗氧化剂可以直接与含氧自由基或C自由基反应,次要抗氧化剂可以与中间形成的氢过氧化物反应(参见C.等人,Antioxidants in Ullmann′s encyclopedia of industrial chemistry,Wiley-VCH Verlag,Weinheim 2015,)。初级抗氧化剂的典型代表是例如酚类抗氧化剂、胺类以及内酯类。次要抗氧化剂的种类是磷化合物,如亚磷酸酯或亚膦酸酯,但也包括有机硫化合物,如硫化物或二硫化物。通常,初级抗氧化剂和次要抗氧化剂在实践中经常结合,产生有益的协同效应。
受阻胺与亚硫酸盐的组合作为塑料和塑料回收材料的稳定剂尚不为人所知。因为目前使用的一些稳定剂也有缺点(例如,亚磷酸酯的水解稳定性和酚类的释放、酚类抗氧化剂的水解稳定性和酚类或降解产物的释放、硫化物稳定剂的气味、酚类或胺类的变色等),仍在寻找新的稳定剂解决方案,包括希望找到不包含酚类抗氧化剂和/或不含酚类的稳定剂解决方案。
用于塑料的无酚类稳定剂解决方案是已知的,通常由受阻胺(HAS=受阻胺稳定剂)与加工稳定剂如内酯、亚磷酸酯或羟胺的组合组成。这些系统描述在例如用于纤维织物的WO 2000020209或WO 2002095095中,或用于γ-辐射聚烯烃应用的US20020086924或US20030195282中。
只有CN 101323956要求保护一种抗腐蚀母料,其包含UV稳定剂作为一种选择和亚硫酸钙作为UV吸收剂;CN 106047284提到了一种用于LED灯的抗静电导热黏合剂,其包含10至20份未指明的亚硫酸盐和受阻胺。
从现有技术中无法得出受阻胺和无机亚硫酸盐组合的稳定效果的结论。
受阻胺与亚硫酸盐的组合作为塑料和塑料回收材料的稳定剂尚不为人所知。
在上述背景下,因此本发明的目的是提供用于稳定有机材料,特别是塑料的新的稳定剂或方法或用途,其是高效的、环境友好的并且具有有利的成本结构。
这个目的是通过独立权利要求的特征实现的。从属权利要求涉及有利的发展。
因此,在第一方面,本发明涉及至少一种稳定剂组合物的用途,该稳定剂组合物包含或组成为至少一种亚硫酸盐和/或至少一种硫代硫酸盐与至少一种聚合或低聚受阻胺组合,用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解。
因此,本发明提出了新的稳定剂组合物和特别是用于稳定塑料的新方法,其表现出高效、环境友好和有利的成本结构。
出乎意料地,用受阻胺和无机亚硫酸盐的组合可以获得良好的稳定效果,并且受阻胺可以部分被便宜的亚硫酸盐替代。
特别地,稳定剂组合物适用于稳定塑料、涂料、润滑剂、液压油、发动机油、涡轮机油、变速器油、金属加工液、化学品或单体。
在另一个优选实施例中,塑料选自原生塑料、塑料回收材料及其混合物或组合。
所述至少一种亚硫酸盐优选为无机亚硫酸盐、无机二亚硫酸盐或无机亚硫酸氢盐,优选为一价金属、二价金属、三价金属或四价金属的盐,所述金属优选为碱金属、碱土金属、铝和/或锌,特别优选选自亚硫酸钠、亚硫酸钾、亚硫酸锂、亚硫酸钙、亚硫酸镁、亚硫酸铝、亚硫酸锌的亚硫酸盐及其混合物和组合,所使用的亚硫酸盐特别为不含结晶水的形式。
硫代硫酸盐特别是一价金属、二价金属、三价金属或四价金属的硫代硫酸盐,该金属优选是碱金属、碱土金属、铝和/或锌,特别优选硫代硫酸钠,硫代硫酸盐特别是以不含结晶水的形式使用。
根据本发明的空间位阻胺类是具有至少一个与相应胺基相邻的烷基、环烷基或芳基的杂环胺。优选的杂环胺是基于哌啶、哌嗪、哌嗪-酮或哌嗪-二酮的衍生物,特别是受阻胺具有2,2’,6,6’-四甲基哌啶单元。
优选地,至少一种聚合或低聚受阻胺具有>1000g/mol的数均分子量,特别地,至少一种聚合或低聚受阻胺选自以下化合物,
其中n在每种情况下表示2至100的整数,优选3至20,特别优选3至10,并且
R表示-O-C(O)-烷基,特别是R表示-O-C(O)-C15H31或-O-C(O)-C17H35,
其中,在N-H基团的情况下,其在每次出现时能够独立地被以下基团替代:N-烷基如N-甲基或N-辛基、N-烷氧基如N-甲氧基或N-辛氧基、N-环烷基如N-环己氧基,和N-(2-羟基-2-甲基丙氧基),
以及它们的混合物和组合。
还优选地至少一种亚硫酸盐和/或硫代硫酸盐的总量和至少一种聚合或低聚受阻胺的总量的重量比为1∶99至99∶1,优选20∶80至80∶20,还优选30∶70至70∶30,特别优选40∶60至60∶40。
优选地,稳定剂组合物适用于稳定塑料,其中塑料特别选自
a)烯烃或二烯烃的聚合物,如聚乙烯(LDPE、LLDPE、VLDPE、ULDPE、MDPE、HDPE、UHMWPE)、茂金属-PE(m-PE)、聚丙烯、聚异丁烯、聚-4-甲基-戊烯-1、聚丁二烯、聚异戊二烯,如天然橡胶(NR)、聚环辛烯、聚亚烷基-一氧化碳共聚物,以及无规结构或嵌段结构形式的共聚物,如聚丙烯-聚乙烯(EP)、EPM或以例如5-亚乙基-2-降冰片烯为共聚单体的EPDM、乙烯-乙酸乙烯酯(EVA)、乙烯丙烯酸酯如乙烯-丙烯酸丁酯、乙烯-丙烯酸及其盐(离聚物),以及三元共聚物如乙烯-丙烯酸-(甲基)丙烯酸缩水甘油酯、接枝聚合物如聚丙烯-接枝-马来酸酐、聚丙烯-接枝-丙烯酸、聚乙烯-接枝-丙烯酸、聚乙烯-聚丙烯酸丁酯-接枝-马来酸酐以及共混物如LDPE/LLDPE或用α-烯烃例如1-丁烯、1-己烯、1-辛烯或1-十八烯作为共聚单体制备的长链支化聚丙烯共聚物,
b)聚苯乙烯、聚甲基苯乙烯、聚α-甲基苯乙烯、聚乙烯萘、聚乙烯联苯、聚乙烯甲苯、苯乙烯-丁二烯(SB)、苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯、苯乙烯异戊二烯、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-丁二烯-丙烯腈(ABS)、苯乙烯-丙烯腈(SAN)、苯乙烯-丙烯腈-丙烯酸酯(ASA)、苯乙烯-乙烯、苯乙烯-马来酸酐聚合物,包括相应的接枝共聚物如丁二烯上的苯乙烯、SBS或SEBS上的马来酸酐、以及甲基丙烯酸甲酯、苯乙烯丁二烯和ABS(MABS)的接枝共聚物、以及水合聚苯乙烯衍生物如聚乙烯环己烷,
c)含卤素聚合物,如聚氯乙烯(PVC)、聚氯丁二烯和聚偏二氯乙烯(PVDC)、氯乙烯和偏二氯乙烯的共聚物或氯乙烯和乙酸乙烯酯的共聚物、氯化聚乙烯、聚偏二氟乙烯、表氯醇的均聚物和共聚物,特别是与环氧乙烷的共聚物(ECO),
