CN1075968A - 新型亚膦酸环亚烷基双酚酯 - Google Patents
新型亚膦酸环亚烷基双酚酯 Download PDFInfo
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- CN1075968A CN1075968A CN93100816A CN93100816A CN1075968A CN 1075968 A CN1075968 A CN 1075968A CN 93100816 A CN93100816 A CN 93100816A CN 93100816 A CN93100816 A CN 93100816A CN 1075968 A CN1075968 A CN 1075968A
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- butyl
- hydrogen
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明公开了新型的式I化合物,作为保护有机
物质不受热、氧化或光诱导降解的稳定剂。
式中n为0,1或2;R和R1是相互独立的C1-4烷基
或一起组成2,3-去氢-1,5-亚戊基;R2和R3是相
互独立的氢、C1-4烷基或C5-6环烷基;若n=1,R4、
R5、R6和R7是相互独立的氢或C1-4烷基;若n=0
和若n=2,它们是相互独立的氢。
Description
本发明涉及新型亚膦酸酯、它们的组合物、它们用作稳定剂以及它们的制备方法。
DE-B-1,237,312和US-A-4,206,111中公开了螺环连接的双亚膦酸酯可用作聚烯烃的稳定剂。除大量其它的亚膦酸酯以外,EP-A-33,395和US-A-4,463,112也包含有一般的亚膦酸双酚酯,其中亚膦酸是用单官能团的醇类来酯化的。具有下列形式的双亚膦酸酯:
(其中Y含有一个杂原子)也被包括在美国专利US-A-3,856,728中。
但仍然需要为那些对氧化,热或光诱导的降解很敏感的有机材料提供有效的稳定剂。
按此,本发明有关于一种具有下式Ⅰ的化合物:
其中n值为0,1或2,
R和R1可彼此独立地是C1-C4烷基,或它们在一起组成一个2,3-去氢-1,5-亚戊基,
R2和R3可彼此独立地是氢、C1-C4烷基或C5-C6环烷基,并且
如果n=1,R4、R5、R6、R7可彼此独立地是氢或C1-C4烷基,或者,如果n=0和如果n=2,则它们都是氢。
其中n值是1或2的式Ⅰ化合物是优选的。
优选的式Ⅰ化合物也包括那些R2和R3可彼此独立地是氢、C1-C4烷基和环己基的化合物。
特别感兴趣的式Ⅰ化合物是那些n值为1的化合物,其中值得特别注意的是那些R4是氢、R5、R6和R7可彼此独立地是氢或甲基的化合物。
更感兴趣的式Ⅰ化合物是那些R2和R3可彼此独立地是氢,甲基,丁基或环己基的化合物,特别有兴趣的是那些R2和R3可彼此独立地是氢,甲基或叔丁基的式Ⅰ化合物。
那些R5、R6、R7是氢,R4是氢或叔丁基的式Ⅰ化合物也是优选的化合物,尤其是那些R4、R5、R6和R7都是氢的化合物。
那些R和R1彼此独立地是甲基或丁基,或它们在一起组成2,3-去氢-1,5-亚戊基的式Ⅰ化合物特别优选的化合物。
如果n=0,就得到具有下式的新的环戊基化合物:
如果n=2或n=1,得到的就是相应的环庚基或未取代的或取代环己基化合物。
R、R1、R2、R3、R4、R5、R6和R7作为C1-C4的烷基可以是线形的,也可以是支链的,即可以是甲基、乙基、1-丙基(正丙基)、2-丙基(异丙基)、1-丁基(正丁基)、2-丁基(第二丁基)、2-甲基丙基(异丁基)或1,1-二甲基乙基(叔丁基)。
式Ⅰ化合物可以通过把具有下式Ⅱ的化合物:
与具有下式Ⅲ的适当的卤代亚膦酸酯:
进行反应而方便地制得(式中X是氯、溴或碘原子,最好是氯原子。取代基R、R1、R2、R3、R4、R5、R6和R7以及指数n的定义与式Ⅰ中的相同)。
本发明也涉及制备式Ⅰ化合物的方法,它包括把式(Ⅱ)化合物与具有式(Ⅲ)的环状卤代亚膦酸酯进行反应。
