CN107001698B - 含磷有机氧基酰亚胺作为塑料阻燃剂的用途,阻燃塑料组合物,其制备方法 - Google Patents
含磷有机氧基酰亚胺作为塑料阻燃剂的用途,阻燃塑料组合物,其制备方法 Download PDFInfo
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- CN107001698B CN107001698B CN201580050282.9A CN201580050282A CN107001698B CN 107001698 B CN107001698 B CN 107001698B CN 201580050282 A CN201580050282 A CN 201580050282A CN 107001698 B CN107001698 B CN 107001698B
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 66
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- 239000011574 phosphorus Substances 0.000 title claims abstract description 62
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 57
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- 239000001257 hydrogen Substances 0.000 claims description 7
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- 125000000547 substituted alkyl group Chemical group 0.000 claims description 7
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- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BHYQWBKCXBXPKM-UHFFFAOYSA-N tris[3-bromo-2,2-bis(bromomethyl)propyl] phosphate Chemical compound BrCC(CBr)(CBr)COP(=O)(OCC(CBr)(CBr)CBr)OCC(CBr)(CBr)CBr BHYQWBKCXBXPKM-UHFFFAOYSA-N 0.000 description 1
- WMXBGWKUWMQWAL-UHFFFAOYSA-H trizinc 1,3,5-triazine-2,4,6-triamine diphosphate Chemical compound N1=C(N)N=C(N)N=C1N.P(=O)([O-])([O-])[O-].[Zn+2].P(=O)([O-])([O-])[O-].[Zn+2].[Zn+2] WMXBGWKUWMQWAL-UHFFFAOYSA-H 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明涉及根据通式(I)的含磷有机氧基酰亚胺作为用于塑料的阻燃剂和/或稳定剂的用途。本发明还涉及其中并入了前述含磷有机氧基酰亚胺的阻燃塑料成型复合物,并涉及用于制备上述塑料组合物的方法。本发明还涉及由前述阻燃塑料组合物制成的模塑件、漆或涂料。
Description
本发明涉及根据以下所示通式I的含磷有机氧基酰亚胺作为塑料的阻燃剂和/或作为塑料的稳定剂的用途。此外,本发明涉及其中并入了前述含磷有机氧基酰亚胺的阻燃塑料模塑复合物,还涉及用于制备前述塑料组合物的方法。此外,本发明涉及稳定的塑料组合物。此外,本发明涉及由前述阻燃塑料组合物制成的模塑制品、漆或涂料。
大多数塑料是可燃的并且相对易燃。为了减少或排除塑料在具体应用中的火灾风险,降低可燃性和使用防火的塑料组合物从而是绝对必要的。为此,一般将阻燃剂添加至塑料,其目的是在特定时间防止着火或显著地延迟火灾蔓延。传统的阻燃剂是基于含氯化合物和含溴化合物(含溴化合物一般与三氧化锑组合)、含磷化合物、含氮化合物和金属氢氧化物,例如氢氧化铝(ATH)或氢氧化镁(MDH)。在当代,由于毒理学和生态毒理学原因,不含卤素的阻燃方案是优选的。
关于阻燃塑料的制备,存在大量的通常基底特异性地用于特定聚合物和特定使用领域的阻燃剂,对应于形成其基础的标准。阻燃塑料被用于例如电气和电子应用、运输领域(火车、航空器、汽车)、织物和建筑。
过去几年开发的基于氮的优选用于聚烯烃的新阻燃剂种类基于所选择的烷氧基胺(例如WO 99/00450)。由于烷氧基胺的裂解,在火灾的情况下产生自由基,该自由基涉及聚合物的分解过程由此产生阻燃效果(C.R.Wilen,R.Pfaendner,J.Appl.Pol.Sci.2013,129,925-944)。除烷氧基胺之外,同时还描述了起阻燃剂或阻燃增效剂作用的其他自由基生成剂,例如偶氮化合物(M.Aubert等人,Macromol.Rapid Commun.2006,27,976-981,WO2005/030852)、腙和吖嗪(M.Aubert等人,Pol.Adv.Technol.2011,22,1529-1538)、偶氮-烷氧基胺(M.Aubert等人,Pol.Degr.Stab.2012,97,1438-1446)、偶氮-膦酸盐/酯(T.Tirri等人,Pol.Degr.Stab.2012,97,375-382)或三氮烯(W.Pawelec等人,Pol.Degr.Stab.2012,97,948-954)。
此外,在DE 10 2013 005 307或DE 10 2014 210 214中描述了基于羟基酰亚胺和聚合酰亚胺的新的自由基生成剂作为阻燃剂的用途。
这些化合物种类优选地与另外的阻燃剂,例如基于其他含氮化合物、含磷化合物、含卤素化合物或含硫化合物组合使用,因此产生协同组合。然而,该组合的一个缺点是使用多于一种化合物,这例如会增加许可成本、产生另外的误差来源和会出现不期望的成分之间的相互作为,如化学反应。
因此,本发明的一个目的是使得能够获得基于非常高效的自由基生成剂的新阻燃剂和协同阻燃成分。此外,所选的化合物可以用作塑料的稳定剂。
该目的通过根据专利权利要求1的含磷有机氧基酰亚胺的用途、通过具有专利权利要求19特征的阻燃和/或稳定的塑料组合物、通过制备阻燃和/或稳定的塑料组合物的方法、通过专利权利要求22的特征以及通过具有专利权利要求23特征的模塑件、漆或涂料来实现。各从属权利要求在此代表有利的发展方案。
本发明因此涉及含磷有机氧基酰亚胺作为塑料的阻燃剂、作为塑料的稳定剂和/或作为塑料的抗氧化剂的用途,其包含至少一个以下所示式I的结构单元
