CN106715560B - 有机氧基酰亚胺在塑料中作为自由基生成剂的用途,生成自由基的方法及该方法的用途 - Google Patents
有机氧基酰亚胺在塑料中作为自由基生成剂的用途,生成自由基的方法及该方法的用途 Download PDFInfo
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- CN106715560B CN106715560B CN201580050105.0A CN201580050105A CN106715560B CN 106715560 B CN106715560 B CN 106715560B CN 201580050105 A CN201580050105 A CN 201580050105A CN 106715560 B CN106715560 B CN 106715560B
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Abstract
本发明涉及式(I)的有机氧基酰亚胺在塑料中作为自由基生成剂的用途。
Description
本发明涉及有机氧基酰亚胺在塑料中作为自由基生成剂的用途。此外,本发明涉及用于在塑料中生成自由基的方法,特别是用于塑料或聚合物的降解反应和交联反应和接枝反应,以及涉及该方法的用途。
不同类型的聚合物的受控制备,特别是聚烯烃(不同分子量、熔融黏度、分子量分布、密度)类型的受控制备一方面可以在合成期间进行,也可以在后续步骤中进行,例如在借助于挤出或注塑的工艺期间进行。已建立的方法从而是添加自由基形成剂,该自由基形成剂相应地在加工温度下引发自由基反应,其之后根据聚合物结构导致聚合物降解,即导致分子量降低,或聚合物增加、即导致分子量增加直至支化和交联。
商业上重要的方法是聚丙烯的降解(被称为“减黏裂化”)以形成具有较低分子量和较窄分子量分布的产物(被称为“受控流变学PP”或“CR-PP”)。得到的产物用于例如聚丙烯纤维的制备(“熔喷法”或“纺粘法”)或用于易流动的薄壁注塑部件(“薄壁注塑”)。用于该方法所使用的常规自由基生成剂是有机过氧化物(参见例如D.Munteanu in H.Zweifel,Plastics Additives Handbook,Munich 2001,第725-811页)。然而,有机过氧化物在处理期间需要大量的安全装置,导致不期望的二次反应,且来自过氧化物的分解产物可以负面地影响聚合物特性,例如长期的稳定性。水性过氧化氢的使用 (WO 2012/000022)从而代表了改进,然而,这里关于技术安全性的处理同样是有挑战的,并且不能在常规可用的加工设备中进行。聚丙烯降解工艺中自由基生成剂的另外的已知替代物是羟基哌啶酯(WO0190113)、不对称的偶氮化合物(WO 2006/106059)或亚氨基氧基三嗪(WO 2014/064064)。然而,这些化合物常常难以合成获得,以至于它们在商业上不重要。
其他工业上重要的工艺是利用自由基形成剂的聚乙烯(例如LDPE、 LLDPE、MDPE)的交联。这些利用添加过氧化物的工艺常常用于管和电缆的生产。此外,转而适用的是所提及的安全方面必须考虑,在此受控二次反应导致不期望的凝胶形成并导致工艺问题。
另外的工业上重要的工艺是在有机过氧化物存在下将单体或不饱和的低聚物接枝到现有的聚合物链上。这些工艺对于马来酸酐接枝的或丙烯酸接枝的聚乙烯或聚丙烯、聚烯烃共聚物和三元共聚物、以及马来酸酐接枝的苯乙烯-丁二烯或苯乙烯-丁二烯-苯乙烯嵌段共聚物和其水合的后续产物的制备是首先重要的。在此另外地,因为过氧化物较低的分解温度,会发生不期望的二次反应,例如降解、凝胶形成和/或变色。
因此,仍存在对以下自由基生成剂的需求:其对由自由基引发的自由基工艺具有改善的控制、具有可调节的引发温度、高的工艺安全和简单的合成可获得性,该自由基生成剂另外可以用作正常加工机器例如挤出机上的添加剂。
因此,本发明的目的是指出规避前述问题的用于塑料的另外的自由基生成剂。
该目的在有机氧基酰亚胺在塑料中作为自由基生成剂的用途方面是通过专利权利要求1实现的,在用于在塑料中生成自由基的方法方面是通过专利权利要求14的特征实现的,在该方法的使用目的方面是通过专利权利要求17的特征实现的。剩余的从属专利权利要求从而代表有利的发展方案。
因此,本发明涉及有机氧基酰亚胺作为塑料中自由基生成剂的用途。根据本发明已知的是包含至少一种以下式I所示的结构单元的有机氧基酰亚胺的用途适合作为塑料中自由基生成剂。
式I从而理解为所示结构单元被包含在有机氧基酰亚胺中。根据本发明使用的氧基酰亚胺从而不应等同于异氰脲酸酯或由其衍生的化合物或化合物种类。
根据本发明的优选实施方案,特别地,包含至少一种以下式II的结构单元的氧基酰亚胺用作塑料的自由基生成剂,R1代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团。
任选地,或者与前述优选的变化方案组合,同样使用包含至少一种下式III的结构单元的桥接氧基酰亚胺,R2代表任选地经取代的亚烷基、亚环烷基、亚芳基、亚杂芳基或桥接酰基基团。
根据本发明使用的氧基酰亚胺从而同样优选无卤素的,即相应的化合物不包含任何卤素原子。
根据优选的变化方案,R2选自以下基团:
–(CH2)n–,其中n=1至18、–CH(CH3)–、–C(CH3)2–、–O–、–S–、–SO2–、–NHCO–、–CO–、–OC(O)O–以及以下所示的基团:
之前所示基团中含有的脂环族或芳香族环体系为未经取代的或被一个或更多个烷基和/或烷氧基基团取代,
Q在每次出现时为相同或不同的,并选自化学键以及基团–(CH2)n–,其中n=1至18、–CH(CH3)–、–C(CH3)2–、–O–、–S–、–SO2–、–NHCO–、O-C(O)-O-、–CO–,
m为0或1至18。
关于特别的优选,基团R2从而是由以下所示结构单元复制的,Q具有上文指示的含义:
特别地,基团R2从而通过以下结构单元给出:
根据特别优选的实施方案,在本发明的该变化方案的情况下,有机氧基酰亚胺具有以下的结构式之一:
R1和R2分别具有上文指示的含义,且R1和R1或R2和R2具有相同的含义。
特别优选的基团R1从而是氢、烷基或酰基基团。
作为塑料中的自由基生成剂,以下所示的化合物是特别合适的,R2具有上文指示的含义。
因此,进行合适的自由基生成剂的选择以使得自由基的形成在各个聚合物的加工温度下在反应和各个加工方法的足够的范围内进行。自由基形成的温度可以通过例如DSC(“差示扫描量热法”)确定。选择的其他标准是反应产物的形成,其可以是例如挥发物并因此可以容易地从产物中去除,或可以是高分子并因此留在产物中而没有任何不利。用于塑料加工工艺的各个加工工艺和温度是本领域技术人员已知的。然而,塑料加工工艺和与其相关的温度也可以从专业文献中推断,例如H.Domininghaus,P.Elsner,P. Eyerer,T.Hirth,Kunststoffe(Plastic materials),第8版,Springer 2012。特别地,关于降解方法,额外添加链转移剂可以是有利的。可能的链转移剂可以选自硫醇、二硫化物、磷酸酯、磷化氢、有机卤化物,例如碘化物、溴化物、氯化物,酸酯、醛或叔胺。优选地,链转移剂具有在各个聚合物的加工温度之上的沸点。特别优选的是硫衍生物,例如硫醇和二硫化物。合适的链转移剂是例如:
特别地,对于分子量增加反应和对于交联反应,除自由基生成剂和聚合物之外,添加另外的多官能化合物可以是有利的。合适的化合物包括
a)基于聚丁二烯或聚异戊二烯的多不饱和的聚合物和低聚物
b)二乙烯基和聚乙烯基化合物,例如二乙烯基苯
c)二烯丙基和聚烯丙基化合物,例如聚烯丙基醚或聚烯丙基酯、三烯丙基异氰脲酸酯、三烯丙基氰尿酸酯、二烯丙基双酚A
d)二马来酰亚胺和聚马来酰亚胺
e)二醇和多元醇的二(甲基)丙烯酸酯和聚(甲基)丙烯酸酯