优选的制造方法是其中所用的具有式(Ⅲ)的环状卤代亚膦酸酯是具有式Ⅲa的氯代亚膦酸酯
(Ⅲa).。特别优选的方法包括在一种碱存在的条件下来进行反应。适当的有机碱包括有机胺类(例如三甲胺、三乙胺、三丁胺、N,N-二甲基苯胺、N,N-二乙基苯胺或吡啶)、氢化物(例如锂、钠或钾的氢化物)、有机金属化合物(例如甲基锂、丁基锂或醇化物(例如甲醇化钠),适当的无机碱有典型的碱金属氢氧化物诸如氢氧化钠或氢氧化钾,或碱金属碳酸盐诸如碳酸钠或碳酸钾,特别方便是使用三乙胺或丁基锂作为碱。
反应可在一种溶剂中方便地进行,由一种离析物开始,最好是具有式(Ⅱ)的双酚,可用碱也可不用碱。
适当的溶剂是脂肪和芳香烃类或脂肪和芳香卤代烃类或醚类。适当的芳香烃类典型地有苯、甲苯和二甲苯,氯代芳香烃类可以是氯代苯。适当的卤代脂肪烃类典型地有二氯甲烷或氯仿。适当的醚类典型地有二乙醚、二丁醚或四氢呋喃。优选的溶剂是芳香烃类,特别是甲苯或二甲苯。
反应可通过在冷却和搅拌的条件下慢慢地加入第二种离析物,最好是具有式Ⅲ的环状卤代亚膦酸酯而方便地进行。温度不是关键性的,最好是在搅拌下把反应混合物的温度保持在-30℃至+50℃的范围内,典型地是0℃至20℃,最好是在5℃至15℃之间。可通过过滤方便地除去沉淀出来的碱的盐酸盐。
离析物最好以1摩尔式Ⅱ化合物对2摩尔式Ⅲ化合物的比例加入,但是也可以用过量的式Ⅲ化合物,典型地可用2.01至2.2当量,加入的碱的量可以变化,从催化量至化学计量的量直到数倍摩尔过量于式Ⅲ化合物的量,但最好是加入的碱量与式Ⅲ化合物是等摩尔量的。
可用通常的后处理方法从反应混合物中析离出式Ⅰ化合物,方便地是通过浓缩,溶于一种溶剂,过滤除去不溶物,结晶并干燥。溶解和过滤可在接近溶剂沸点的温度进行,用于后处理的适当溶剂和上面叙述过的相同。烃类诸如石油英或石油醚是特别有用的溶剂。
具有式Ⅱ的双酚类是已知的化合物,它可用Houben Weyl(译注:指Houben Weyl编著的“Methoden der Organischen Chemie”一书)第4版第Ⅵ/1c卷第1028-1030页所叙述的方法来制备。(Thieme-Verlag出版,Stuttgart,1976)。卤代亚膦酸酯的制备方法也是已知的,典型地是通过把三卤化磷与适当的1,3-二醇,按照Houben-Weyl第4版第Ⅻ/2卷第45-50页所叙述的方法进行反应(Thieme-Verlag出版,Stuttgart,1964)。
式Ⅰ化合物对于使有机物对氧化、热或光诱导的降解有更好的稳定性方面具有优良的适应性。按此,本发明也涉及一种包含(a)一种对氧化、热或光诱导的降解反应是敏感的有机物和(b)至少一种式(Ⅰ)化合物的组合物;以及使用式(Ⅰ)化合物来使这类有机物稳定化。
这类有机物的实例有:
1.单烯和双烯的高聚物,例如聚丙烯、聚异丁烯、聚1-丁烯,聚4-甲基-1-戊烯;聚异戊二烯或聚丁二烯,以及环状烯烃的高聚物,例如环戊烯或降冰片烯的高聚物;聚乙烯(它可被任意地交联)例如高密度聚乙烯(HDPE),低密度聚乙烯(LDPE),线形低密度聚乙烯(LLDPE),支链低密度聚乙烯(BLDPE)。
聚烯烃类,如上节所举的单烯烃的高聚物的实例,最好是聚乙烯和聚丙烯,可用不同的方法,特别是下面列举的方法来制备:
a)游离基聚合(通常在高压和高温条件下)
b)用一种催化剂进行的催化聚合,这种催化剂通常包含一种或多于一种周期表中的第Ⅳb族,Ⅴb族,Ⅵb族或第Ⅷ族的金属,这些金属通常有一种或多于一种配位体,典型地有氧化物、卤化物、醇化物、酯、醚、胺、烷基、烯基和/或芳基等,它们可以是π配位的或σ配位的,这些金属络合物可以以游离的形式存在,也可以固定在底物上,典型的底物有活化的氯化镁,氯化钛(Ⅲ),氧化铝或氧化硅。这些催化剂可以溶于聚合反应的介质中,也可以不溶;催化剂可以本身用于聚合反应中,也可以应用进一步的活化剂,典型的活化剂有金属烷基化物、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基环氧化物;所说的金属是周期表中的第Ⅰa,Ⅱa和/或Ⅲa族的元素。活化剂可以方便地进一步用酯、醚、胺或硅醚基团来修饰,这些催化剂体系通常被称为Phillips,Standard Oil Imdiana,Ziegler(-Natta),TNZ(Dupont),金属茂或单点催化剂(SSC)。