d)不饱和酯的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯如聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸丁酯、聚丙烯酸月桂酯、聚丙烯酸硬脂酯、聚丙烯酸缩水甘油酯、聚甲基丙烯酸缩水甘油酯、聚丙烯腈、聚丙烯酰胺、共聚物如聚丙烯腈-聚丙烯酸烷醇酯,
e)不饱和醇及其衍生物的聚合物,如聚乙烯醇、聚乙酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙酯、聚烯丙基三聚氰胺,
f)聚缩醛,例如聚甲醛(POM)或与例如丁醛、聚苯乙醚的共聚物,以及与聚苯乙烯或聚酰胺的共混物,
g)环醚的聚合物,如聚乙二醇、聚丙二醇、聚环氧乙烷、聚环氧丙烷、聚四氢呋喃,
h)聚苯醚及其与聚苯乙烯和/或聚酰亚胺的共混物,
i)来自羟基封端的聚醚或聚酯与芳香族或脂族异氰酸酯如2,4-或2,6-甲苯二异氰酸酯或亚甲基二苯基二异氰酸酯的聚氨酯,特别是线性聚氨酯(TPU)、聚脲,
j)聚酰胺,如聚酰胺-6、聚酰胺-6.6、聚酰胺-6.10、聚酰胺-4.6、聚酰胺-4.10、聚酰胺-6.12、聚酰胺-10.10、聚酰胺-10.12、聚酰胺-12.12、聚酰胺11、聚酰胺12以及(部分)芳族聚酰胺,如聚苯二甲酰胺,如由对苯二甲酸和/或间苯二甲酸与脂族二胺如六亚甲基二胺或间苯二甲胺制备的聚酰胺,或者由脂族二羧酸如己二酸或癸二酸与芳族二胺如1,4-或1,3-二氨基苯制备的聚酰胺,不同聚酰胺如PA-6和PA 6.6的共混物或聚酰胺和聚烯烃的共混物如PA/PP,
k)聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚(醚)酮、聚砜、聚醚砜、聚芳砜、聚苯硫醚、聚苯并咪唑、聚乙内酰脲、
l)脂肪族或芳香族二羧酸与二醇或羟基羧酸的聚酯,如聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTI)、聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸1,4-二羟甲基环己烷酯、聚羟基苯甲酸酯、聚羟基萘二甲酸酯、聚乳酸(PLA)、聚羟基丁酸酯(PHB)、聚羟基戊酸酯(PHV)、聚丁二酸乙二醇酯、聚丁二酸丁二醇酯、聚己内酯,
m)聚碳酸酯、聚酯碳酸酯、及其共混物如PC/ABS、PC/PBT、PC/PET/PBT、PC/PA,
n)纤维素衍生物如硝酸纤维素、醋酸纤维素、丙酸纤维素、丁酸纤维素,
o)组成为双官能或多官能环氧化合物与例如基于胺、酸酐、双氰胺、硫醇、异氰酸酯的硬化剂或催化作用硬化剂的组合的环氧树脂,
p)酚类树脂如酚醛树脂、脲醛树脂、三聚氰胺甲醛树脂,
q)由不饱和二羧酸和二醇与乙烯基化合物例如苯乙烯形成的不饱和聚酯树脂、醇酸树脂、烯丙基树脂,
r)硅氧烷,例如乙烯基封端的例如基于二甲基硅氧烷、甲基苯基硅氧烷或二苯基硅氧烷,
s)以及上述聚合物的两种或多于两种的混合物、组合或共混物。
如果在a)至r)中指定的聚合物是共聚物,它们可以是无规、嵌段或梯度结构的形式。
此外,所述聚合物可以以线性、带支链的、星形或超支化结构的形式存在。
如果在a)至r)中指定的聚合物是有规立构聚合物,它们可以以全同立构、立体定向共聚物的形式存在,但也可以以无规立构形式或立体嵌段共聚物的形式存在。
此外,在a)至r)中指定的聚合物可以具有非结晶形态和(部分)结晶形态。
如果需要的话,a)中提到的聚烯烃也可以是交联的,例如交联聚乙烯,然后称为X-PE。
此外,本发明化合物可用于稳定橡胶和弹性体。这些可以是天然橡胶(NR)或合成橡胶材料。
塑料回收材料,特别是热塑性回收材料,也是优选的塑料。
特别优选的热塑性回收材料选自烯烃或二烯烃的聚合物,如聚乙烯,特别是LDPE、LLDPE、VLDPE、ULDPE、MDPE、HDPE和UHMWPE、茂金属-PE(m-PE)、聚丙烯、聚异丁烯、聚-4-甲基-戊烯-1、聚丁二烯、聚异戊二烯、聚环辛烯、聚亚烷基-一氧化碳共聚物,以及无规结构或嵌段结构形式的相应共聚物,如聚丙烯-聚乙烯(EP)、EPM或EPDM、乙烯-醋酸乙烯酯(EVA)、乙烯-丙烯酸酯如乙烯-丙烯酸丁酯、乙烯-丙烯酸-丙烯酸缩水甘油酯,和相应的接枝聚合物,如聚丙烯马来酸酐、聚丙烯-g-丙烯酸和聚乙烯丙烯酸。
非常特别优选地,一种热塑性塑料是聚烯烃回收材料。例如,热塑性回收材料可以是聚丙烯,特别是聚丙烯回收材料均聚物或共聚物,或聚乙烯,特别是聚乙烯回收材料,例如HDPE、LDPE、LLDPE或其混合物。
此外,还可以使用选自以下的添加剂:初级和/或次要抗氧化剂、UV吸收剂、光稳定剂、金属减活剂、填料减活剂、抗臭氧剂、成核剂、抗核剂、抗冲击改性剂、增塑剂、润滑剂、流变改性剂、触变剂、扩链剂、加工助剂、脱模助剂、阻燃剂、颜料、染料、荧光增白剂、抗微生物活性剂、抗静电剂、滑爽剂、防结块剂、偶联剂、交联剂、抗交联剂、亲水剂、疏水剂、黏结促进剂、分散剂、增溶剂、除氧剂、除酸剂、发泡剂、降解添加剂、消泡剂、除臭剂、标记剂、防雾剂、填料和增强剂。
在优选的实施方案中,组合物特别包含亚磷酸酯或亚膦酸酯、填料或除酸剂。
合适的酚类抗氧化剂有:
烷基化的单酚,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、线性或带支链的壬基苯酚如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;
烷基硫代甲基苯酚,如2,4-二辛基硫代甲基-6-叔丁基苯酚、2,4-二辛基硫代甲基-6-甲基苯酚、2,4-二辛基硫代甲基-6-乙基苯酚、2,6-二-十二烷基硫代甲基-4-壬基苯酚;
对苯二酚和烷基化的对苯二酚,如2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基对苯二酚、2,5-二叔戊基对苯二酚、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基对苯二酚、2,5-二叔丁基-4-羟基苯甲醚、3,5-二叔丁基-4-羟基苯甲醚、3,5-二叔丁基-4-羟基苯基硬脂酸酯、双(3,5-二叔丁基-4-羟基苯基)己二酸酯;
生育酚,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);
羟基化的硫代二苯醚,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-羟苯基)二硫化物;
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-壬基苯酚]、2,2’-亚甲基双[6-(α,α-二甲基苄基)-4-壬基苯酚]、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;