R1选自含磷基团。
现已证明,借助于包含氧基酰亚胺基团和至少一个磷基团的分子,可以进一步提高氧基酰亚胺的阻燃效果。这些选定的结构至今还未被以上指出的单个申请所明确包含。同时,这些产品中许多可以由可大规模使用的起始化合物廉价地生产。
以上所示的含磷有机氧基酰亚胺中包含的基团R1从而包含至少一个磷原子。基团R1从而还可以表示包含多个磷原子的基团。特别地,重复根据式I的结构是可能的,即,在分子中存在多个所示的氧基酰亚胺基团。
使得能够获得具有高效率的新阻燃剂和阻燃成分的目的优选地通过使用分子中包含至少一个氧基酰亚胺基团和至少一个磷基团二者、即通式Ia、Ib、Ic的至少一个结构单元的化合物来实现,条件是这些结构不包含任何卤素。
R1为直接键、任选地经取代的烷基、环烷基、芳基或杂芳基基团,其不包含卤素。
R2为O或S
根据本发明,优选的是式I中的上述基团R1选自以下基团
-X-Y
X表示直接化学键、未经取代或经取代的亚烷基基团、未经取代或经取代的亚环烷基基团、未经取代或经取代的芳基基团、未经取代或经取代的杂芳基基团或酰基基团,所述酰基基团的羰基与氧原子键合,其酸基与Y键合,
Y表示含磷基团,其通过磷原子与X化学交联,其中磷原子具有-3至5的化合价,特别是-2、-1、0、+1、+2、+3、+4或+5。
在上述基团X-Y中,有利的是基团Y选自以下所示的基团
Z每次出现时是相同或不同的,其选自直链或带支链的和/或未经取代或经取代的烷基基团、未经取代或经取代的芳基基团、未经取代或经取代的杂芳基基团或酰基基团,所述酰基基团的羰基与磷原子或A或B键合,前述基团能够被至少一个另外的根据以上所示式I的结构单元取代和/或被至少一个另外的基团R1取代,以及选自以上所示式I的结构单元和基团-X-Y,
A每次出现时是相同或不同的,表示氧或硫,
B每次出现时是相同或不同的,表示氮,和
D每次出现时是相同或不同的,其选自直链或带支链的和/或未经取代或经取代的烷基基团、未经取代或经取代的芳基基团、未经取代或经取代的杂芳基基团,前述基团能够任选地被至少一个另外的根据以上所示式I的结构单元取代和/或被至少一个另外的基团R1取代。
特别地,含磷有机氧基酰亚胺是不含卤素的,即相应的化合物不包含卤素原子。
优选的含磷有机氧基酰亚胺具有以下结构:
E-R1
E表示以下所示的基团,E通过氧原子与R1键合,
R1是如上所定义的,
R1′每次出现时是相同或不同的,表示氢、直链或带支链的烷基基团、直链或带支链的烯基基团、芳香族基团、杂芳香族基团,或在基团R1′键合形成环的情况下,该环能够是饱和或不饱和的、经取代或未经取代的,和/或至少一个或两个基团R1′、或键合以形成环的基团R1′包含至少一个另外的以上所示式I的结构单元。
特别地,含磷有机氧基酰亚胺具有以下式之一:
E和R1'具有前述的定义。
特别优选的举例使用的有机含磷氧基酰亚胺在下文示出:
根据第一优选实施方案,含磷有机氧基酰亚胺包含通式I的结构单元,并具有以下式之一
根据本发明的含磷有机氧基酰亚胺的另一优选实施方案具有两个通式I的结构单元,并具有以下所示式之一
在前述两个实施方案的情况下,在此适用的是:
n表示0、1、2、3或4,和
R2选自任选地经取代的亚烷基、亚环烷基、亚芳基、亚杂芳基或桥酰基基团。
另一优选实施方案规定含磷有机氧基酰亚胺包含三个通式I的结构单元,并具有以下式
基团R1的定义在此与上述定义相同。
在前述式中,基团R2在此优选地定义如下:R2在此优选选自以下基团
–(CH2)n–,其中n=1至18,–CH(CH3)–、–C(CH3)2–、–CH(CF3)–、–C(CH3)2–、–O–、–S–、–SO2–、–NHCO–、–CO–、–O-C(O)O–以及以下所示的基团
先前所示的基团中包含的脂环族或芳香族环体系是未经取代的或被一个或更多个烷基和/或烷氧基基团取代的,
Q在每次出现时是相同或不同的,其选自化学键以及以下基团
–(CH2)n–,其中n=1至18,–CH(CH3)–、–C(CH3)2–、–CH(CF3)–、–C(CF3)2–、–O–、–S–、–SO2–、–NHCO–、–CO–、–O–C(O)-O-,和
m为0或1至3。
特别优选地,基团R2在此通过以下所示结构单元再现,Q具有上述含义:
特别地,基团R2在此可以通过以下结构单元给出:
特别优选的含磷有机氧基酰亚胺在此选自以下所示化合物:
y为1或2,
Alk表示直链或带支链的、经取代或未经取代的烷基基团,和
Ar表示经取代或未经取代的芳基基团或杂芳基基团。
同样地,含磷有机氧基酰亚胺以聚合物或共聚物的形式存在是可能的。聚合物在此由以下所示的重复单元构成,共聚物包含至少一个以下所示的结构单元:
塑料在此优选为热塑性聚合物,特别是选自
a)由烯烃或二烯制得的聚合物,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,包括相应的接枝共聚物,例如在丁二烯上接枝的苯乙烯、在SBS或SEBS上接枝的马来酸酐、以及由甲基丙烯酸甲酯、苯乙烯-丁二烯和ABS制得的接枝共聚物(MABS),
c)含卤素聚合物,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制得的共聚物、或由氯乙烯和醋酸乙烯酯制得的共聚物、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、聚丙烯酸硬脂醇酯、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-聚丙烯酸烷基酯,聚甲基丙烯酰亚胺,
e)由不饱和醇及其衍生物制得的聚合物,例如聚乙烯醇、聚醋酸乙烯酯、聚乙烯醇缩丁醛,
f)聚缩醛,例如聚甲醛(POM)或其与例如正丁醛的共聚物,
g)聚苯醚及其与聚苯乙烯或聚酰胺的共混物,
h)环醚的聚合物,例如聚乙二醇、聚丙二醇、聚环氧乙烷、聚环氧丙烷、聚四氢呋喃,
i)由羟基封端的聚醚或聚酯和芳香族或脂肪族异氰酸酯制得的聚氨酯,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)芳香族聚酰胺,例如,如由对苯二甲酸和/或间苯二甲酸与脂肪族二胺、或者由脂肪族二羧酸如己二酸或癸二酸与芳香族二胺如1,4-二氨基苯或1,3-二氨基苯制备的聚苯二甲酰胺,不同的聚酰胺例如PA-6和PA6.6的共混物,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制得或者由羟基羧酸制得的聚酯,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、聚对苯二甲酸-1,4-环己烷二醇酯、聚羟基苯甲酸酯、聚羟基萘甲酸酯、聚乳酸(PLA)、聚羟基丁酸酯(PHB)、聚羟基戊酸酯(PVH),
m)聚碳酸酯、聚酯碳酸酯及其共混物,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)刚性或弹性的、非热塑性的塑料,
p)以及前述聚合物中两种或更多种的混合物、组合或共混物。