2.上述1中所叙述的高聚物的混合物,例如聚丙烯和聚异丁烯的混合物、聚丙烯和聚乙烯的混合物(例如PP/HDPE,PP/LDPE)以及不同类型的聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯或双烯彼此形成的共聚物或与其它乙烯基单体形成的共聚物,例如乙烯/丙烯共聚物、线形低密度聚乙烯(LLDPE)以及它与低密度聚乙烯(LDPE)的混合物、丙烯/1-丁烯共聚物、丙烯/异丁烯共聚物、乙烯/1-丁烯共聚物、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、丙烯/丁二烯共聚物、异丁烯/异戊二烯共聚物、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/酪酸乙烯基酯共聚物以及它们与一氧化碳的共聚物,或乙烯/丙烯酸共聚物和它们的盐(离聚物),以及乙烯与丙烯和一种双烯诸如己二烯、二环戊二烯或亚乙基-降冰片烯的三元共聚物。以及这类共聚物彼此之间以及与上述1中所叙述的高聚物形成的混合物,例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-醋酸乙烯酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA以及间聚的或无规聚合的聚烯烃/一氧化碳共聚物,以及它们与别的高聚物,例如聚酰胺所形成的混合物。
4.烃类树脂(例如C5-C9)包括它们的氢化修饰物(例如粘合剂)以及聚亚烷基与淀粉的混合物。
5.聚苯乙烯、聚(对甲基苯乙烯)、聚(α-甲基苯乙烯)。
6.苯乙烯或α-甲基苯乙烯与双烯或丙烯酸衍生物的共聚物,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、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,高冲击强度苯乙烯共聚物和其它高聚物的混合物,例如与聚丙烯酸酯、一种双烯高聚物或一种乙烯/丙烯/双烯的三元共聚物;以及苯乙烯的嵌段共聚物,诸如苯乙烯/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。
7.苯乙烯或α-苯乙烯的接枝共聚物,例如苯乙烯在聚丁二烯上、苯乙烯在聚丁二烯-苯乙烯上或聚丁二烯-丙烯腈共聚物上;苯乙烯和丙烯腈(或甲基丙烯腈)在聚丁二烯上;苯乙烯、丙烯腈和甲基丙烯酸甲酯在聚丁二烯上;苯乙烯和马来酸酐在聚丁二烯上;苯乙烯、丙烯腈和马来酸酐或马来亚酰胺在聚丁二烯上;苯乙烯或马来亚酰胺在聚丁二烯上;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯在聚丁二烯上;苯乙烯和丙烯腈在乙烯/丙烯/二烯三元聚合物上;苯乙烯和丙烯腈在丙烯酸多烷基酯或甲基丙烯酸多烷基酯上、苯乙烯和丙烯腈在丙烯酸酯/丁二烯共聚物上,以及它们与6)中所列共聚物形成的混合物,例如被称为ABS,MBS,ASA,或AES高聚物的共聚混合物。
8.含卤素的高聚物诸如聚氯丙烯、氯化橡胶、氯化或磺化聚乙烯、乙烯和氯化乙烯的共聚物、氯代环氧丙烷的均聚物和共聚物,特别是含卤乙烯基化合物的高聚物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯以及它们的共聚物诸如氯乙烯/偏二氯乙烯、氯乙烯/醋酸乙烯酯或偏二氯乙烯/醋酸乙烯酯的共聚物。
9.由α、β-不饱和酸衍生的高聚物以及它们的衍生物,诸如聚丙烯酸酯和聚甲基丙烯酸酯;用丙烯酸丁酯冲击修饰的聚甲基丙烯酸甲酯、聚丙烯酰胺和聚丙烯腈。