O-苄基、N-苄基和S-苄基化合物,如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄基醚、十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯、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)硫化物、异辛基-3,5-二叔丁基-4-羟基苄基巯基乙酸酯;
羟基苄基化的丙二酸酯,如二-十八烷基-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯、二-十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、二-十二烷基巯基乙基-2,2-双(3,5-二叔丁基-4-羟基苄基)丙二酸酯、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;
芳香族羟基苄基化合物,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;
三嗪化合物,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;
苄基膦酸酯,如2,5-二叔丁基-4-羟基苄基膦酸二甲基酯、3,5-二叔丁基-4-羟基苄基膦酸二乙基酯、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;
酰基氨基酚,如4-羟基月桂酰苯胺、4-羟基硬脂酰苯胺、辛基-N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸酯;
β-(3,5-二叔丁基-4-羟基苯基)丙酸与一元或多元醇的酯,该一元或多元醇例如为甲醇、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、硫代二甘醇、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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;
β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇的酯,该一元醇或多元醇例如为甲醇、乙醇、正辛醇、异辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、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;
β-(3,5-二环己基-4-羟苯基)丙酸与一元醇或多元醇的酯,该一元醇或多元醇例如为甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;
(3,5-二叔丁基-4-羟苯基)乙酸与一元醇或多元醇的酯,该一元醇或多元醇例如为甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二甘醇、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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷;
β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺,如N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)六亚甲基二酰胺、N,N′-双(3,5-二叔丁基-4-羟基苯基丙酰基)酰肼、N,N′-双[2-(3-[3,5-二叔丁基-4-羟苯基]丙酰氧基)乙基]草酰胺(XL-1,由Uniroyal销售);
抗坏血酸(维生素C)。
特别优选的酚类抗氧化剂为以下结构:
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其中,在上述化合物中,n是整数并且为2至10。
进一步优选的酚类抗氧化剂是基于可再生原料的酚类抗氧化剂,如α-、β-、γ-、δ-生育酚及其混合物(维生素E)、生育三烯酚、生育单烯酚、泛醇、羟基酪醇、黄酮类和黄烷醇,如白杨素、槲皮素、橙皮苷、新橙皮苷、柚皮苷、桑色素、山萘酚、非瑟酮、橡精、木犀草素、芹菜素、花旗松素、异黄酮如染料木素、染料木苷、大豆苷元、黄豆苷、刺芒柄花素、花青素如飞燕草素和锦葵色素、姜黄素、鼠尾草酸、鼠尾草酚、迷迭香酸、鞣酸和白藜芦醇,及具有醇类基团的类胡萝卜素如β-隐黄素、叶黄素、玉米黄质或虾青素。
优选的填料是碳酸钙、硅酸盐、滑石、云母、高岭土、金属氧化物和金属氢氧化物、炭黑、石墨、木粉或天然产品纤维如纤维素。其他合适的填料为水滑石或沸石或层状硅酸盐如蒙脱石、膨润土、贝得石、云母、锂蒙脱石、皂石、蛭石、水黑云母(ledikite)、麦羟硅钠石、伊利石、高岭石、硅灰石、绿坡缕石。
合适的次要抗氧化剂尤其是亚磷酸酯或亚膦酸酯,如亚磷酸三苯酯、亚磷酸二苯基烷醇酯、亚磷酸苯基二烷醇酯、亚磷酸三(壬基苯基)酯、亚磷酸三月桂酯、亚磷酸-三-十八烷醇酯、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、三硬脂基山梨醇三亚磷酸酯、四(2,4-二叔丁基苯基)-4,4′-亚联苯基二亚膦酸酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂膦、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂膦、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]、2-乙基己基(3,3′,5,5′-四叔丁基-1,1′-联苯-2,2′-二基)亚磷酸酯、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。
特别优选的亚磷酸酯/亚膦酸酯是:
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其中n=3至100。
非常特别优选的是,亚磷酸三-(2,4-二叔丁基苯基)亚磷酸酯用作次要抗氧化剂。其中n=3至100。