如果在a)至o)下指出的聚合物涉及共聚物,则这些共聚物可以以统计(“无规”)、嵌段或“递变”结构的形式存在。
如果在a)至o)下指出的聚合物涉及有规立构聚合物,则这些聚合物可以以全同立构、立体定向的形式、也可以以无规立构形式或作为立构嵌段共聚物存在。
此外,在a)至o)下指出的聚合物可以具有非晶的和(部分)结晶的形态。
任选地,在a)下提及的聚烯烃还可以交联地存在,例如于是被称为X-PE的交联聚乙烯。
提及的聚合物a)至o)在此不仅可以以原始材料存在,还可以以回收料,例如以生产废料或“消费后”回收料的形式存在。
根据本发明的阻燃剂可以特别地在以下刚性或弹性、非热塑性塑料中使用:
a)环氧树脂,其由与例如基于胺、酸酐、二氰基二酰胺、硫醇、异氰酸酯的硬化剂或起催化作用的硬化剂组合的双官能团或多官能团的环氧化合物制得,
b)酚树脂,例如苯酚-甲醛树脂、脲-甲醛树脂、三聚氰胺-甲醛树脂,
c)由不饱和的二羧酸和二醇制得的不饱和聚酯树脂,
d)硅树脂,
e)由双官能团或多官能团的异氰酸盐/酯和多元醇制得的作为反应产物的聚氨酯,聚脲,
f)醇酸树脂,烯丙树脂。
非常特别优选地,在聚烯烃,优选聚丙烯和/或聚乙烯及其共聚物和共混物的情况下,使用根据本发明的阻燃剂。
此外,优选的是至少一种含磷有机氧基酰亚胺与选自以下的至少一种另外的阻燃剂组合使用:
a)无机阻燃剂,例如Al(OH)3,Mg(OH)2,AlO(OH),MgCO3,层状硅酸盐如蒙脱石或海泡石,非有机改性或有机改性的复盐如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,以及Sb2O3,Sb2O5,MoO3,锡酸锌,羟基锡酸锌,
b)含氮阻燃剂,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、三聚氰胺磷酸盐、二三聚氰胺磷酸盐、三聚氰胺焦磷酸盐、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,聚-[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,乙二胺甲基膦酸盐,
c)自由基形成剂,例如烷氧基胺、羟胺酯、偶氮化合物、二枯基或聚枯基、不含磷的羟基酰亚胺或其衍生物,例如羟基酰亚胺酯或羟基酰亚胺醚,
d)含磷阻燃剂,例如无机或有机膦酸盐/酯,例如膦酸铝、膦酸酯、甲基膦酸的低聚和聚合衍生物、红磷、磷酸盐/酯,例如间苯二酚二磷酸盐/酯、双酚-A-二磷酸盐/酯及其低聚物、磷酸三苯酯、磷酸乙二胺、次膦酸盐,例如次磷酸及其衍生物的盐,例如烷基次膦酸盐,例如二乙基次膦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)及其经取代的化合物,
e)基于氯和溴的含卤素阻燃剂,例如多溴代二苯醚如十溴代二苯醚、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、溴代二苯基乙烷、三-(2,3-二溴丙基)异氰脲酸酯、四溴双酚-A-双(2,3)二溴丙基醚)、亚乙基双(四溴邻苯二甲酰亚胺)、四溴-双酚A、溴代聚苯乙烯、溴代聚丁二烯或聚苯乙烯-溴代聚丁二烯共聚物、溴代环氧树脂、聚丙烯酸五溴苄酯、溴代聚苯醚,其任选地与Sb2O3和/或Sb2O5组合,
f)硼酸盐,例如硼酸锌或硼酸钙,其任选地在作为载体材料的二氧化硅上,
g)含硫化合物,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,
h)防滴剂,例如聚四氟乙烯,
i)含硅化合物,例如聚苯基硅氧烷,
j)碳改性物,例如碳纳米管(CNT)或石墨烯,
以及其组合或混合物。
在e)下提及的含卤素阻燃剂常常涉及例如从公司Albemarle、Chemtura/GreatLakes或ICL-IP可商购获得的市售产品。
特别地,在根据式I至IV的根据本发明使用的化合物与作为另外的阻燃剂的至少一种自由基形成剂组合的情况下,产生协同效应。
在本发明的意义上,自由基形成剂是能够借助于热和光诱导的裂解产生自由基的化合物。此处用于本申请的合适的自由基形成剂是满足以下条件的的那些自由基形成剂:在塑料或涂料加工过程、即在加工期间具有足够的热稳定性,仍不形成或仅形成很少量的自由基,并仅在较高温度下自发产生自由基,例如仅在着火的情况下发生。涂料和塑料加工过程的各个加工工艺和温度是本领域技术人员已知的。然而,塑料加工工艺和相关温度也可以从专业文献中获得,例如H.Domininghaus,P.Elsner,P.Eyerer,T.Hirth,Kunststoffe(Plastic materials),第8版,Springer 2012。
自由基形成剂从而优选地选自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,或选自亚氨基氧基三嗪。
合适的偶氮化合物的制备在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。
特别地,所使用的自由基形成剂在此选自
a)根据以下所示结构式的N-烷氧基胺,
R3表示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表示烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
Z表示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还能够形成可以任选地被酯基、醚基、胺基、酰胺基、羧基或氨基甲酸酯基取代的闭合环,
E表示烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
b)根据以下所示结构式的偶氮化合物,
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,和
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具有前述的含义,优选为甲基,
d)和/或根据以下所示结构式的聚枯基,
R7具有前述的含义,优选为甲基,2<n<100。
先前提及的所示结构的N-烷氧基胺的典型实例在此是:
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)癸二酸酯;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)己二酸酯;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)-4-十八酰氧基-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)癸二酸酯;双(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)己二酸酯;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'-碳酸酯;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,其为用2-氯-4,6-双(二丁基氨基)-S-三嗪封端的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-三嗪的缩合产物;脂肪族羟胺,例如二硬脂酰胺;以及以下式的化合物