f)有机官能硅烷
有机官能硅烷的典型实例是:
Y-(CH2)n-SiX3
其中n=0至3;Y=CH2=CH-、CH2=C(CH3)COO-、NH2-、SH-、Cl-; X=-OR(R=Me、Et)、-OCOCH3。
二马来酰亚胺和聚马来酰亚胺的典型实例是:
二醇和多元醇的二(甲基)丙烯酸酯和聚(甲基)丙烯酸酯的典型实例是:
其中n=2-5
其中n=1-5
其中R=H或甲基和m=0至10,n=2至10 烯丙基化合物的典型实例是:
在根据本发明的自由基形成剂的引发下,接枝反应在不饱和单体的存在下实施,所述不饱和单体通过反应借助于化学键键合到聚合物骨架上。合适的不饱和单体特别地是马来酸酐、衣康酸酐、N-烷基马来酰亚胺、丙烯酸、甲基丙烯酸、丙烯酸酯、甲基丙烯酸酯,例如(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂基酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸羟基乙酯。
此外,可以有利的是在另外的硝酰基自由基的存在下实施交联或接枝反应。借助于添加硝酰基自由基,可以调节交联或接枝反应,即反应可以更好地被控制,这导致工艺较少的二次反应。合适的硝酰基自由基是例如:
R1至R10代表任选地经取代的烷基基团、苯基、羟基、烷氧基或酯基团并且是可以以名称TEMPO、Hydroxy-TEMPO或Oxo-TEMPO商购获得的。以下硝酰基自由基是特别优选的:
此外,可以有利的是根据本发明的氧基酰亚胺的降解、交联或接枝反应在另外添加催化作用的化合物下进行。这种化合物可以是例如过渡金属例如铜、锰或铁的金属盐,例如乙酸盐的形式,例如乙酸亚铜(I)。
此外,可以有利的是根据本发明的自由基形成剂与至少一种另外的自由基形成剂组合,例如与不同种类的自由基形成剂和/或具有不同分解温度的自由基形成剂组合。选择自由基形成的温度使得该形成在各个聚合物的加工温度下进行。具有不同分解温度的自由基形成剂的组合在多阶段工艺的情况下是有利的,因此例如在低温的情况下可以进行聚乙烯的预交联和在较高温度的情况下可以进行聚乙烯的进一步交联。
在本发明的意义上,自由基形成剂是能够通过热裂解和光诱导裂解产生自由基的化合物。这里用于本申请合适的自由基形成剂是为其中进行降解、交联或接枝的塑料或涂料加工工艺递送足够量用于反应的自由基的那些。
因此,其他自由基形成剂优选地选自N-烷氧基胺、-C-C-自由基形成剂、具有偶氮基团(-N=N-)的自由基形成剂、具有肼基团(-NH-HN-)的自由基形成剂、具有腙基团(>C=N-NH-)的自由基形成剂、具有吖嗪基团 (>C=N-N=C<)的自由基形成剂、具有三氮烯基团(-N=N-N<)的自由基形成剂和亚氨基氧基三嗪。
合适的偶氮化合物的制备在例如M.Aubert等人,Macromol.Sci.Eng. 2007,292,707–714或在WO 2008101845中描述,腙和吖嗪的制备在M. Aubert等人,Pol.Adv.Technol.2011,22,1529–1538中描述,三氮烯的制备在W.Pawelec等人,Pol.Degr.Stab.2012,97,948–954中描述。亚氨基氧基三嗪的合成在WO 2014/064064中描述。
过氧化物是可商购获得的化合物,其可以从例如United Initiators获得。合适的过氧化物是例如:
2,5-二甲基-2,5-二(叔丁基过氧基)己烷、2,5-二甲基-2,5-二(叔丁基过氧基)己炔-3,3,6,6,9,9-五甲基-3-(乙酸乙酯)-1,2,4,5-四氧基环壬烷、叔丁基氢过氧化物、过氧化氢、二枯基过氧化物、叔丁基过氧基异丙基碳酸酯、二叔丁基过氧化物、对氯苯甲酰过氧化物、二苯甲酰二过氧化物、叔丁基枯基过氧化物、叔丁基羟基乙基过氧化物、二叔戊基过氧化物、2,5-二甲基亚己烯-2,5-二过异壬酸酯、乙酰环己烷磺酰基过氧化物、二异丙基过氧基二碳酸酯、叔戊基过氧化新癸酸酯、叔丁基过氧化新癸酸酯、叔丁基过氧化新戊酸酯、叔戊基过氧化新戊酸酯、双(2,4-二氯苯甲酰)过氧化物、二异壬酰基过氧化物、二癸酰基过氧化物、二辛酰基过氧化物、二月桂酰基过氧化物、双(2-甲基苯甲酰)过氧化物、二琥珀酰基过氧化物、二乙酰基过氧化物、二苯甲酰基过氧化物、叔丁基过氧化-2-乙基己酸酯、双(4-氯代苯甲酰基)过氧化物、叔丁基过氧化异丁酸酯、叔丁基过氧化马来酸酯、1,1-双(叔丁基过氧基)-3,5,5-三甲基环己烷、1,1-双(叔丁基过氧化氢过氧化物。
由此,至少一种另外的自由基形成剂特别优选地选自
a)根据以下所示结构式的N-烷氧基胺,
R3代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团,特别是C1至C4烷基基团,
R4代表烷氧基、芳氧基、环烷氧基、芳烷氧基、酰氧基基团,
Z代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团,两个基团Z还能够形成闭合的环,其能够任选地被酯基团、醚基团、胺基团、酰胺基团、羧基基团、尿烷基团取代,
b)根据以下所示结构式的偶氮化合物,
R5-N=N-R5或
R5表示烷基、环烷基或芳基基团,
R6在每次出现时是相同或不同的,表示直链或带支链的烷基基团,
R7在每次出现时是相同或不同的,表示氢或者直链或带支链的烷基基团,
R8在每次出现时是相同或不同的,表示烷基、烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
c)根据以下所示结构式的二枯基,
R7具有之前指示的含义,优选为甲基,
d)和/或根据以下所示结构式的聚枯基,
R7具有之前指示的含义,优选为甲基,2<n<100。
之前提及的所指示结构的N-烷氧基胺的典型实例从而是:
1-环己氧基-2,2,6,6-四甲基-4-十八基氨基哌啶;双(1-辛氧基-2,2,6,6- 四甲基哌啶-4-基)癸二酸盐;2,4-双[1-环己氧基-2,2,6,6-四甲基哌啶-4-基) 丁基氨基]-6-(2-羟基乙基氨基-S-三嗪);双(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)己二酸盐;2,4-双[(1-环己氧基-2,2,6,6-四甲基哌啶-4-基)丁基氨基]-6-氯-S-三嗪;1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶; 1-(2-羟基-2-甲基丙氧基)-4-氧-2,2,6,6-四甲基哌啶;1-(2-羟基-2-甲基丙氧基)-4-八癸酰基氧-2,2,6,6-四甲基哌啶;双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6- 四甲基哌啶-4-基)癸二酸盐;双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶 -4-基)己二酸盐;2,4-双{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4- 基]-N-丁基氨基}-6-(2-羟基乙基氨基)-S-三嗪);4-哌啶醇,2,2,6,6-四甲基-1-(十一烷氧基)-4,4’-碳酸盐;2,4-双[(1-环己氧基-2,2,6,6-四甲基哌啶-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;低聚化合物,其为4,4’-六亚甲基-双(氨基-2,2,6,6-四甲基哌啶)和2,4-二氯-6-[(1-环己氧基-2,2,6,6-四甲基-4-基)丁基氨基]-S-三嗪的缩聚产物,以2-氯-4,6-双 (二丁基氨基)-S-三嗪封端的;脂肪族羟胺,例如二硬脂酰羟胺;以及下式的化合物:
其中n=1–15。