非常特别优选的是,亚磷酸三-(2,4-二叔丁基苯基)亚磷酸酯用作次要抗氧化剂。
优选的亚膦酸盐是:
合适的次要抗氧化剂还有有机硫化合物如硫化物和二硫化物,例如二硬脂基硫代二丙酸酯、二月桂基硫代二丙酸酯;二-十三烷基二硫代丙酸酯、二-十四烷基硫代二丙酸酯、1,1′-[2,2-双[[3-(十二烷基硫代)-1-氧代丙氧基]甲基]-1,3-丙二基]丙酸酯。优选以下结构:
合适的除酸剂(“抗酸剂”)有一价金属、二价金属、三价金属或四价金属——优选碱金属、碱土金属、铝或锌的盐,特别是与脂肪酸形成的盐如硬脂酸钙、硬脂酸镁、硬脂酸锌、硬脂酸铝、月桂酸钙、山嵛酸钙、乳酸钙、硬脂酰-2-乳酸钙。合适的除酸剂的其他类别有水滑石,特别是基于铝、镁和锌的合成水滑石,水钙铝石、沸石、碱土金属氧化物,特别是氧化钙和氧化镁及氧化锌,碱土金属碳酸盐,特别是碳酸钙、碳酸镁、白云石,以及氢氧化物,特别是水镁石(氢氧化镁)。
此外,合适的共稳定剂是多元醇,特别是糖醇或环醇。多元醇是例如季戊四醇、二季戊四醇、三季戊四醇、短链聚醚多元醇或短链聚酯多元醇,以及具有醇基的超支化聚合物/低聚物或树枝状聚合物,例如:
优选地,所述至少一种糖醇选自苏糖醇、赤藓糖醇、半乳糖醇、甘露醇、核糖醇、山梨醇、木糖醇、阿拉伯糖醇、异麦芽糖醇、乳糖醇、麦芽糖醇、阿卓糖醇、艾杜糖醇、麦芽三糖醇以及具有多元醇端基的氢化寡糖和氢化多糖及其混合物。特别优选的是选自赤藓糖醇、甘露醇、异麦芽糖醇、麦芽糖醇及其混合物的至少一种优选的糖醇。
其它合适的糖醇的实例是庚醇和辛糖醇:内消旋-甘油-别-庚糖醇、D-甘油-D-他-庚糖醇、D-甘油-D-甘露糖庚糖醇、内消旋-甘油-古洛庚糖醇、D-甘油-D-半乳糖庚糖醇(甘露庚糖醇),D-甘油-D-葡萄糖庚糖醇,L-甘油-D-葡萄糖庚糖醇,D-赤型-L-半乳糖辛糖醇,D-苏型-L-半乳糖辛糖醇。
特别地,所述至少一种环醇可以选自肌醇(肌-肌醇、环己二醇、D-手性肌醇、L-手性肌醇、黏液肌醇、新肌醇、别肌醇、表肌醇和顺式肌醇)、1,2,3,4-四羟基环己烷、1,2,3,4,5-五羟基环己烷、槲皮醇、(1R,2S,3R,4S,5R,6S)-5,6-二甲氧基-1,2,3,4-环己烷四醇(viscumitol)、(1R,2R,3S,4S,5R,6S)-6-甲氧基-1,2,3,4,5-环己烷五醇、牛弥菜醇、(1R,2S,3S,4S,5S,6S)-6-甲氧基-1,2,3,4,5-环己烷五醇、松醇、(1R,2R,3R,4S,5R,6S)-3,6-二甲氧基-1,2,4,5-环己烷四醇、白坚木醇、西塞醇、奎尼酸、莽草酸和(1S,2S,3S,4R)-5-(羟甲基)-5-环己烯-1,2,3,4-四醇(valienol),其中优选肌-肌醇。
合适的光稳定剂是例如基于2-(2′-羟基苯基)苯并三唑、2-羟基苯并甲酮、苯甲酸的酯、丙烯酸酯、草酰胺和2-(2-羟基苯基)-1,3,5-三嗪的化合物。
合适的2-(2′-羟基苯基)苯并三唑有例如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-甲氧基羰基乙基)苯基)-5-氯苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)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;[R-CH2CH2-COO-CH2CH2-]-2,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。
合适的2-羟基苯并甲酮有例如2-羟基苯并甲酮的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。
合适的丙烯酸酯有例如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-甲氧羰基肉桂酸甲酯、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-甲氧羰基-对甲氧基肉桂酸甲酯和N-(β-甲氧羰基-β-氰基乙烯基)-2-甲基吲哚啉。
合适的苯甲酸的酯有例如水杨酸4-叔丁基苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰基间苯二酚、双(4-叔丁基苯甲酰基)间苯二酚、苯甲酰基间苯二酚、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、十六烷基-3,5-二叔丁基-4-羟基苯甲酸酯、十八烷基-3,5-二叔丁基-4-羟基苯甲酸酯、2-甲基-4,6-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯。
合适的草酰胺有例如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-甲氧基-二取代的草酰替苯胺和对-甲氧基-二取代的草酰替苯胺的混合物以及邻-乙氧基-二取代的草酰替苯胺和对-乙氧基-二取代的草酰替苯胺的混合物。
合适的2-(2-羟基苯基)-1,3,5-三嗪有例如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。
合适的金属减活剂有例如N,N′-二苯基草酰胺、N-水杨酰基-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-水杨酰基氨基-1,2,4-三唑、双(苯亚甲基)草酰二酰肼、草酰替苯胺、间苯二甲酰二酰肼、癸二酰-双苯酰肼、N,N′-二乙酰基己二酰二酰肼、N,N′-双(水杨酰基)氧基二酰肼、N,N′-双(水杨酰基)硫代丙酰二酰肼。
特别优选的金属减活剂是:
合适的低分子受阻胺为例如1,1-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产物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合产物、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-丁烷四羧酸酯、1,1′-(1,2-乙烷二基)-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-硬脂基氧基-2,2,6,6-四甲基哌啶、N,N′-双(2,2,6,6-四甲基-4-哌啶基)己二胺与4-吗啉代-2,6-二氯-1,3,5-三嗪的线性或环状缩合产物、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]癸烷与环氧氯丙烷的反应产物。