其中n=1至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)。二枯基和聚枯基是例如从UnitedInitiator可获得的市售产品。
特别地,至少一种另外的阻燃剂还可以是含磷阻燃剂。优选的含磷阻燃剂在此是以下结构的次磷酸盐:
R1和R2优选地是相同或不同的,选自直链或带支链的C1-C6烷基和/或芳基;R3选自C1-C6亚烷基,M选自Mg、Ca、Al、Sb、Sn、Ge、Ti、Fe、Zr、Ce、Bi、Sr、Mn、Li、Na、K、Zn和/或质子化的含氮碱,优选钙离子、镁离子、铝离子和/或锌离子;m=1至4,优选2或3;n=1至4,优选1或3;x=1至4,优选1或2。在特别优选的实施方案中,R1=烷基,R2=烷基,M=Al或Zn。
根据本发明的次膦酸盐的特别优选的实例是通过Clariant SE可商购获得的产品Exolit OP(RTM)。
更优选的含磷阻燃剂是具有根据以下式的结构的次磷酸的金属盐
Met是金属,其选自元素周期表的第I族、第II族、第III族和第IV族,n是与相应金属离子Met的电荷相对应的1至4的数。Metn+是例如Na+、Ca2+、Mg2+、Zn2+、Ti4+或Al3+,其中Ca2+、Zn2+和Al3+是特别优选的。
上述次磷酸的盐部分地是例如通过Italmatch Chemical以名称Phoslite(RTM)可商购获得的。
更优选的含磷阻燃剂是膦酸酯或具有根据以下式的结构的膦酸二芳基酯:
R8和R10=H、烷基,优选C1-C4烷基,R9=C1-C4烷基,u=1至5,v=1至5。
相应的结构也可以以膦酸酯低聚物、聚合物和共聚物的形式存在。直链或带支链的膦酸酯低聚物和聚合物是现有技术已知的。关于带支链的膦酸酯低聚物和聚合物,参考美国专利US 2 716 101、US 3 326 852、US 4 328 174、US 4 331 614、US 4 374 971、US 4415 719、US 5 216 113、US 5 334 692、US 3 442 854、US 6 291 630B1、US 6 861 499B2和US 7 816 486B2。关于膦酸酯低聚物,参考美国专利申请US 2005/0020800 A1、US 2007/0219295 A1和US 2008/0045673 A1。关于直链的膦酸酯低聚物和聚合物,参考美国专利文件US 3 946 093、US 3 919 363、US 6 288 210B1、US 2 682 522和US 2 891 915。
低聚的和聚合的膦酸酯是例如可通过FRX Polymers以商品名Nofia(RTM)获得的。
更优选的一组含磷阻燃剂是具有例如以下结构的基于氧杂磷杂菲氧化物的化合物及其衍生物:
M为金属,其选自元素周期表的第2族、第3族、第12族或第13族,x=2或3,n≥10,m=0至25,R=H、卤素或具有1至32个C原子的脂肪族或芳香族基团,R1=H、C1-C6烷基。
基于氧杂磷杂菲氧化物的产品是例如由Schill and Seilacher GmbH以商品名Ukanol(RTM)销售的。其他化合物可以根据例如专利说明书WO 2013020696、WO2010135398、WO 03070736、WO 2006084488、WO 2006084489、WO 2011000019、WO2013068437、WO 2013072295来制备。
其他协同作用的含磷阻燃剂是具有根据以下式之一的结构的环状膦酸酯:
A1和A2彼此独立地表示经取代或未经取代的直链或带支链的具有1至4个碳原子的烷基、经取代或未经取代的苄基、经取代或未经取代的苯基、经取代或未经取代的萘基,A3和A4彼此独立地是甲基或乙基,A5是直链或带支链的具有1至4个碳原子的烷基或是可以分别具有最多3个甲基基团的苯基或苄基基团。
环状膦酸酯例如是由Thor GmbH公司以商品名Aflammit(RTM)销售的,或者可以根据EP 2450401制备。
其他协同作用的含磷阻燃剂是磷腈,特别是聚合磷腈。相应的产品可以例如通过Otsuka Chemicals以名称SPB-100商购获得。
至少一种另外的阻燃剂还可以特别地是含氮阻燃剂。优选的含氮阻燃剂是三聚氰胺多磷酸盐、三聚氰胺氰脲酸盐、三聚氰胺-金属磷酸盐、多-[2,4-(哌嗪-1,4-基)]-6-(吗啉-4-基)-1,3,5-三嗪]、多磷酸铵。这些化合物是市售产品,并可以通过BASF SE以商品名Melapur(RTM)、通过Budenheim Chemische Fabrik以商品名Budit(RTM)、通过Clariant以商品名Exolit(RTM)、通过Huber Chemicals以商品名Safire(RTM)或通过MCATechnologies GmbH以商品名MCA PPM Triazine获得。
根据本发明的含磷有机氧基酰亚胺与膦酸盐/酯和/或(聚)磷腈的组合是非常特别地优选的。
优选地,含磷有机氧基酰亚胺和至少一种另外的阻燃剂以99:1至1:99、优选5:95至50:50、特别优选10:90至30:70的重量比使用。
同样任选和优选的是前述含磷有机氧基酰亚胺与至少一种含磷化合物组合使用。含磷化合物在此与前述的含磷阻燃剂不相同。这些含磷化合物在此可以特别地选自有机亚磷酸盐/酯或亚膦酸盐/酯。合适的化合物于是是例如: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、二亚磷酸二硬脂基季戊四醇酯、亚磷酸三-(2,4-二叔丁基苯基)酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,4-二-枯基苯基)季戊四醇酯、二亚磷酸双(2,6-二叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸基氧基季戊四醇酯、二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂山梨醇酯、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]-1,3,2-二氧杂磷杂环辛烷、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]、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。