上述化合物部分地是市售产品并以以下商品名出售:由BASF SE出售的FLAMESTABNOR 116(RTM),TINUVIN NOR 371(RTM),IRGATEC CR 76(RTM),由Clariant出售的HostavinNOW(RTM)或由Adeka出售的ADK Stab LA 81(RTM)。二枯基和聚枯基是可以从例如UnitedInitiator获得的可商购产品。
塑料可以优选地包含一般的添加剂,例如选自以下的添加剂:UV吸收剂、光稳定剂、稳定剂、羟胺、苯并呋喃酮、阻燃剂、成核剂、冲击强度增强剂、增塑剂、润滑剂、流变改性剂、加工助剂、颜料、着色剂、光学增白剂、抗菌活性物质、抗静电剂、滑爽剂、抗粘连剂、耦合剂、链增长剂、分散剂、相容剂、氧捕集剂、酸捕集剂、标记剂或防雾剂。在优选的实施方案中,所述组合物特别地包含例如:酸捕集剂,其基于长链酸的盐如硬脂酸钙、硬脂酸镁、硬脂酸锌、乳酸钙、硬脂酰-2乳酸钙或者基于水滑石的盐,和/或稳定剂,其选自酚类抗氧化剂和亚磷酸酯/盐,和/或光稳定剂,其选自受阻胺(HALS)和/或分散剂。
合适的光稳定剂是例如基于2-(2’-羟苯基)苯并三唑类、2-羟基二苯甲酮类、苯甲酸的酯、丙烯酸酯/盐类、草酰胺类和2-(2-羟苯基)-1,3,5-三嗪类的化合物。
合适的2-(2’-羟苯基)苯并三唑类是例如2-(2’-羟基-5’-甲基苯基)苯并三唑、2-(3’,5’-二叔丁基-2’-羟苯基)苯并三唑、2-(5’-叔丁基-2’-羟苯基)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’- 羟苯基)-5-氯代苯并三唑,2-(3’-叔丁基-2’-羟基-5’-甲基苯基-5-氯代苯并三唑、2-(3’-仲丁基-5’-叔丁基-2’-羟苯基)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’-羟苯基)苯并三唑、2-(3’,5’-双(α,α-二甲基苄基)-2’-羟苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧基羰基乙基)苯基)-5-氯代苯并三唑、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)羰基乙基]-2’-羟苯基)-5-氯代苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧基羰基乙基)苯基)-5- 氯代苯并三唑、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’-羟苯基]-2H-苯并三唑与聚乙二醇 300的再酯化反应产物;[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-羟基二苯甲酮类例如2-羟基二苯甲酮的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。
合适的丙烯酸酯类例如乙基-α-氰基-β,β-二苯基丙烯酸酯、异辛基-α-氰基-β,β-二苯基丙烯酸酯、甲基-α-甲酯基肉桂酸酯、甲基-α-氰基-β-甲基-对- 甲氧基肉桂酸酯、丁基-α-氰基-β-甲基-对-甲氧基肉桂酸酯、甲基-α-甲酯基- 对-甲氧基肉桂酸酯和N-(β-甲酯基-β-氰基乙烯基)-2-甲基吲哚啉。
合适的苯甲酸的酯例如4-叔丁基苯基水杨酸酯、水杨酸苯酯、辛基苯基水杨酸酯、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、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、六癸基-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(ethoxanilide)和其与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和邻-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-羟苯基)-1,3,5-三嗪类是例如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-4-三癸氧基苯基)-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/三癸氧基-2-羟基丙氧基)-2-羟苯基]-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)-2-羟基丙氧基]苯基}-4,6-双(2,4-二甲基苯基-1,3,5-三嗪。
合适的金属失活剂是例如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、异邻苯二甲酰基二肼、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。
特别地,以下结构适合作为金属失活剂:
合适的酚类抗氧化剂是例如:
烷基化的单酚,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、直链的或带支链的壬基苯酚,例如2,6-二壬基-4-甲基苯酚、 2,4-二甲基-6-(1’-甲基十一-1’-基)苯酚、2,4-二甲基-6-(1’-甲基十七-1’-基)苯酚、2,4-二甲基-6-(1’-甲基三癸-1’-基)苯酚及其混合物;
烷基硫代甲基苯酚,例如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,例如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-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、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,例如α-、β-、γ-、δ-生育酚以及这些(维生素E)的混合物;
羟基化的硫代二苯醚,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/盐]、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]对苯二酸酯/盐、1,1-双-(3,5-二甲基-2-羟苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟苯基)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-、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, 十八烷基-4-羟基-3,5-二甲基苄基巯基乙酸酯/盐、十三烷基-4-羟基-3,5-二叔丁基苄基巯基乙酸酯/盐、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)二硫代对苯二酸酯/盐、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/盐;
羟基苄基化的丙二酸酯/盐,例如二十八烷基-2,2-双(3,5-二叔丁基-2-羟基苄基)丙二酸酯/盐、二十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯/盐,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/盐、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 /盐;