在每种情况下,包含在上述结构中的还有空间位阻的N-H,N-烷基如N-甲基或N-辛基,N-烷氧基衍生物如N-甲氧基或N-辛氧基,环烷基衍生物如N-环己氧基和N-(2-羟基-2-甲基丙氧基)类似物。
优选的受阻胺还具有以下结构:
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合适的分散剂是,例如:
聚丙烯酸酯,例如具有长链侧基的共聚物、聚丙烯酸酯嵌段共聚物、烷基酰胺:例如N,N′-1,2-乙烷二基双十八烷酰胺脱水山梨糖醇酯,例如单硬脂基脱水山梨糖醇酯、钛酸酯和锆酸酯,具有官能团的反应性共聚物,例如聚丙烯-co-丙烯酸、聚丙烯-co-马来酸酐、聚乙烯-co-甲基丙烯酸缩水甘油酯、聚苯乙烯-alt-马来酸酐-聚硅氧烷:例如二甲基硅烷二醇-环氧乙烷共聚物、聚苯基硅氧烷共聚物,两亲共聚物:例如聚乙烯聚环氧乙烷嵌段共聚物、树枝状聚合物,例如含有羟基基团的树枝状聚合物。
合适的抗成核剂是吖嗪染料,如苯胺黑。
合适的阻燃剂尤其是:
无机阻燃剂如Al(OH)3、Mg(OH)2、AlO(OH)、MgCO3、层状硅酸盐如未改性或有机改性的蒙脱石或海泡石,复盐,如Mg-Al-硅酸盐、POSS(多面体低聚倍半硅氧烷)化合物、碳酸钙镁石、水菱镁矿或埃洛石和Sb2O3、Sb2O5、MoO3、锡酸锌、羟基锡酸锌,
含氮的阻燃剂如三聚氰胺、蜜勒胺、蜜白胺、聚[(8-氨基-1,3,4,6,7,9,9b-七氮杂非那烯-2,5-亚基)亚氨基](melon)、三聚氰胺衍生物、三聚氰胺缩合产物或三聚氰胺盐、苯并胍胺、聚异氰脲酸酯、尿囊素、磷腈,特别是氰尿酸三聚氰胺、磷酸三聚氰胺、磷酸二三聚氰胺、焦磷酸三聚氰胺、多磷酸三聚氰胺、三聚氰胺金属磷酸盐,如三聚氰胺磷酸铝、三聚氰胺磷酸锌、三聚氰胺磷酸镁以及相应的焦磷酸盐和多磷酸盐、聚[2,4-(哌嗪-1,4-基)-6-(吗啉-4-基)-1,3,5-三嗪]、多磷酸铵、硼酸三聚氰胺、氢溴酸三聚氰胺,
自由基形成剂,如烷氧基胺、羟胺酯、偶氮化合物、三氮烯化合物、二硫化物、多硫化物、硫醇、硫化秋兰姆、二硫代氨基甲酸盐、巯基苯并噻唑、次磺酰胺、次磺酰亚胺、二枯基或多枯基、羟基酰亚胺及其衍生物,如羟基酰亚胺酯或羟基酰亚胺醚,
含磷阻燃剂如红磷,磷酸酯如间苯二酚二磷酸酯、双酚A二磷酸酯及其低聚物,磷酸三苯酯,乙二胺二磷酸盐,次膦酸盐如次磷酸盐及其衍生物如烷基次膦酸盐,例如,二乙基次膦酸铝或二乙基次膦酸锌或次膦酸铝,亚磷酸铝、膦酸铝、膦酸酯、甲烷膦酸的低聚物和高聚物衍生物、9,10-二氢-9-氧杂-10-磷酰基菲-10-氧化物(DOPO)及其被取代的化合物,
含卤素的基于氯和基于溴的阻燃剂,如多溴化二苯醚,例如十溴二苯醚、三(3-溴-2,2-双(溴甲基)丙基)磷酸酯、三(三溴新戊基)磷酸酯、四溴邻苯二甲酸、1,2-双(三溴苯氧基)乙烷、六溴环十二烷、溴化二苯乙烷、三(2,3-二溴丙基)异氰脲酸酯、亚乙基双(四溴邻苯二甲酰亚胺)、四溴双酚A、溴化聚苯乙烯、溴化聚丁二烯或聚苯乙烯溴化聚丁二烯共聚物、溴化聚苯醚、溴化环氧树脂、聚丙烯酸五溴苄酯,任选地与Sb2O3和/或Sb2O5组合,
硼酸盐如硼酸锌或硼酸钙,任选地在载体材料如二氧化硅上的硼酸盐,
含硫化合物,如单质硫、二硫化物和多硫化物、硫化秋兰姆、二硫代氨基甲酸盐、巯基苯并噻唑和次磺酰胺,
抗滴落剂如聚四氟乙烯,
含硅化合物如聚苯硅氧烷,
碳改性材料,如碳纳米管(CNT)、可膨胀石墨或石墨烯,
及其组合或混合物。
合适的增塑剂是例如邻苯二甲酸酯、己二酸酯、柠檬酸的酯、1,2-环己烷二羧酸的酯、偏苯三酸酯、异山梨酯、磷酸酯、环氧化物如环氧化大豆油或脂肪族聚酯。
合适的润滑剂和加工助剂是如聚乙烯蜡、聚丙烯蜡、脂肪酸的盐如硬脂酸钙、硬脂酸锌或褐煤蜡的盐、酰胺蜡如芥酸酰胺或油酸酰胺、含氟聚合物、有机硅或新烷氧基钛酸酯和锆酸酯。
合适的颜料可以是无机性质的或有机性质的。无机颜料是,例如二氧化钛、氧化锌、硫化锌、铁氧化物、群青、炭黑;有机颜料是,例如蒽醌、蒽酮、苯并咪唑酮、喹吖啶酮、二酮吡咯并吡咯、二嗪、靛蒽醌、异吲哚酮、偶氮化合物、苝、酞菁或吡喃酮。其他合适的颜料为基于金属的效果颜料或基于金属氧化物的珠光颜料。
合适的荧光增白剂是,例如双苯并唑、苯基香豆素或双(苯乙烯基)联苯和特别是下式的荧光增白剂:
合适的填料减活剂是,例如聚硅氧烷、聚丙烯酸酯,特别是嵌段共聚物如聚甲基丙烯酸聚环氧烷或聚(甲基)丙烯酸缩水甘油酯及其与例如苯乙烯和环氧化物的共聚物,例如具有以下结构:
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此外,在优选的实施方案中,本发明涉及稳定剂组合物与至少一种添加剂的组合的用途,特别地,所述至少一种添加剂选自初级抗氧化剂、除亚磷酸酯和亚膦酸酯以外的次要抗氧化剂、UV吸收剂、光稳定剂、金属减活剂、填料减活剂、抗臭氧剂、成核剂、抗成核剂、抗冲击改性剂、润滑剂、流变改性剂、触变剂、扩链剂、加工助剂、脱模助剂、阻燃剂、颜料、染料、荧光增白剂、抗微生物活性剂、抗静电剂、滑爽剂、防结块剂、偶联剂、交联剂、抗交联剂、亲水剂、疏水剂、黏结促进剂、分散剂、增溶剂、除氧剂、除酸剂、发泡剂、降解添加剂、消泡剂、除臭剂、标记剂、防雾剂、填料和增强剂及其混合物。
本发明还涉及由至少一种亚硫酸盐和/或至少一种硫代硫酸盐与至少一种聚合或低聚受阻胺的组合组成的稳定剂组合物,其用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解。
根据优选的实施方案,规定至少一种亚硫酸盐和/或硫代硫酸盐的总量与至少一种聚合或低聚受阻胺的总量的重量比为1∶99至99∶1,优选20∶80至80∶20,还优选30∶70至70∶30,特别优选40∶60至60∶40。
本发明还涉及母料,其包含10重量%至90重量%的根据前述两项权利要求之一的稳定剂组合物,和90重量%至10重量%的热塑性塑料,特别是塑料回收材料、原生塑料或它们的混合物。
本发明还涉及组合物,特别是塑料组合物,包含或组成为
A)根据本发明的稳定剂组合物和
B)待稳定的有机材料,特别是塑料。
本组合物的优选实施方案规定该组合物包含或由以下组成
(A)0.01重量%至10.00重量%,优选0.02重量%至5.00%,特别优选0.05重量%至2.00重量%的稳定剂组合物,
(B)85.00重量%至99.98重量%,优选96重量%至99.90重量%的至少一种塑料,和
(C)0.01重量%至5.00重量%,优选0.05重量%至1.00重量%至少一种添加剂。