此外,有利的是含磷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20重量%、特别优选以1重量%至10重量%使用。
此外,本发明涉及一种阻燃的和/或稳定的、特别是(光)氧化稳定的塑料组合物,其包含以下成分或由以下成分组成:
a)60至99.9重量份、优选60至98重量份、特别优选70至95重量份的至少一种塑料,特别是至少一种热塑性聚合物,
b)0.1至40重量份、优选1至25重量份、特别优选2.5至15重量份的至少一种含磷有机氧基酰亚胺,其包含至少一个以下所示式I的结构单元,
c)0至25重量份、优选1至20重量份、特别优选2.5至15重量份的至少一种另外的阻燃剂,以及
d)0至25重量份、优选1至20重量份、特别优选2.5至15重量份的至少一种另外的含磷化合物。
组合物中所使用的氧基酰亚胺盐和/或阻燃剂对应于上述氧基酰亚胺盐或阻燃剂。特别地,优选的是阻燃剂是膦酸盐/酯或(聚)磷腈。
优选的组合物由以下组成:
(A)60至98份的至少一种热塑性聚合物,
(B)0.1至20份的至少一种含磷氧基酰亚胺,
(C)1至20份的另外的阻燃剂。
为了根据本发明的组合物,使用所有先前描述的氧基酰亚胺。
特别地,其中至少一个、优选全部磷原子以低氧化态即-2、-1、0、+1、+2、或+3存在的上述含磷有机氧基酰亚胺此外还可以用作稳定剂,例如以便在加工期间防止塑料被氧化并因此具有抗氧化作用。
作为抗氧化剂的特别优选的化合物在此是具有亚磷酸酯或亚膦酸酯基团的氧基酰亚胺。借助于稳定化,延迟或防止了对塑料的(光)氧化性损伤。因此,本发明的另一个目的由此是包含处于低氧化态的上述含磷氧基酰亚胺作为稳定剂的稳定的塑料,以及制备该稳定的塑料的方法。
关于塑料,特别是热塑性聚合物以及含磷有机氧基酰亚胺,在此参考上文已经说明的定义和解释。所有前述实施方案同样适用于但不限于阻燃塑料组合物。
在阻燃塑料组合物的情况下,在此更有利的是还包含
e)最多40重量份的至少一种增强材料或填充材料,和/或
f)最多5重量份的选自以下的至少一种添加剂:酚类抗氧化剂、亚磷酸盐/酯、酸捕集剂、受阻胺、分散剂及其组合。
阻燃塑料组合物可以包含添加剂,其选自:UV吸收剂、光稳定剂、稳定剂、羟胺、苯并呋喃酮、成核剂、冲击强度增强剂、增塑剂、润滑剂、流变改性剂、链增长剂、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、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,组合物特别地包含例如基于长链酸的盐的酸捕集剂,如硬脂酸钙、硬脂酸镁、硬脂酸锌、乳酸钙,或者基于水滑石的酸捕集剂,和/或选自酚类抗氧化剂和亚磷酸盐/酯的稳定剂,和/或选自受阻胺(HALS)的光稳定剂,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、2-羟基二苯甲酮、苯甲酸的酯、丙烯酸盐/酯、草酰胺和2-(2-羟苯基)-1,3,5-三嗪的化合物。
合适的2-(2'-羟苯基)苯并三唑是例如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-羟基二苯甲酮是例如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。
合适的丙烯酸盐/酯是例如乙基-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-p-甲氧基肉桂酸酯、丁基-α-氰基-β-甲基-p-甲氧基肉桂酸酯、甲基-α-甲酯基-p-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。
合适的苯甲酸的酯是例如4-叔丁基苯基水杨酸酯、苯基水杨酸酯、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。
合适的草酰胺是例如4,4'-二辛氧基草酰苯胺、2,2'-二乙氧基草酰苯胺、2,2'-二辛氧基-5,5'-二叔丁基草酰苯胺(tert-butoxanilide)、2,2'-二(十二烷氧基)-5,5'-二叔丁基草酰苯胺、2-乙氧基-2'-乙基草酰苯胺、N,N'-双(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2'-乙基草酰苯胺(ethoxanilide)及其与2-乙氧基-2'-乙基-5,4'-二叔丁基草酰苯胺的混合物、与邻甲氧基-二取代的草酰苯胺和对甲氧基-二取代的草酰苯胺的混合物、和与邻乙氧基-二取代的草酰苯胺和对乙氧基-二取代的草酰苯胺的混合物。
合适的2-(2-羟基苯基)-1,3,5-三嗪是例如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-4-三癸氧基苯基)-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/十三烷氧基-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。
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,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-羟苯基)己二酸酯;
生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚以及这些的混合物(维生素E);
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-羟基苯基)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]对苯二酸酯、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-苄基、N-苄基和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、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盐/酯,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、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,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-羟苄基)异氰脲酸酯;
苄基膦酸盐/酯,例如二甲基-2,5-二叔丁基-4-羟基苄基膦酸酯、二乙基-3,5-二叔丁基-4-羟基苄基膦酸酯、二(十八烷基)-3,5-二叔丁基-4-羟基苄基膦酸酯、二(十八烷基)-5-叔丁基-4-羟基-3-甲基苄基膦酸酯、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;