芳香族羟基苄基化合物,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;
三嗪化合物,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-羟苄基)异氰脲酸酯/盐、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯/盐、2,4,6- 三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)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/盐;
苄基膦酸酯/盐,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯/盐、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯/盐、二十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯/盐、二十八烷基-5-叔丁基-4-羟基-3-甲基苄基膦酸酯/盐、3,5-二叔丁基-4-羟基苄基膦酸的单乙酯的钙盐;
酰胺基苯酚,例如4-羟基月桂酰基苯胺、4-羟基硬脂酰基苯胺、辛基 -N-(3,5-二叔丁基-4-羟苯基)氨基甲酸酯/盐;
β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇的酯,所述一元醇或多元醇为例如甲醇、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、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N’-双(羟基乙基)草酰胺、3- 硫代十一烷醇、3-硫代十五烷醇、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,
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,所述一元醇或多元醇例如甲醇、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、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N’-双(羟基乙基)草酰胺、3- 硫代十一烷醇、3-硫代十五烷醇、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;
β-(3,5-二环己基-4-羟基苯基)丙酸与一元醇或多元醇的酯,所述一元醇或多元醇为例如甲醇、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、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N’-双(羟基乙基)草酰胺、3-硫代十一烷醇、3-硫代十五烷醇、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;
3,5-二叔丁基-4-羟基苯基)乙酸与一元醇或多元醇的酯,所述一元醇或多元醇为例如甲醇、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、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟基乙基)异氰脲酸酯、N,N’-双(羟基乙基)草酰胺、3-硫代十一烷醇、 3-硫代十五烷醇、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,
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-羟基苯基]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是:
十八烷基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯/盐、季戊四醇-四[3-(3,5-二叔丁基-4-羟苯基)丙酸酯、三(3,5-二叔丁基-4-羟苯基)异氰脲酸酯/盐、1,3,5- 三甲基-2,4,6-三(3,5-二叔丁基-4-羟苯基)异氰脲酸酯/盐、1,3,5-三甲基-2,4,6- 三(3,5-二叔丁基-4-羟苄基)苯、三乙二醇-双[3-(3-叔丁基-4-羟基-5-甲基苯基) 丙酸酯/盐、N,N’-己烷-1,6-二基-双[3-(3,5-二叔丁基-4-羟苯基)丙酸酰胺。
合适的亚磷酸酯/盐/亚膦酸酯/盐例如:
三苯基亚磷酸酯/盐、二苯基烷基亚磷酸酯/盐、苯基二烷基亚磷酸酯/ 盐、三(壬基苯基)亚磷酸酯/盐、三月桂基亚磷酸酯/盐、三十八烷基亚磷酸酯/盐、二硬脂酰季戊四醇二亚磷酸酯/盐、三-(2,4-二叔丁基苯基)亚磷酸酯/ 盐、二异癸基季戊四醇二亚磷酸酯/盐、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯/盐、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯/盐、双(2,6-二叔丁基-4- 甲基苯基)季戊四醇二亚磷酸酯/盐、二异癸氧基季戊四醇二亚磷酸酯/盐、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯/盐、双(2,4,6-三(叔丁基苯基)季戊四醇二亚磷酸酯/盐、三硬脂酰山梨醇三亚磷酸酯/盐、四(2,4-二叔丁基苯基)-4,4’-亚联苯基二亚磷酸、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并 [d,g]-1,3,2-二氧杂磷杂环辛烷、双(2,4-二叔丁基-6-甲基苯基)甲基亚磷酸酯/ 盐、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯/盐、6-氟-2,4,8,10-四叔丁基 -12-甲基二苯并[d,g]-1,3,2-二氧杂磷杂环辛烷、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/盐]、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/盐、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:
其他合适的稳定剂是胺类抗氧化剂。合适的胺类抗氧化剂例如:
N,N’-二异丙基-对-亚苯基二胺、N,N’-二仲丁基-对-亚苯基二胺、N,N’- 双(1,4-二甲基戊基)-对-亚苯基二胺、N,N’-双(1-乙基-3-甲基戊基)-对-亚苯基二胺、N,N’-双(1-甲基戊基)-对-亚苯基二胺、N,N’-二环己基-对-亚苯基二胺、 N,N’-二苯基-对-亚苯基二胺、N,N’-双(2-萘基)-对-亚苯基二胺、N-异丙基 -N’-苯基-对-亚苯基二胺、N-(1,3-二甲基丁基)-N’-苯基-对-亚苯基二胺、 N-(1-甲基庚基)-N’-苯基-对-亚苯基二胺、N-环己基-N’-苯基-对-亚苯基二胺、 4-(对-甲苯氨磺酰)二苯基胺、N,N’-二甲基-N,N’-二仲丁基-对-亚苯基二胺、二苯胺、N-烯丙基二苯基胺、4-异丙氧基二苯基胺、N-苯基-1-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化的二苯基胺、例如p,p’-二- 叔辛基二苯基胺、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、(o-甲苯基)双胍、双[4-(1’,3’-二甲基丁基)苯基]胺、叔辛基化的N-苯基-1-萘胺、单烷基化和二烷基化的叔丁基/叔辛基二苯基胺的混合物、单烷基化和二烷基化的壬基二苯基胺的混合物、单烷基化和二烷基化的十二烷基二苯基胺的混合物、单烷基化和二烷基化的异丙基/异己基二苯基胺的混合物、单烷基化和二烷基化的叔丁基二苯基胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单烷基化和二烷基化的叔丁基/叔辛基吩噻嗪的混合物、单烷基化和二烷基化的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-烯乙基及其混合物或组合。