还有利的实施方案规定,基于100重量份的组分(A)至(C),包含最多80重量份,优选0.1重量份至60重量份,特别优选1重量份至50重量份的至少一种增塑剂、填料和/或增强剂。
此外,本发明涉及可由根据本发明的组合物生产的模塑料或模制部件,特别是以下形式:箔或膜;包装,例如用于食品或化妆产品、洗涤剂、化妆品或黏合剂的包装;中空体,特别是瓶子、袋子、螺旋盖罐;储存和运输容器,例如箱子、板条箱、滚桶、桶;汽车、铁路、飞机、船舶和机器部件,如保险杠、装饰部件、配件和功能部件、室内装潢品;建筑应用制品,如型材、建筑膜、屋顶膜、电缆管道、房屋覆盖层、隔音屏障、排水管道、异型板、地板覆盖物、托盘;道路和景观应用制品,如灯塔基座、标杆、栅栏、土工织物;电气和电子应用制品,例如电视机、计算机、移动电话、洗衣机、洗碗机、咖啡机、钻孔机、连接器、存储介质的外壳零件和附件;电缆绝缘体;来自添加或生成制造工艺的部件,如熔融层积成型(FLM)、层压成型(LLM)、选择性激光烧结(SLS)和其他3D打印工艺;用于例如水、气、污水、灌溉、排水管的管道;卫生用品,如尿布或作为一次性尿布、卫生巾和卫生棉条的组成部分;家具和纺织品应用制品,如窗帘和室内装潢、操作台面;泡沫、胶带、注塑部件、纤维和其他挤出物;家居、休闲和运动用品,如球、网球拍、滑雪板、花盆、雨桶、衣架;农业应用制品,如温室、覆盖物、隧道或穿孔用的膜、花盆、膜如土工膜;药物和作物保护应用制品,如活性成分和生物活性物质的包封材料;以及缝线、绷带、矫形器和假肢。
此外,本发明涉及氧化稳定、热稳定和/或光化稳定热塑性塑料,特别是抗氧化降解、热降解和/或光化降解的方法,该方法是通过将至少一种根据本发明的稳定剂组合物添加、补充或结合到塑料中来实现的。
优选地,根据本发明的添加剂组合,其可以以粉末、液体、油、压实的形式存在于载体材料上,作为颗粒、溶液或薄片,与待稳定的聚合物混合,并将聚合物基质转移到熔体中,然后冷却。或者,也可以将一种或多于一种添加剂引入熔融状态的聚合物熔体中。
在向聚合物组合物中添加其它组分的情况下,这些组分可以以液体、粉末、颗粒或压实产品的形式单独添加到聚合物中,或者与如上所述的根据本发明的添加剂组合物一起添加。
如有必要,通过常规加工方法将上述添加剂组合物和其他添加剂掺入塑料中,优选通过混合机、捏合机或挤出机。优选的加工机器是挤出机,如单螺杆挤出机、双螺杆挤出机、行星辊式挤出机、环式挤出机和共捏合机,它们优选配有真空脱气装置。可以在空气条件下进行加工,必要时也可以在惰性气体条件下进行加工。
本发明的另一方面涉及根据本发明的上述组合物用于生产以下制品的用途:箔或膜;包装,例如用于食品或化妆产品、洗涤剂、化妆品或黏合剂的包装;中空体,特别是瓶子、袋子、螺旋盖罐;储存和运输容器,如箱子、板条箱、滚桶、桶;汽车、铁路、飞机、船舶和机器部件,例如保险杠、装饰部件、配件和功能部件、室内装潢制品;建筑应用制品,如型材、建筑膜、屋面膜、电缆管道、房屋覆盖层、隔音屏障、排水管道、异型板、地板覆盖物、托盘;道路和景观应用制品,如灯塔基座、标杆、栅栏、土工织物;电气和电子应用制品,如电视机、计算机、移动电话、洗衣机、洗碗机、咖啡机、钻孔机、连接器、存储介质的外壳零件和附件;电缆绝缘体;来自添加或生成制造工艺的部件,如熔融层积成型(FLM)、层压成型(LLM)、选择性激光烧结(SLS)和其他3D打印工艺;用于如水、气体、污水、灌溉、排水管的管道;卫生用品,如尿布或作为一次性尿布、卫生巾和卫生棉条的组成部分;家具和纺织品应用制品,如窗帘和室内装潢制品、操作台面;泡沫、胶带、注塑部件、纤维和其他挤出物;家居、休闲和运动用品,如球、网球拍、滑雪板、花盆、雨桶、衣架;农业应用制品,如温室、覆盖物、隧道或穿孔用的膜、花盆、膜如土工膜;药物和作物保护应用制品,如活性成分和生物活性物质的包封材料;以及缝线、绷带、矫形器和假肢。
参考以下示例性实施例更详细地描述本发明,而不将本发明限制于所呈现的具体实施例。
示例性实施例
为了测试根据本发明的稳定剂组合物的效果,将聚乳酸(PLA)(Luminy L175,供应商:Total Corbion)连同表1中所列的成分,以及从电池外壳研磨材料中回收的消费后聚丙烯回收材料(供应商:BSB·布劳巴赫)连同表2中所列的添加剂,在双螺杆微型挤出机(Micro 5cc,制造商DSM)中以连续模式在200rpm下在210℃下以熔体形式循环30分钟。30分钟后,测量力吸收。该力是熔体韧性的度量,因此也是聚合物分子量的度量。剩余力越高,聚合物的降解越低。在每种情况下都给出了两次测试的平均值。
表1:PLA的稳定化
*Sabostab 119的分子式:
表2:聚丙烯电池壳回收料的稳定性
**Tinuvin NOR 371的分子式:
(Tinuvin NOR 371(RTM),CAS 565450-39-7)
根据本发明的组合产生非常好的稳定效果以及有利的成本结构。
出乎意料地,用受阻胺和无机亚硫酸盐的组合可以获得良好的稳定效果,并且受阻胺可以部分被便宜的亚硫酸盐替代。
提供了新的稳定剂组合物和特别是稳定塑料的新方法,它们是高效的、环境友好的并具有有利的成本结构。
Claims (21)
1.至少一种稳定剂组合物用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解的用途,所述稳定剂组合物包含或组成为至少一种亚硫酸盐和/或至少一种硫代硫酸盐与至少一种聚合或低聚受阻胺的组合。
2.根据权利要求1所述的用途,其用于稳定塑料、涂料、润滑剂、液压油、发动机油、涡轮机油、变速器油、金属加工液、化学品或单体。
3.根据前述权利要求所述的用途,其特征在于,所述塑料选自原生塑料、塑料回收材料及其混合物或组合。
4.根据前述权利要求中任一项所述的用途,其特征在于
所述至少一种亚硫酸盐是无机亚硫酸盐、无机二亚硫酸盐或无机亚硫酸氢盐,优选一价金属、二价金属、三价金属或四价金属的盐,所述金属优选为碱金属、碱土金属、铝和/或锌,特别优选选自亚硫酸钠、亚硫酸钾、亚硫酸锂、亚硫酸钙、亚硫酸镁、亚硫酸铝、亚硫酸锌的亚硫酸盐及其混合物和组合,所使用的亚硫酸盐特别为不含结晶水的形式,和/或
所述至少一种硫代硫酸盐是一价金属、二价金属、三价金属或四价金属的硫代硫酸盐,所述金属优选为碱金属、碱土金属、铝和/或锌,特别优选硫代硫酸钠,所述硫代硫酸盐特别以不含结晶水的形式使用。
5.根据前述权利要求中任一项所述的用途,其特征在于,所述至少一种聚合或低聚受阻胺具有>1000g/mol的数均分子量,特别是所述至少一种聚合或低聚受阻胺选自以下化合物