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、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,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-羟苯基)丙酸的酰胺,例如N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)六亚甲基二酰胺、N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)六亚甲基二酰胺、N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)六亚甲基二酰胺、N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)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(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、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、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯基)异氰脲酸酯、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、三乙二醇-双[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、N,N'-己-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/亚膦酸酯是例如:
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、二亚磷酸二硬脂基季戊四醇酯、亚磷酸三-(2,4-二叔丁基苯基)酯、二亚磷酸二异癸基季戊四醇酯、二亚磷酸双(2,4-二叔丁基苯基)季戊四醇酯、二亚磷酸双(2,4-二-枯基苯基)季戊四醇酯、二亚磷酸双(2,6-二叔丁基-4-甲基苯基)季戊四醇酯、二亚磷酸二异癸基氧基季戊四醇酯、二亚磷酸双(2,4-二叔丁基-6-甲基苯基)季戊四醇酯、二亚磷酸双(2,4,6-三(叔丁基苯基)季戊四醇酯、三亚磷酸三硬脂山梨醇酯、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]-1,3,2-二氧杂磷杂环辛烷、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]、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。
其他合适的稳定剂是胺类抗氧化剂。合适的胺类抗氧化剂是例如:
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-(对甲苯磺酰氨基)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-萘胺、N-(4-叔辛基苯基)-1-萘胺、N-苯基-2-萘胺、辛基化的二苯胺,例如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/叔辛基二苯胺的混合物、单烷基化和二烷基化的壬基二苯胺的混合物、单烷基化和二烷基化的十二烷基二苯胺的混合物、单烷基化和二烷基化的异丙基/异己基二苯胺的混合物、单烷基化和二烷基化的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,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下式的Genox EP(Addivant):
其他合适的稳定剂是硫代协作剂。合适的硫代协作剂是例如二硬脂基硫代二丙酸酯、二月桂基二丙酸酯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、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-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、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-吗啉基-2,6-二氯-1,3,5-三嗪的直链或环状的缩合产物、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。
合适的分散剂是例如:
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聚糖酯,例如山梨聚糖单硬脂酸酯,钛酸盐/酯和锆酸盐/酯,与官能团的反应性共聚物,例如聚丙烯-丙烯酸共聚物、聚丙烯-马来酸酐共聚物、聚乙烯-缩水甘油基甲基丙烯酸酯共聚物、聚苯乙烯-马来酸酐-聚硅氧烷交替共聚物: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,两亲性共聚物:例如聚乙烯-聚环氧乙烷嵌段共聚物,树状聚合物,例如含羟基的树状聚合物。
合适的成核剂是例如滑石,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,以及三酰胺,例如根据以下结构的三酰胺
合适的填充材料和增强材料是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,例如纤维素或合成纤维。其他合适的填充材料是水滑石或沸石或层状硅酸盐,例如蒙脱石、膨润土、拜来石(beidelite)、云母、水辉石、皂石、蛭石、ledikite、麦羟硅钠石(magadite)、伊利石、高岭土、钙硅石、凹凸棒石。
合适的颜料可以具有无机或有机性质。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、酞菁或皮蒽酮。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。
用于缩聚聚合物如聚酯或聚酰胺的直链分子重量增加的合适的链增长剂是例如二环氧化物、双唑啉、双唑酮、双嗪、二异氰酸盐/酯、二酸酐、双酰基内酰胺、双马来酰亚胺、二氰酸盐/酯、碳二亚胺。其他合适的链增长剂是聚合化合物,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。