其他合适的胺类抗氧化剂是羟胺或N-氧化物(硝酮),例如N,N-二烷基羟胺、N,N-二苄基羟胺、N,N-二月桂基羟胺、N,N-二硬脂酰基羟胺、N- 苄基-α-苯基硝酮、N-十八烷基-α-十六烷基硝酮以及根据以下式的Genox EP (Addivant):
其他合适的稳定剂是硫代增效剂。合适的硫代增效剂例如二硬脂酰硫代二丙酸酯/盐、二月桂酰二丙酸酯/盐或根据以下式的化合物:
其他合适的稳定剂,特别是用于聚酰胺的稳定剂是铜盐,例如铜(I)碘化物、铜(I)溴化物或铜复合物,例如三苯基膦-铜(I)复合物。
合适的受阻胺是例如:1,1-双(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯/盐、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯/盐、双(1-辛氧基-2,2,6,6-四甲基-4- 哌啶基)癸二酸酯/盐、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/盐、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合产物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯代-1,3,5-三嗪的直链的或环状的缩合产物、三(2,2,6,6-四甲基-4- 哌啶基)次氮基三乙酸酯/盐、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯/盐、1,1’-(1,2-乙二基)-双(3,3,5,5-四甲基哌嗪酮)、4-苯甲酰-2,2,6,6-四甲基哌啶、4-硬脂酰氧基-2,2,6,6-四甲基哌啶、N,N’-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-吗啉代-2,6-二氯代-1,3,5-三嗪的直链的或环状的缩合产物、7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧杂螺-[4,5]癸烷和表氯醇的反应产物。
合适的阻燃剂例如:
a)无机阻燃剂,例如Al(OH)3、Mg(OH)2、AlO(OH)、MgCO3、层状硅酸盐,例如蒙脱石或海泡石,非有机改性或有机改性的复盐,例如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、埃洛石以及Sb2O3、Sb2O5、MoO3、锡酸锌、羟基锡酸锌,
b)含氮的阻燃剂,例如三聚氰胺、蜜勒胺、蜜白胺、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、(聚)磷腈,特别是三聚氰胺氰脲酸盐,磷酸三聚氰胺、磷酸二三聚氰胺、焦磷酸三聚氰胺、三聚氰胺多磷酸盐、三聚氰胺-甲基膦酸盐、三聚氰胺-金属磷酸盐,例如三聚氰胺铝磷酸盐、三聚氰胺锌磷酸盐、三聚氰胺镁磷酸盐,以及相应的焦磷酸盐和多磷酸盐、乙二胺甲基膦酸盐、多 -[2,4-(哌嗪-1,4-基)-6-(吗啉-4-基)-1,3,5-三嗪]、多磷酸铵、三聚氰胺硼酸盐、三聚氰胺氢溴酸盐,
c)含磷的阻燃剂,例如无机或有机膦酸盐,例如铝膦酸盐、膦酸酯、甲基膦酸的低聚和聚合衍生物、红磷、磷酸盐,例如间苯二酚二磷酸盐、双酚-A-二磷酸盐和其低聚物、三苯基磷酸盐、乙二胺二磷酸盐、次膦酸酯 /盐,例如次磷酸及其衍生物的盐,例如烷基次膦酸盐,例如二乙基次磷酸铝或二乙基次膦酸锌或次磷酸铝、亚磷酸铝、磷酸铝、9,10-二氢-9-氧杂-10- 磷酰基菲-10-氧化物(DOPO)和其经取代的化合物,
d)基于氯和溴的含卤素的阻燃剂,例如多溴二苯醚,例如十溴二苯醚、三(3-溴-2,2-双(溴甲基)丙基磷酸盐、三(三溴新戊基)磷酸盐、四溴邻苯二甲酸、1,2-双(三溴苯氧基)乙烷、六溴环十二烷、溴化二苯基乙烷、三-(2,3-二溴丙基)异氰脲酸盐、亚乙基双(四溴邻苯二甲酰亚胺)、四溴双酚-A-双(2,3)二溴丙基醚、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、溴化环氧树脂、聚五溴苄基丙烯酸盐,其任选地与Sb2O3和/或Sb2O5组合,
e)硼酸盐/酯,例如硼酸锌或硼酸钙,其任选地在载体材料例如在二氧化硅上,
f)含硫的化合物,例如单质硫、二硫化物和多硫化物、秋兰姆硫化物、二硫代氨基甲酸盐/酯、巯基苯并噻唑和次磺酰胺,
g)防滴剂,例如聚四氟乙烯,
h)含硅的化合物,例如聚苯基硅氧烷,
i)碳改性物,例如碳纳米管(CNT)或石墨烯
以及在此的组合或混合物。
合适的分散剂例如:
聚丙烯酸酯,例如与长链侧基的共聚物、聚丙烯酸酯嵌段共聚物、烷基酰胺:例如N,N’-1,2-乙二基双十八烷酰胺山梨糖醇酯,例如山梨醇单硬脂酸酯、钛酸酯和锆酸酯、与官能基团的反应性共聚物,例如聚丙烯-共-丙烯酸、聚丙烯-共-马来酸酐、聚乙烯-共-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-亚乙基氧共聚物、聚苯基硅氧烷共聚物、两亲性共聚物:例如聚乙烯-嵌段-聚氧化乙烯、树状聚合物,例如含羟基的树状聚合物。
合适的成核剂例如滑石,单官能团和多官能团羧酸例如苯甲酸、琥珀酸、己二酸的碱金属或碱土金属盐,例如苯甲酸钠、甘油锌、羟基-双(4-叔丁基) 苯甲酸铝、亚苄基山梨醇,例如1,3:2,4-双(亚苄基)山梨醇或1,3:2,4-双(4-甲基亚苄基)山梨醇、2,2’-亚甲基-双-(4,6-二叔丁基苯基)磷酸酯/盐,以及三酰胺,例如根据以下结构的三酰胺:
合适的填料和增强材料例如合成的或天然的材料,例如碳酸钙、硅酸盐、玻璃纤维、玻璃球(实心或空心)、滑石、云母、高岭土、硫酸钡、金属氧化物和金属氢氧化物、炭黑、石墨、碳纳米管、石墨烯、天然产物的锯屑或纤维,例如纤维素、合成纤维或金属纤维。其他合适的填料是水滑石或沸石或层状硅酸盐,例如蒙脱石、膨润土、铝膨润石、云母、水辉石、皂石、蛭石、三八面体伊利石(ledikite)、麦羟硅钠石(magadiite)、伊来石、高岭土、钙硅石、凹凸棒石。
用于缩聚聚合物如聚酯或聚酰胺的直链分子重量增加合适的链增长剂例如二环氧化合物、双唑啉、双唑酮、双嗪、二异氰酸酯/盐、二酸酐、双酰基内酰胺、双马来酰亚胺、二氰酸酯/盐、碳化二酰亚胺。其他合适的链增长剂是聚合物,例如聚苯乙烯-聚丙烯酸酯-聚(甲基)丙烯酸缩水甘油酯共聚物、聚苯乙烯-马来酸酐共聚物和聚乙烯-马来酸酐共聚物。
合适的颜料可以具有无机或有机性质。合适的无机颜料例如二氧化钛、氧化锌、硫化锌、铁氧化物、群青、炭黑。合适的有机颜料例如蒽醌、蒽嵌蒽醌、苯并咪唑酮(benzimidazolones)、喹吖啶酮、二酮吡咯并吡咯 (diketopyrrolopyrroles)、二嗪、靛蒽醌、异吲哚啉酮、偶氮化合物、二萘嵌苯、酞菁、皮蒽酮。其他合适的颜料是基于金属的效应颜料或基于金属氧化物的珠光颜料。
光学增白剂例如双苯并唑、苯基香豆素或双(苯乙烯基)联苯,特别是下式的光学增白剂:
合适的填充失活剂例如基于缩水甘油基的环氧化物,例如双酚-A-二缩水甘油醚或双酚-F-二缩水甘油醚和其低聚物或聚合物树脂、聚硅氧烷,聚丙烯酸酯,特别是嵌段共聚物,例如聚甲基丙烯酸-聚亚烷基氧或聚苯乙烯- 聚丙烯酸酯-聚(甲基)丙烯酸缩水甘油酯共聚物。
合适的抗静电剂例如乙氧基化的烷基胺、脂肪酸酯、烷基磺酸酯和聚合物,例如聚醚酰胺或共聚物,其包含丙烯酸的盐,例如聚乙烯-聚丙烯酸酯-聚丙烯酸-Na共聚物。
根据本发明,之前所示的有机氧基酰亚胺可以用于以下塑料的改性(降解、交联、接枝):
a)由烯烃或二烯得到的聚合物,例如聚乙烯(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、聚环辛烯、聚烯烃-一氧化碳共聚物以及统计结构或嵌段结构形式的共聚物,例如聚丙烯-聚乙烯 (EP)、EPM或EPDM、乙烯-醋酸乙烯酯(EVA),乙烯-丙烯酸酯,例如乙烯-丙烯酸丁酯、乙烯-丙烯酸及其盐(离子聚合物)以及三元共聚物,例如乙烯-丙烯酸-丙烯酸缩水甘油酯、接枝聚合物,例如聚丙烯-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,
b)聚苯乙烯、聚甲基苯乙烯、聚乙烯基萘、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-丙烯酸酯(ASA)、苯乙烯-乙烯、苯乙烯-马来酸酐聚合物,其包括相应的接枝共聚物,例如丁二烯上接枝苯乙烯、SBS或SEBS上接枝马来酸酐、以及由甲基丙烯酸甲酯、苯乙烯-丁二烯和ABS得到的接枝共聚物(MABS),
c)含卤素的聚合物,例如聚氯乙烯(PVC)、聚氯丁二烯和聚偏二氯乙烯(PVDC)、由氯乙烯和偏二氯乙烯得到的共聚物或由氯乙烯和醋酸乙烯酯得到的共聚物、氯代聚乙烯、聚偏二氟乙烯。
d)不饱和酯的聚合物,例如聚丙烯酸酯和聚甲基丙酸酯,例如聚甲基丙烯酸甲酯(PMMA)、聚丙烯酸丁酯、聚丙烯酸月桂酯、聚丙烯酸硬脂酸酯、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,例如聚丙烯腈-聚丙烯酸烷基酯、聚甲基丙烯酰亚胺,
e)由不饱和醇和衍生物得到的聚合物,例如聚乙烯醇、聚醋酸乙烯酯、聚乙烯醇缩丁醛,
f)聚缩醛,例如聚氧亚甲基(POM)或与例如正丁醛的共聚物,
g)聚苯醚和与聚苯乙烯或聚酰胺的共混合物,
h)环醚的聚合物,例如聚乙二醇、聚丙二醇、聚氧化乙烯、聚氧化丙烯,
i)由羟基封端的聚醚或聚酯和芳香族或脂肪族异氰酸酯得到的聚氨酯,特别是直链聚氨酯、聚脲,
j)聚酰胺,例如聚酰胺-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-12.12、聚酰胺11、聚酰胺12以及(部分地)芳香族聚酰胺,例如,由对苯二甲酸和/或间苯二甲酸和脂肪族二胺,或者由脂肪族二羧酸例如己二酸或癸二酸和芳香族二胺例如1,4-或1,3-二氨基苯制备的聚对苯二甲酰胺,不同的聚酰胺的共混物,例如PA-6和PA6.6,或者聚酰胺和聚烯烃的共混物,例如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)由脂肪族或芳香族二羧酸和二醇得到或者由羟基羧酸得到的聚酯,例如,聚对苯二甲酸乙二酯(PET)、聚对苯二甲酸丁二酯(PBT)、聚对苯二甲酸丙二酯、聚萘二甲酸乙二酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、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),
m)聚碳酸酯、聚酯碳酸酯以及共混物,例如PC/ABS、PC/PBT、 PC/PET/PBT、PC/PA,
n)纤维素衍生物,例如硝酸纤维素、醋酸纤维素、丙酸纤维素、丁酸纤维素,
o)以及两种或更多种前述聚合物得到的混合物、组合或共混物。
当a)至n)示出的聚合物涉及共聚物时,这些可以以统计(“无规”)、嵌段或“递变”结构的形式存在。
当a)至n)示出的聚合物涉及有规立构聚合物时,这些可以以全同立构、立体定向、无规立构的形式或者以立构嵌段结构存在。
此外,a)至n)示出的聚合物可以具有非晶和(部分地)结晶的形态。
在此,a)至n)提及的聚合物不仅可以以原材料存在,还可以以回收料的形式,例如以生产废料或“消费后”回收料存在。
根据本发明,初始提及的式I的氧基酰亚胺可以在以下硬塑性或弹性、非热塑性塑料中用作自由基生成剂:
a)环氧树脂,其由二官能团或多官能团的环氧化合物结合例如基于胺、酸酐、双氰胺、硫醇、异氰酸盐的硬化剂或催化地起作用的硬化剂组成,
b)酚树脂,例如酚-甲醛树脂、脲-甲醛树脂、三聚氰胺-甲醛树脂,
c)由不饱和二羧酸和二醇得到的不饱和聚酯树脂,
d)硅酮,
e)由二官能团或多官能团的异氰酸酯和多元醇得到的作为反应产物的聚氨酯,聚脲,
f)醇酸树脂,烯丙树脂。
关于非常特别的优选,根据本发明的自由基生成剂用于聚烯烃,优选聚丙烯和/或聚乙烯和其共聚物和共混物情况下的改性,以及用于不饱和聚酯树脂。
关于非常特别的优选,根据本发明的自由基生成剂优选用于聚丙烯的分子量降低和/或用于聚乙烯或不饱和聚酯树脂及其共聚物和共混物的交联,以及用于不饱和单体在聚丙烯或聚乙烯上的接枝。关于交联反应,羟基酰亚胺和羟基酰亚胺醚是特别优选的。
特别地,在根据本发明使用的氧基酰亚胺与至少一种其他自由基形成剂组合的情况下,产生协同效应。在此,其他自由基形成剂优选地选自上文描述并优选被使用的自由基形成剂。为了避免重复,参考之前关于其他自由基形成剂的实施方案。
在根据本发明使用的氧基酰亚胺与至少一种其他自由基形成剂组合使用的情况下,优选的是在本发明的情况下前述化合物以99:1至1:99、优选 5:95至95:5、特别优选10:90至90:10的重量比(氧基酰亚胺:其他自由基形成剂)使用。
此外,在本发明中有利的是有机氧基酰亚胺相对于塑料以0.01重量%至30重量%、优选以0.1重量%至10重量%、特别优选以0.5重量%至5 重量%使用。
此外,本发明涉及用于在塑料中生成自由基的方法,其中将包含至少一种前述式I的结构单元的至少一种有机氧基酰亚胺与塑料或与包含至少一种塑料的至少一种模塑料混合并活化。在活化期间,自由基由此释放。特别地,活化是用热或通过照射实现的。特别优选地,活化在塑料或包含塑料的模塑料的成型方法期间同时地进行,特别地通过注塑或挤出。在这些方法中,将塑料加热至它们的塑化温度以上,从塑化温度开始,塑料或包含塑料的模塑料以塑化的状态存在。
此外,本发明涉及前述方法用于塑料的改性的用途。
特别优选地,根据本发明的氧基酰亚胺用作聚合物、特别是聚烯烃、特别是聚丙烯的受控降解,或用于聚合物、特别是聚烯烃或不饱和聚酯的交联的自由基生成剂,用作不饱和化合物接枝到聚合物、特别是聚烯烃上的自由基形成剂。
关于可以用于根据本发明的方法或该方法的使用目的的有机氧基酰亚胺的具体细节,参考之前给出的实施方案。所有上述的优选的实施方案同样无限制地适用于上述根据本发明的方法或根据本发明的方法的根据本发明的用途。
参照之后的实施方案更详细地描述本发明,而不将本发明限制于实施例。
实施例1:聚丙烯的分子量减小
在指示的温度下,在以400rmp的螺杆转速、11mm的双螺杆挤出机 (Process 11ofThermo Scientific)上进行添加自由基生成剂的聚丙烯样品(Moplen HP 500N)的挤出。首先使期望比例的聚合物和添加剂通过混合均化并经由容积计量供于挤出。之后,根据ISO1133在230℃/2.16kg下确定成颗粒的挤出样品的MVR(熔体体积速率),并借助于高温凝胶渗透色谱确定分子量的平均重量。
表1:聚丙烯的成分以及熔体体积流动速率和分子量的分析结果
n.d.=未确定
氧基酰亚胺1=N-羟基邻苯二甲酰亚胺
氧基酰亚胺2(根据WO 2014154636制备)