其中n在每种情况下表示2至100的整数,优选3至20,特别优选3至10,并且
R表示-O-C(O)-C15H31或-O-C(O)-C17H35,
其中,在N-H基团的情况下,其在每次出现时能够独立地被以下基团替代:N-烷基如N-甲基或N-辛基、N-烷氧基如N-甲氧基或N-辛氧基、N-环烷基如N-环己氧基,和N-(2-羟基-2-甲基丙氧基),
以及它们的混合物和组合。
6.根据前述权利要求中任一项所述的用途,其特征在于,相对于待稳定的有机材料,所述稳定剂组合物以0.01重量%至10.00重量%的重量比使用,优选0.02重量%至5.00重量%,特别优选0.05重量%至2.00重量%。
7.根据前述权利要求中任一项所述的用途,其特征在于
至少一种亚硫酸盐和/或硫代硫酸盐的总量和至少一种聚合或低聚受阻胺的总量的重量比为1∶99至99∶1,优选20∶80至80∶20,还优选30∶70至70∶30,特别优选40∶60至60∶40。
8.根据前述权利要求中任一项所述的用途,其用于稳定塑料,其中所述塑料选自
a)烯烃或二烯烃的聚合物,如聚乙烯(LDPE、LLDPE、VLDPE、ULDPE、MDPE、HDPE、UHMWPE)、茂金属-PE(m-PE)、聚丙烯、聚异丁烯、聚-4-甲基-戊烯-1、聚丁二烯、聚异戊二烯,如天然橡胶(NR)、聚环辛烯、聚亚烷基-一氧化碳共聚物、以及无规结构或嵌段结构形式的共聚物,如聚丙烯-聚乙烯(EP)、EPM或以例如5-亚乙基-2-降冰片烯为共聚单体的EPDM、乙烯-乙酸乙烯酯(EVA)、乙烯丙烯酸酯例如乙烯-丙烯酸丁酯、乙烯-丙烯酸及其盐(离聚物),以及三元共聚物例如乙烯-丙烯酸-(甲基)丙烯酸缩水甘油酯、接枝聚合物如聚丙烯-接枝-马来酸酐、聚丙烯-接枝-丙烯酸、聚乙烯-接枝-丙烯酸、聚乙烯-聚丙烯酸丁酯-接枝-马来酸酐、以及共混物例如LDPE/LLDPE或用α-烯烃例如1-丁烯、1-己烯、1-辛烯或1-十八烯作为共聚单体制备的长链支化聚丙烯共聚物,
b)聚苯乙烯、聚甲基苯乙烯、聚α-甲基苯乙烯、聚乙烯萘、聚乙烯联苯、聚乙烯甲苯、苯乙烯-丁二烯(SB)、苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯-丁烯-苯乙烯(SEBS)、苯乙烯-乙烯-丙烯-苯乙烯、苯乙烯异戊二烯、苯乙烯-异戊二烯-苯乙烯(SIS)、苯乙烯-丁二烯-丙烯腈(ABS)、苯乙烯-丙烯腈(SAN)、苯乙烯-丙烯腈-丙烯酸酯(ASA)、苯乙烯-乙烯、苯乙烯-马来酸酐聚合物,包括相应的接枝共聚物例如丁二烯上的苯乙烯、SBS或SEBS上的马来酸酐、以及甲基丙烯酸甲酯、苯乙烯丁二烯和ABS(MABS)的接枝共聚物、以及水合聚苯乙烯衍生物例如聚乙烯环己烷,
c)含卤素聚合物,如聚氯乙烯(PVC)、聚氯丁二烯和聚偏二氯乙烯(PVDC)、氯乙烯和偏二氯乙烯的共聚物或氯乙烯和乙酸乙烯酯的共聚物、氯化聚乙烯、聚偏二氟乙烯、表氯醇的均聚物和共聚物,特别是与环氧乙烷的共聚物(ECO),
d)不饱和酯的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯例如聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸丁酯、聚丙烯酸月桂酯、聚丙烯酸硬脂酯、聚丙烯酸缩水甘油酯、聚甲基丙烯酸缩水甘油酯、聚丙烯腈、聚丙烯酰胺、共聚物如聚丙烯腈-聚丙烯酸烷醇酯,
e)不饱和醇及其衍生物的聚合物,如聚乙烯醇、聚乙酸乙烯酯、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙酯、聚烯丙基三聚氰胺,
f)聚缩醛,如聚甲醛(POM)或与例如丁醛、聚苯乙醚的共聚物,以及与聚苯乙烯或聚酰胺的共混物,
g)环醚的聚合物,如聚乙二醇、聚丙二醇、聚环氧乙烷、聚环氧丙烷、聚四氢呋喃,
h)聚苯醚及其与聚苯乙烯和/或聚酰亚胺的共混物,
i)来自羟基封端的聚醚或聚酯与芳香族或脂族异氰酸酯如2,4-或2,6-甲苯二异氰酸酯或亚甲基二苯基二异氰酸酯的聚氨酯,特别是线性聚氨酯(TPU)、聚脲,
j)聚酰胺,如聚酰胺-6、聚酰胺-6.6、聚酰胺-6.10、聚酰胺-4.6、聚酰胺-4.10、聚酰胺-6.12、聚酰胺-10.10、聚酰胺-10.12、聚酰胺-12.12、聚酰胺11、聚酰胺12以及(部分)芳族聚酰胺,例如聚苯二甲酰胺,如由对苯二甲酸和/或间苯二甲酸与脂族二胺如六亚甲基二胺或间苯二甲胺制备的聚酰胺,或者由脂肪族二羧酸如己二酸或癸二酸与芳香族二胺如1,4-或1,3-二氨基苯制备的聚酰胺,不同聚酰胺如PA-6和PA 6.6的共混物,或聚酰胺和聚烯烃的共混物如PA/PP,
k)聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚(醚)酮、聚砜、聚醚砜、聚芳砜、聚苯硫醚、聚苯并咪唑、聚乙内酰脲,
l)脂肪族或芳香族二羧酸与二醇或羟基羧酸的聚酯,如聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯(PBT)、聚对苯二甲酸丙二醇酯(PTI)、聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸1,4-二羟甲基环己烷酯、聚羟基苯甲酸酯、聚羟基萘二甲酸酯、聚乳酸(PLA)、聚羟基丁酸酯(PHB)、聚羟基戊酸酯(PHV)、聚丁二酸乙二醇酯、聚丁二酸丁二醇酯、聚己内酯,
m)聚碳酸酯、聚酯碳酸酯、及其共混物如PC/ABS、PC/PBT、PC/PET/PBT、PC/PA,
n)纤维素衍生物,如硝酸纤维素、醋酸纤维素、丙酸纤维素、丁酸纤维素,
o)组成为双官能或多官能环氧化合物与例如基于胺、酸酐、双氰胺、硫醇、异氰酸酯的硬化剂或催化作用硬化剂的组合的环氧树脂,
p)酚类树脂如酚醛树脂、脲醛树脂、三聚氰胺甲醛树脂,
q)由不饱和二羧酸和二醇与乙烯基化合物例如苯乙烯形成的不饱和聚酯树脂、醇酸树脂、烯丙基树脂,
r)硅氧烷,例如乙烯基封端的例如基于二甲基硅氧烷、甲基苯基硅氧烷或二苯基硅氧烷,
s)以及上述聚合物中的两种或多于两种的混合物、组合或共混物。
9.根据前述权利要求中任一项所述的用途,其特征在于,所述稳定剂组合物与至少一种添加剂组合使用,特别地,至少一种添加剂选自初级抗氧化剂、除亚磷酸酯和亚膦酸酯以外的次要抗氧化剂、UV吸收剂、光稳定剂、金属减活剂、填料减活剂、抗臭氧剂、成核剂、抗成核剂、抗冲击改性剂、润滑剂、流变改性剂、触变剂、扩链剂、加工助剂、脱模助剂、阻燃剂、颜料、染料、荧光增白剂、抗微生物活性剂、抗静电剂、滑爽剂、防结块剂、偶联剂、交联剂、抗交联剂、亲水剂、疏水剂、黏结促进剂、分散剂、增溶剂、除氧剂、除酸剂、发泡剂、降解添加剂、消泡剂、除臭剂、标记剂、防雾剂、填料和增强剂及其混合物。