合适的填料失活剂是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-二缩水甘油醚及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-聚环氧烷。
合适的抗静电剂是例如乙氧基化的烷基胺、脂肪酸酯、磺酸烷基酯和聚合物,例如聚醚酰胺。
此外,本发明涉及制备前述阻燃和/或稳定的、特别是(光)氧化稳定的塑料组合物的方法,其中在60至99.9重量份、优选60至98重量份、特别优选70至95重量份的至少一种塑料,特别是至少一种热塑性聚合物中引入以下成分
a)0.1至40重量份、优选1至25重量份、特别优选2.5至15重量份的至少一种含磷有机氧基酰亚胺,其包含至少一个以下所示式I的结构单元,
b)在之前、之后或同时地,0至25重量份、优选2.5至15重量份的至少一种另外的阻燃剂。
关于优选可使用的含磷有机氧基酰亚胺,参考先前给出的解释。
本发明的另一主题是由前述阻燃塑料组合物能够制备的模塑件、漆或涂料,其特别是通过挤出、注塑、吹塑、压制工艺制备的注塑件、箔、涂料、泡沫、纤维、电缆和管的形式,例如用于家用电器、车辆部件、消费品、家具、织物。
根据本发明所使用的阻燃剂特别适合用于热塑性、弹性和刚性的塑料,其特别是通过挤出、注塑、吹塑、压延、压制工艺、纺丝工艺、旋转模塑或刷涂和涂覆工艺制备的注塑件、箔或薄膜(film)、涂料或漆、泡沫、纤维、电缆和管、型材、中空体、条、膜(membrane)如土工膜或黏合剂的形式,例如用于电气和电子工业、建筑工业、运输工业(汽车、航空器、船、火车)、用于医学应用、用于家用电器、车辆部件、消费品、包装、家具、织物。其他使用领域是清漆、漆和涂料。
根据本发明可以使用的或可以被包含在阻燃塑料组合物中的含磷有机氧基酰亚胺的特别优选的实例是以下所示的,而不将先前所示的发明限制于这些具体结构:
任选地,根据本发明的含磷氧基酰亚胺还可以具有聚合结构,例如具有以下重复单元:
塑料中上述阻燃剂和另外的添加剂的并入是通过普通加工方法进行的,优选通过混合机、捏合机和挤出机将聚合物熔化并与阻燃剂和添加剂混合。作为加工机器,优选挤出机,例如单螺杆挤出机、双螺杆挤出机、行星滚轴挤出机、环形挤出机,共捏合机,其优选配备有真空脱气装置。加工从而可以在空气或任选地在惰性气体条件下进行。不同的阻燃剂和添加剂从而可以分别地或者作为混合物以液体、粉末、颗粒或经压实的产品的形式或者也可以以包含例如50%至80%的根据本发明的组合物的母料或浓缩物的形式进行添加。
参照以下实施例更详细地说明本发明,但不将本发明限制于此。
A)根据本发明的含磷氧基酰亚胺的合成
合成实施例1:
磷酰基-三-N-氧基邻苯二甲酰亚胺的合成
在惰性气体下,向N-氧基邻苯二甲酰亚胺钠(18.41g;9.9毫摩尔)在纯THF(125ml)中的分散体逐滴添加磷酰氯(3.0ml;3.3毫摩尔),之后将混合物搅拌两天,结果是分散体脱色。通过过滤分离不可溶成分,在旋转蒸发仪上去除溶剂后不进一步清洗而获得包含产物的混合物。
1H-NMR(500MHz,DMSO):δ=7.82(S)ppm。
13C-NMR(126MHz,DMSO):δ=164.05,134.47,128.73,122.91,39.52ppm。
31P-NMR(202MHz,DMSO):δ=0.31,-11.76ppm。
合成实施例2:
苯氧基磷酰基-双-N-氧基邻苯二甲酰亚胺的合成
在惰性气体下,向N-氧基邻苯二甲酰亚胺钠(18.0g;9.7毫摩尔)在纯THF(125ml)中的分散体逐滴添加二氯磷酸苯酯(7.1ml;4.7毫摩尔),之后将混合物搅拌两天,结果是分散体脱色。通过过滤分离不可溶成分,在旋转蒸发仪上去除溶剂后不进一步清洗而获得包含产物的混合物。
1H-NMR(300MHz,DMSO);δ=7.82(S),7.33–7.31(m)
31P-NMR(122MHz,DMSO);δ=-6.58。
合成实施例3:
10-氯-9,10-二氢-9-氧杂-10-磷杂菲-N-羟基邻苯二甲酰亚胺加合物的合成:
向N-羟基邻苯二甲酰亚胺(6.95g;42.6毫摩尔)和三乙胺(5.9ml;42毫摩尔)在纯THF(100ml)中的溶液逐滴添加10-氯-9,10-二氢-9-氧杂-10-磷杂菲(10g;42.6毫摩尔)在纯THF(50ml)中的溶液,之后将混合物在环境温度下搅拌12小时,结果是溶液脱色。反应结束后,将过滤出产物,用水清洗,之后通过在甲苯中重结晶来获得纯产物形式的产物。
1H NMR(300MHz,CDCl3):δ=8.27(ddd,J=7.7,1.5,0.6Hz,1H),8.05(d,J=8.0Hz,1H),7.99(dd,J=8.0,1.6Hz,1H),7.86-7.80(m,2H),7.80–7.77(m,1H),7.77–7.71(m,2H),7.59(td,J=7.6,1.0Hz,1H),7.45,(ddd,J=8.5,7.0,1.6Hz,1H),7.39–7.34(m,1H),7.31(ddd,J=8.0,7.1,1.6Hz,1H)。
31P NMR(122MHz,CDCl3):δ=2.58。
合成实施例4:
二苯氧基磷酰基-N-氧基苯二甲酰亚胺的合成:
向N-羟基邻苯二甲酰亚胺(15.18g;93毫摩尔)和三乙胺(13ml;93毫摩尔)在纯DCM(400ml)中的溶液逐滴添加二苯氧基磷酰氯(19.3g;93毫摩尔),之后将混合物在环境温度下搅拌12小时,结果是溶液脱色。反应结束后,将溶液分别用200ml的水,然后用200ml的10%NaHCO3溶液清洗三次。在氯化钙上干燥和去除溶剂后,通过在DCM/己烷=1:1中重结晶来获得产物。
1H-NMR(300MHz,CDCl3):δ=7.93–7.85(m,2H),7.85-7.76(m,2H),7.48–7.36(m,8H),7.36–7.20(m,2H)。
31P-NMR(122MHz,CDCl3):δ=-11.68ppm。
B)根据本发明的阻燃塑料混合物的制备和测试
在190℃的温度以150rpm的螺杆转速在11mm双螺杆挤出机(Thermo Scientific的Process 11)上进行聚丙烯样品(DOW C766-03)的挤出。首先通过混合使期望比例的聚合物和添加剂均匀化,并经由体积计量供给至挤出。
燃烧测试的测试件是使用10t液压机(Werner&Pfleiderer)在220℃的温度和2t的压力下由粒料制备的。为此,将粒料填充到压模中,并将其转移到已经预热的压力机中。在0.5t的压力下,首先使粒料熔化60秒。熔化时间结束之后,将压力升高至2t,再保持恒定3分钟。在维持恒定压力的同时,将模具冷却至60℃,此后移出测试件。测试件具有根据标准的以下尺寸:127.5×12.5×1.5。
表1中包含的根据本发明的实施例和比较例是根据DIN EN 60695-11-10测试的,获得了根据标准的燃烧时间和分级:
表1:聚丙烯的组成和燃烧测试的结果
二乙基次膦酸铝(Exolit OP 1230,制造商:Clariant SE)