出人意料地,显示与比较例相比,具有根据本发明的氧基酰亚胺的组合物具有更高的MVR(=较低的分子量),同样地,在GPC测量中具有更低的分子量。随着氧基酰亚胺浓度的增加和加工温度的增加,分子量进一步降低。
实施例2:聚乙烯的分子量增加
在200℃下,在以300rpm的螺杆转速、11mm双螺杆挤出机(Process 11of ThermoScientific)上,经由与N-羟基邻苯二甲酰亚胺(NHPI)的反应性挤出实现PE类型(可从ExxonMobil获得)的分子量增加。根据ISO 1133,在190℃的温度和5kg或10kg的重量下进行熔体体积流动速率(MVR)分析。
表2:聚乙烯的成分和熔体体积流动速率的分析结果
参考根据本发明的实施例的MVR值相对于比较例的显著降低,表明熔体黏度的增加,这可以归因于分子量的增加。因此,可以确定借助于本发明中所述方法分子量的受控增加。
Claims (62)
1.包含以下式I所示的至少一种结构单元的有机氧基酰亚胺作为塑料中自由基生成剂的用途
其中所述有机氧基酰亚胺具有以下式之一
R1代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团;R2代表任选地经取代的亚烷基、亚环烷基、亚芳基、亚杂芳基或桥接酰基基团、–O–、–S–、–SO2–、或–NHCO–;且R1和R1、或R2和R2分别具有相同的含义;
其中所述有机氧基酰亚胺与塑料或包含至少一种塑料的模塑料混合并活化,所述活化在塑料或包含至少一种塑料的模塑料的成型工艺期间进行。
2.根据权利要求1所述的用途,其特征在于R2选自以下基团:
–(CH2)n–,其中n=1至18,–CH(CH3)–、–C(CH3)2–、–O–、–S–、–SO2–、–NHCO–、–CO–以及以下所示的基团,
之前所示基团中含有的脂环族或芳香族环体系为未经取代的或被一个或更多个烷基和/或烷氧基基团取代,
Q在每次出现时为相同或不同的,并选自化学键以及基团–(CH2)n–,其中n=1至18,–CH(CH3)–、–C(CH3)2–、–O–、–S–、–SO2–、–NHCO–、–CO–、OC(O)–O–,
m为0或1至18。
3.根据权利要求1或2所述的用途,其特征在于R1=H、R1=烷基或R1=酰基。
4.根据权利要求1或2所述的用途,其特征在于根据式I的所述有机氧基酰亚胺与至少一种链转移剂组合使用。
5.根据权利要求4所述的用途,其特征在于所述链转移剂是选自硫醇、二硫化物、磷化氢、有机卤化物、酯、醛或叔胺的至少一种链转移剂。
6.根据权利要求4所述的用途,其特征在于所述链转移剂是磷酸酯。
7.根据权利要求4所述的用途,其特征在于所述链转移剂是具有在塑料的加工温度之上的沸点的链转移剂。
8.根据权利要求5所述的用途,其特征在于所述有机卤化物是碘化物、溴化物、氯化物。
9.根据权利要求1或2所述的用途,其特征在于根据式I的所述有机氧基酰亚胺与选自以下的至少一种多官能化合物组合使用:
a)基于聚丁二烯或聚异戊二烯的多不饱和的聚合物和低聚物,
b)二乙烯基和聚乙烯基化合物,
c)二烯丙基和聚烯丙基化合物,
d)二马来酰亚胺和聚马来酰亚胺,
e)二醇和多元醇的二(甲基)丙烯酸酯和聚(甲基)丙烯酸酯,和/或
f)有机官能硅烷。
10.根据权利要求9所述的用途,其特征在于二乙烯基和聚乙烯基化合物是二乙烯基苯。
11.根据权利要求9所述的用途,其特征在于二烯丙基和聚烯丙基化合物是聚烯丙基醚或聚烯丙基酯、三烯丙基异氰脲酸酯、三烯丙基氰尿酸酯、二烯丙基双酚A。
12.根据权利要求1或2所述的用途,其特征在于根据式I的所述有机氧基酰亚胺与至少一种硝酰基自由基组合使用。
13.根据权利要求1或2所述的用途,其特征在于根据式I的所述有机氧基酰亚胺与至少一种催化化合物组合使用。
14.根据权利要求13所述的用途,其特征在于所述催化化合物选自过渡金属的金属盐。
15.根据权利要求14所述的用途,其特征在于所述过渡金属是铜、锰或铁。
16.根据权利要求14所述的用途,其特征在于所述过渡金属的金属盐是乙酸盐的形式。
17.根据权利要求14所述的用途,其特征在于所述过渡金属的金属盐是乙酸亚铜(I)。
18.根据权利要求1或2所述的用途,其特征在于根据式I的所述有机氧基酰亚胺与至少一种另外的自由基形成剂一起使用。
19.根据权利要求18所述的用途,其特征在于所述另外的自由基形成剂选自N-烷氧基胺、-C-C-自由基形成剂、具有偶氮基团的自由基形成剂、具有肼基团的自由基形成剂、具有腙基团的自由基形成剂、具有吖嗪基团的自由基形成剂、具有三氮烯基团的自由基形成剂、具有二硫化物或多硫化物基团的自由基形成剂、具有硫醇基团的自由基形成剂、秋兰姆硫化物、二硫代氨基甲酸盐、巯基苯并噻唑和次磺酰胺。
20.根据权利要求18所述的用途,其特征在于所述另外的自由基形成剂选自:
a)根据以下所示结构式的N-烷氧基胺,
R3代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团,
R4代表烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
Z代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团,两个Z基团还能够形成闭合的环,其可以任选地被酯基团、醚基团、胺基团、酰胺基团、羧基基团、尿烷基团取代,
b)根据以下所示结构式的偶氮化合物,
R5-N=N-R5或
R5表示烷基、环烷基或芳基基团,
R6在每次出现时是相同或不同的,表示直链或带支链的烷基基团,
R7在每次出现时是相同或不同的,表示氢或者直链或带支链的烷基基团,
R8在每次出现时是相同或不同的,表示烷基、烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
c)根据以下所示结构式的二亚枯基,
R7具有之前指示的含义,
d)和/或根据以下所示结构式的聚亚枯基,
R7具有之前指示的含义,2<n<100。
21.根据权利要求20所述的用途,其特征在于R3是C1至C4烷基基团。
22.根据权利要求20所述的用途,其特征在于R7是甲基。
23.根据权利要求1或2所述的用途,其特征在于,所述塑料为热塑性、弹性或热固性聚合物。
24.根据权利要求23所述的用途,其特征在于所述塑料是热塑性聚合物。
25.根据权利要求23所述的用途,其特征在于所述塑料选自以下:
a)由烯烃或二烯得到的聚合物,
b)聚苯乙烯、聚甲基苯乙烯、聚乙烯基萘、苯乙烯-丁二烯、苯乙烯-丁二烯-苯乙烯、苯乙烯-乙烯-丁烯-苯乙烯、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、苯乙烯-丁二烯-丙烯腈、苯乙烯-丙烯腈-丙烯酸酯、苯乙烯-乙烯、苯乙烯-马来酸酐聚合物,其包括相应的接枝共聚物,
c)含卤素的聚合物,
d)不饱和酯的聚合物、聚丙烯腈、聚丙烯酰胺、共聚物,
e)由不饱和醇和衍生物得到的聚合物,
f)聚缩醛,
g)聚苯醚和与聚苯乙烯或聚酰胺的共混物,
h)环醚的聚合物,
i)由羟基封端的聚醚或聚酯和芳香族或脂肪族异氰酸酯得到的聚氨酯、聚脲,
j)聚酰胺,不同聚酰胺的共混物,或者聚酰胺和聚烯烃的共混物,
k)聚酰亚胺、聚酰胺酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚酮、聚醚酮、聚砜、聚苯硫醚、聚苯并咪唑、聚乙内酰脲,
l)由脂肪族或芳香族二羧酸和二醇得到或者由羟基羧酸得到的聚酯,
m)聚碳酸酯、聚酯碳酸酯以及共混物,
n)纤维素衍生物,
o)非热塑性的或热固性的塑料,
p)以及两种或更多种前述聚合物得到的混合物、组合或共混物。
26.根据权利要求25所述的用途,其特征在于所述塑料是聚醚砜或聚芳砜。