10.一种用于稳定有机材料,特别是抗氧化降解、热降解和/或光化降解的稳定剂组合物,其组成为至少一种亚硫酸盐和/或至少一种硫代硫酸盐与至少一种聚合或低聚受阻胺的组合。
11.根据前述权利要求所述的稳定剂组合物,其特征在于
至少一种亚硫酸盐和/或硫代硫酸盐的总量与至少一种聚合或低聚受阻胺的总量的重量比为1∶99至99∶1,优选20∶80至80∶20,还优选30∶70至70∶30,特别优选40∶60至60∶40。
12.一种母料,包含
10重量%至90重量%的根据前述两项权利要求中任一项所述的稳定剂组合物,和
90重量%至10重量%的热塑性塑料,特别是塑料回收材料、原生塑料或它们的混合物。
13.一种组合物,特别是塑料组合物,包含或组成为
A)根据权利要求10至11中任一项所述的稳定剂组合物,和
B)待稳定的有机材料,特别是塑料。
14.根据前述权利要求所述的组合物,其特征在于所述组合物包含或组成为
(A)0.01重量%至10.00重量%,优选0.02重量%至5.00重量%,特别优选0.05重量%至2.00重量%的稳定剂组合物,
(B)85.00重量%至99.98重量%,优选96重量%至99.90重量%的至少一种塑料,和
(C)0.01重量%至5.00重量%,优选0.05重量%至1.00重量%的至少一种添加剂。
15.根据前述权利要求所述的组合物,其特征在于,所述至少一种添加剂选自初级抗氧化剂、除亚磷酸酯和亚膦酸酯之外的次要抗氧化剂、UV吸收剂、光稳定剂、金属减活剂、填料减活剂、抗臭氧剂、成核剂、抗成核剂、抗冲击改性剂、润滑剂、流变改性剂、触变剂、扩链剂、加工助剂、脱模助剂、阻燃剂、颜料、染料、荧光增白剂、抗微生物活性剂、抗静电剂、滑爽剂、防结块剂、偶联剂、交联剂、抗交联剂、亲水剂、疏水剂、黏结促进剂、分散剂、增溶剂、除氧剂、除酸剂、发泡剂、降解添加剂、消泡剂、除臭剂、标记剂、防雾剂、填料和增强剂及其混合物。
16.根据前述两项权利要求中任一项所述的组合物,其特征在于,基于100重量份的(A)至(C)组分,包含最多80重量份,优选0.1至60重量份,特别优选1至50重量份的至少一种增塑剂、填料和/或增强剂。
17.根据前述两项权利要求中任一项所述的组合物,其特征在于
a)亚磷酸酯或亚膦酸酯选自下列化合物
其中n=3至100
b)填料和/或增强剂选自碳酸钙、硅酸盐、滑石、云母、高岭土、金属氧化物、金属氢氧化物、炭黑、石墨、木粉、天然产品纤维如纤维素、玻璃纤维、碳纤维、聚芳酰胺纤维和其它合成聚合物纤维、水滑石、沸石和/或层状硅酸盐如蒙脱土、膨润土、贝得石、云母、锂蒙脱石、皂石、蛭石、水黑云母、麦羟硅钠石、伊利石、高岭石、硅灰石、绿坡缕石,和
c)除酸剂选自一价金属、二价金属、三价金属或四价金属的盐,优选碱金属、碱土金属、铝或锌的盐,特别是与脂肪酸形成的盐,例如硬脂酸钙、硬脂酸镁、硬脂酸锌、硬脂酸铝、月桂酸钙、山嵛酸钙、乳酸钙、硬脂酰-2-乳酸钙,其它种类的合适除酸剂是水滑石,特别是基于铝、镁和锌的合成水滑石,水钙铝石、沸石、碱土金属氧化物,特别是氧化钙和氧化镁以及氧化锌,碱土金属碳酸盐,特别是碳酸钙、碳酸镁和白云石,以及氢氧化物,特别是水镁石(氢氧化镁)。
18.一种能够由根据权利要求13至17中任一项所述的组合物生产的模塑料或模制部件,特别是以下形式
箔或膜;
包装,例如用于食品或化妆产品、洗涤剂、化妆品或黏合剂的包装;
中空体,特别是瓶子、袋子、螺旋盖罐;储存和运输容器,如箱子、板条箱、滚桶、桶;
汽车、铁路、飞机、船舶和机器部件,例如保险杠、装饰部件、配件和功能部件、室内装潢制品;
建筑应用制品,如型材、建筑膜、屋顶膜、电缆管道、房屋覆盖层、隔音屏障、排水管道、异型板、地板覆盖物、托盘;
道路和景观应用制品,如灯塔基座、标杆、栅栏、土工织物;
电气和电子应用制品,如电视机、计算机、移动电话、洗衣机、洗碗机、咖啡机、钻孔机、连接器、存储介质的外壳零件和附件;
电缆绝缘体;
来自添加或生成制造工艺的部件,如熔融层积成型(FLM)、层压成型(LLM)、选择性激光烧结(SLS)和其他3D打印工艺;
用于如水、气体、污水、灌溉、排水管的管道;
卫生用品,如尿布或作为一次性尿布、卫生巾和卫生棉条的组成部分;
家具和纺织品应用制品,如窗帘和室内装潢制品、操作台面;
泡沫、胶带、注塑部件、纤维和其他挤出物;
家居、休闲和运动用品,如球、网球拍、滑雪板、花盆、雨桶、衣架;
农业应用制品,如温室、覆盖物、隧道或穿孔用的膜、花盆、膜如土工膜;
药物和作物保护应用制品,如活性成分和生物活性物质的包封材料;
以及缝线、绷带、矫形器和假肢。
19.一种用于氧化稳定、热稳定和/或光化稳定热塑性塑料,特别是抗氧化降解、热降解和/或光化降解的方法,所述方法是通过向热塑性塑料中添加、补充或掺入至少一种根据权利要求10至11中任一项所述的稳定剂组合物来实现的。
20.根据前述权利要求所述的方法,其特征在于,热稳定发生在热塑性塑料的热加工过程中,该热加工特别发生在非质子条件下。
21.根据权利要求13至17中任一项所述的组合物在用于生产以下制品中的用途:
箔或膜;
包装,例如用于食品或化妆产品、洗涤剂、化妆品或黏合剂的包装;
中空体,特别是瓶子、袋子、螺旋盖罐;储存和运输容器,如箱子、板条箱、滚桶、桶;
汽车、铁路、飞机、船舶和机器部件,例如保险杠、装饰部件、配件和功能部件、室内装潢制品;
建筑应用制品,如型材、建筑膜、屋顶膜、电缆管道、房屋覆盖层、隔音屏障、排水管道、异型板、地板覆盖物、托盘;
道路和景观应用制品,如灯塔基座、标杆、栅栏、土工织物;
电气和电子应用制品,如电视机、计算机、移动电话、洗衣机、洗碗机、咖啡机、钻孔机、连接器、存储介质的外壳零件和附件;
电缆绝缘体;
来自添加或生成制造工艺的部件,如熔融层积成型(FLM)、层压成型(LLM)、选择性激光烧结(SLS)和其他3D打印工艺;
用于如水、气体,污水、灌溉、排水管的管道;
卫生用品,如尿布或作为一次性尿布、卫生巾和卫生棉条的组成部分;
家具和纺织品应用制品,如窗帘和室内装潢制品、操作台面;
泡沫、胶带、注塑部件、纤维和其他挤出物;
家居、休闲和运动用品,如球、网球拍、滑雪板、花盆、雨桶、衣架;
农业应用制品,如温室、覆盖物、隧道或穿孔用的膜、花盆、膜如土工膜;
药物和作物保护应用制品,如活性成分和生物活性物质的包封材料;
以及缝线、绷带、矫形器和假肢。
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