根据本发明的实施例在移除火源后自动灭火,并且相对于比较例具有出人意料地减少的燃烧时间,获得符合V-2的分级。
Claims (19)
2.根据权利要求1所述的用途,其特征在于,所述塑料是热塑性聚合物。
3.根据权利要求2所述的用途,其特征在于,所述热塑性聚合物选自
a)由烯烃或二烯制得的聚合物,
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,包括相应的接枝共聚物,以及由甲基丙烯酸甲酯、苯乙烯-丁二烯和丙烯腈制得的接枝共聚物,
c)含卤素聚合物,
d)不饱和酯的聚合物,
e)由不饱和醇及其衍生物制得的聚合物,
f)聚缩醛,
g)聚苯醚及其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制得的聚氨酯,
j)聚酰胺,不同的聚酰胺的共混物,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制得或者由羟基羧酸制得的聚酯,
m)聚碳酸酯、聚酯碳酸酯及其共混物,
n)纤维素衍生物,
o)刚性或弹性的、非热塑性的塑料,以及
p)前述聚合物中两种或更多种的混合物、组合或共混物。
4.根据权利要求3所述的用途,其特征在于,所述含卤素聚合物为由氯乙烯和偏二氯乙烯制得的共聚物、或由氯乙烯和醋酸乙烯酯制得的共聚物、氯代聚乙烯、聚偏二氟乙烯。
5.根据权利要求1所述的用途,其特征在于,至少一种含磷不含卤素的有机氧基酰亚胺与选自以下的至少一种另外的阻燃剂组合使用:
a)无机阻燃剂,
b)含氮阻燃剂,
c)自由基形成剂,
d)含磷阻燃剂,
e)基于氯和溴的含卤素阻燃剂,
f)硼酸盐,
g)含硫化合物,
h)防滴剂,
i)含硅化合物,
j)碳改性物,
以及其组合或混合物。
6.根据权利要求5所述的用途,其特征在于,所述无机阻燃剂为层状硅酸盐,非有机改性或有机改性的复盐,以及Sb2O3,Sb2O5,MoO3,锡酸锌、羟基锡酸锌。
7.根据权利要求5所述的用途,其特征在于,所述自由基形成剂选自
a)根据以下所示结构式的N-烷氧基胺,
R3表示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表示烷氧基、芳氧基、环烷氧基、芳烷氧基或酰氧基基团,
Z表示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还能够形成可以任选地被酯基、醚基、胺基、酰胺基、羧基或氨基甲酸酯基取代的闭合环,
b)根据以下所示结构式的偶氮化合物,
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,和
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具有前述的含义,
d)和/或根据以下所示结构式的聚枯基,
R7具有前述的含义。
8.根据权利要求5至7中任一项所述的用途,其特征在于,所述含磷不含卤素的有机氧基酰亚胺和所述至少一种另外的阻燃剂以99:1至1:99的重量比使用。
9.根据权利要求1所述的用途,其特征在于,所述含磷不含卤素的有机氧基酰亚胺与至少一种含磷化合物组合使用。
10.根据权利要求1所述的用途,其特征在于,所述含磷不含卤素的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。
12.根据权利要求11所述的阻燃塑料组合物,其特征在于,所述塑料为热塑性聚合物。
13.根据权利要求11所述的阻燃塑料组合物,其特征在于,还包含
a)最多40重量份的至少一种增强材料或填充材料,和/或
b)最多5重量份的选自以下的至少一种添加剂:酚类抗氧化剂、亚磷酸盐/酯、酸捕集剂、受阻胺、分散剂及其组合。
14.根据权利要求11所述的阻燃塑料组合物,其特征在于,还包含
a)最多40重量份的至少一种增强材料或填充材料,和/或
b)最多5重量份的至少一种添加剂,
所述添加剂选自:UV吸收剂、稳定剂、成核剂、冲击强度增强剂、增塑剂、润滑剂、流变改性剂、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、分散剂、相容剂、氧捕集剂、酸捕集剂、标记剂或防雾剂。
15.根据权利要求11所述的阻燃塑料组合物,其特征在于,还包含
a)最多40重量份的至少一种增强材料或填充材料,和/或
b)最多5重量份的至少一种添加剂,
所述添加剂是羟胺或苯并呋喃酮。
16.根据权利要求11所述的阻燃塑料组合物,其特征在于,还包含
a)最多40重量份的至少一种增强材料或填充材料,和/或
b)最多5重量份的至少一种添加剂,
所述添加剂是加工助剂。
17.根据权利要求14所述的阻燃塑料组合物,其特征在于,所述稳定剂为光稳定剂。
19.一种由根据权利要求11所述的阻燃塑料组合物能够制成的模塑件或涂料。
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PCT/EP2015/071251 WO2016042040A1 (de) | 2014-09-18 | 2015-09-16 | Verwendung von phosphorhaltigen organischen oxyimiden als flammschutzmittel und/oder als stabilisatoren für kunststoffe, flammgeschützte und/oder stabilisierte kunststoffzusammensetzung, verfahren zu deren herstellung sowie formteile, lacke und beschichtungen |
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WO2023242699A1 (en) * | 2022-06-13 | 2023-12-21 | Inamdar Yusuf A S | A composition for an intumescent paint |
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EP3194487A1 (de) | 2017-07-26 |
JP2017535626A (ja) | 2017-11-30 |
EP3194482A1 (de) | 2017-07-26 |
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 |
CN106715560B (zh) | 2019-08-27 |
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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