27.根据权利要求25所述的用途,其特征在于所述由烯烃或二烯得到的聚合物是聚乙烯、茂金属-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、聚烯烃-一氧化碳共聚物以及统计结构或嵌段结构形式的共聚物。
28.根据权利要求27所述的用途,其特征在于所述聚乙烯是LDPE、LLDPE、VLDPE、ULDPE、MDPE、HDPE、UHMWPE。
29.根据权利要求27所述的用途,其特征在于所述统计结构或嵌段结构形式的共聚物是聚丙烯-聚乙烯、EPM或EPDM、乙烯-醋酸乙烯酯、乙烯-丙烯酸酯、乙烯-丙烯酸及离子聚合物、以及三元共聚物、接枝聚合物。
30.根据权利要求29所述的用途,其特征在于所述乙烯-丙烯酸酯是乙烯-丙烯酸丁酯。
31.根据权利要求29所述的用途,其特征在于所述离子聚合物是乙烯-丙烯酸的盐。
32.根据权利要求29所述的用途,其特征在于所述三元共聚物是乙烯-丙烯酸-丙烯酸缩水甘油酯。
33.根据权利要求29所述的用途,其特征在于所述接枝聚合物是聚丙烯接枝马来酸酐、聚丙烯接枝丙烯酸、聚乙烯接枝丙烯酸或聚乙烯聚丙烯酸丁酯接枝马来酸酐。
34.根据权利要求25所述的用途,其特征在于所述相应的接枝共聚物是丁二烯上接枝苯乙烯、SBS或SEBS上接枝马来酸酐、以及由甲基丙烯酸甲酯、苯乙烯-丁二烯和ABS得到的接枝共聚物。
35.根据权利要求25所述的用途,其特征在于所述含卤素的聚合物是聚氯乙烯、聚氯丁二烯和聚偏二氯乙烯,由氯乙烯和偏二氯乙烯得到的共聚物,或由氯乙烯和醋酸乙烯酯得到的共聚物、氯代聚乙烯、聚偏二氟乙烯。
36.根据权利要求25所述的用途,其特征在于所述不饱和酯的聚合物是聚丙烯酸酯和聚甲基丙烯酸酯。
37.根据权利要求36所述的用途,其特征在于所述聚丙烯酸酯和聚甲基丙烯酸酯是聚甲基丙烯酸甲酯、聚丙烯酸丁酯、聚丙烯酸月桂酯、和聚丙烯酸硬脂基酯。
38.根据权利要求25所述的用途,其特征在于d)中的所述共聚物是聚丙烯腈-聚丙烯酸烷基酯。
39.根据权利要求25所述的用途,其特征在于所述由不饱和醇和衍生物得到的聚合物是聚乙烯醇、聚醋酸乙烯酯和聚乙烯醇缩丁醛。
40.根据权利要求25所述的用途,其特征在于所述聚缩醛是聚氧亚甲基或共聚物。
41.根据权利要求40所述的用途,其特征在于所述共聚物是与正丁醛的共聚物。
42.根据权利要求25所述的用途,其特征在于所述环醚的聚合物是聚乙二醇、聚丙二醇、聚氧化乙烯、聚氧化丙烯和聚四氢呋喃。
43.根据权利要求25所述的用途,其特征在于所述聚氨酯是直链聚氨酯。
44.根据权利要求25所述的用途,其特征在于所述聚酰胺是聚酰胺-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-12.12、聚酰胺11、聚酰胺12以及芳香族聚酰胺和部分芳香族聚酰胺。
45.根据权利要求44所述的用途,其特征在于所述部分芳香族聚酰胺是聚苯二酰胺。
46.根据权利要求45所述的用途,其特征在于所述聚苯二酰胺是由对苯二甲酸和/或间苯二甲酸和脂肪族二胺,或者由脂肪族二羧酸与芳香族二胺制备的。
47.根据权利要求46所述的用途,其特征在于所述脂肪族二羧酸是己二酸或癸二酸。
48.根据权利要求46所述的用途,其特征在于所述芳香族二胺是1,4-或1,3-二氨基苯。
49.根据权利要求25所述的用途,其特征在于所述不同聚酰胺的共混物是PA-6和PA6.6的共混物。
50.根据权利要求25所述的用途,其特征在于所述聚酰胺和聚烯烃的共混物是PA/PP的共混物。
51.根据权利要求25所述的用途,其特征在于所述由脂肪族或芳香族二羧酸和二醇得到或者由羟基羧酸得到的聚酯是聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚对苯二甲酸丙二酯、聚萘二甲酸乙二酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、聚羟基苯甲酸酯、聚羟基萘二甲酸酯、聚乳酸。
52.根据权利要求25所述的用途,其特征在于m)中的共混物是PC/ABS、PC/PBT、PC/PET/PBT、PC/PA。
53.根据权利要求25所述的用途,其特征在于所述纤维素衍生物是硝酸纤维素、醋酸纤维素、丙酸纤维素、丁酸纤维素。
54.根据权利要求1或2所述的用途,其特征在于所述有机氧基酰亚胺相对于所述塑料以0.01重量%至30重量%使用。
55.根据权利要求54所述的用途,其特征在于所述有机氧基酰亚胺相对于所述塑料以0.1重量%至10重量%使用。
56.根据权利要求55所述的用途,其特征在于所述有机氧基酰亚胺相对于所述塑料以0.2重量%至5重量%使用。
57.根据权利要求1或2所述的用途,所述自由基的生成用于塑料的改性、增加塑料的分子量、塑料的支化或交联、塑料的分子量减小、影响塑料的分子量分布、塑料上不饱和单体的接枝。
58.一种用于在塑料中生成自由基的方法,其中,将至少一种包含以下式I所示的结构单元的有机氧基酰亚胺与塑料或包含至少一种塑料的模塑料混合并活化:
其中所述有机氧基酰亚胺具有以下式之一
R1代表氢或任选地经取代的烷基、环烷基、芳基、杂芳基或酰基基团;R2代表任选地经取代的亚烷基、亚环烷基、亚芳基、亚杂芳基或桥接酰基基团;且R1和R1、或R2和R2分别具有相同的含义;
其中所述活化在塑料或包含至少一种塑料的模塑料的成型工艺期间进行。
59.根据权利要求58所述的方法,其特征在于所述成型工艺是注塑或挤出。
60.根据权利要求58或59所述的方法,其特征在于所述活化是用热或通过照射实现的。
61.根据权利要求58至60中任一项所述的方法用于塑料的改性、增加塑料的分子量、塑料的支化或交联、塑料的分子量减小、影响塑料的分子量分布、塑料上不饱和单体的接枝的用途。
62.根据权利要求61所述的用途,其用于聚丙烯的分子量减小或聚乙烯的交联。
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EP3194487A1 (de) | 2017-07-26 |
JP2017535626A (ja) | 2017-11-30 |
EP3194482A1 (de) | 2017-07-26 |
CN107001698B (zh) | 2020-05-26 |
US20170260366A1 (en) | 2017-09-14 |
EP3194487B1 (de) | 2022-11-02 |
WO2016042040A1 (de) | 2016-03-24 |
JP6775493B2 (ja) | 2020-10-28 |
ES2932651T3 (es) | 2023-01-23 |
US10364340B2 (en) | 2019-07-30 |
CN107001698A (zh) | 2017-08-01 |
KR102464951B1 (ko) | 2022-11-08 |
EP3194482C0 (de) | 2024-05-08 |
CN106715560A (zh) | 2017-05-24 |
JP2017527679A (ja) | 2017-09-21 |
EP3194482B1 (de) | 2024-05-08 |
US20170260363A1 (en) | 2017-09-14 |
KR102444647B1 (ko) | 2022-09-20 |
DE102014218811A1 (de) | 2016-03-24 |
JP6623217B2 (ja) | 2019-12-18 |
KR20170057346A (ko) | 2017-05-24 |
US10544284B2 (en) | 2020-01-28 |
WO2016042038A1 (de) | 2016-03-24 |
KR20170057381A (ko) | 2017-05-24 |
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