10.在9)中所叙述的单体彼此之间或者与别的不饱和单体之间形成的共聚物,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/卤乙烯共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11.由不饱和醇和胺或酰基衍生物或它们的缩醛所衍生的高聚物,例如聚乙烯醇、聚醋酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚马来酸乙烯酯、聚乙烯基丁醛,聚邻苯二甲酸烯丙基酯或聚烯丙基蜜胺以及它们与1)中所叙述的烯烃形成的共聚物。
12.环状醚的均聚物和共聚物,诸如聚亚烷基二醇、聚环氧乙烷、聚环氧丙烷或它们与联缩水甘油醚所形成的共聚物。
13.聚缩醛类诸如聚氧化亚甲基和那些含有环氧乙烷作为共聚用单体的聚氧化亚甲基;用热塑性聚氨基甲酸酯修饰的聚缩醛类,丙烯酸酯类或MBS。
14.聚苯氧和聚苯硫,以及聚苯氧和苯乙烯高聚物或聚酰胺的混合物。
15.由一方面是羟基终止的聚醚、聚酯或聚丁二烯,另一方面是脂肪或芳香聚异氰酸酯所衍生的聚氨基甲酸酯类以及它们的前体。
16.由二胺和二羧酸和/或由氨基羧酸或相应的内酰胺所衍生的聚酰胺和共聚酰胺,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开始的芳香聚酰胺;由六亚甲基二胺和间苯二甲酸或/和对苯二甲酸制备的聚酰胺,可用或不用高弹体作为修饰剂,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;也可以是上述聚酰胺与聚烯烃、烯烃共聚物、离聚物或化学键的或接枝的高弹体形成的嵌段共聚物;也可以是与聚醚类例如聚乙二醇、聚丙二醇、或聚1,4-亚丁基二醇形成的嵌段共聚物;还有用EPDM或ABS修饰过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-亚胺和聚苯并咪唑类。
18.由二羧酸和二醇和/或由羟基羧酸或相应的内酯衍生的聚酯类,例如聚对苯二甲酸乙二醇酯、聚对苯二甲酸1.4-丁二醇酯、聚对苯二甲酸-1.4-二羟甲基环己烷酯、聚羟基苯甲酸酯以及由羟基终止的聚醚衍生的嵌段共聚醚酯类;还有用聚碳酸酯或MBS修饰的聚酯类。
19.聚碳酸酯和聚酯碳酸酯。
20.聚砜、聚醚砜和聚醚酮类。
21.由一方面是醛类,另一方面是酚类、脲和蜜胺类衍生的交联高聚物,诸如酚/甲醛树脂,脲/甲醛树脂和蜜胺/甲醛树脂。
22.干性和非干性醇酸树脂。
23.由饱和和不饱和的二羧酸与多元醇衍生的、並以乙烯基化合物作为交联剂的不饱和聚酯树脂以及低可燃性的它们的含卤修饰物。
24.由取代的丙烯酸酯衍生的可交联的丙烯酸树脂,例如环氧丙烯酸酯,氨基甲酸酯丙烯酸酯或聚酯丙烯酸酯。
25.用蜜胺树脂、脲树脂、聚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。
26.由聚环氧化合物衍生的交联的环氧树脂,例如由联缩水甘油醚或由环状脂肪二环氧化物衍生的交联环氧树脂。
27.天然高聚物诸如纤维素、橡胶、明胶以及经化学修饰的它们的同系衍生物,例如醋酸纤维素、丙酸纤维素、丁酸纤维素或纤维素醚诸如甲基纤维素,以及松脂类及它们的衍生物。
28.上述高聚物的掺和物(高聚物混体)、例如PP/EPOM、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和共聚物、PA/HDPE、PA/PP、PA/PPO。
29.天然存在的和合成的有机物,它们是纯的单体化合物或这类化合物组成的混合物,例如矿物油、动物和植物脂肪、油和蜡,或基于合成酯类的油、脂肪和蜡(例如苯二甲酸酯类、己二酸酯类、磷酸酯类或偏苯三甲酸酯类)以及合成酯类与矿物油类以任何重量比例组成的混合物,典型地是那些用于纺纱的组合物以及这类物质在水溶液中形成的乳液。
30.天然橡胶或合成橡胶的水溶液乳液,例如天然橡胶或羧化苯乙烯/丁二烯共聚物的胶乳。
欲被保护的作为组份(a)的有机物最好是天然的、半合成的或,更好是,合成的有机物。特别优选的有机物有热塑性的高聚物,最好是PVC或聚烯烃,特别是聚乙烯和聚丙烯(PP)。
本发明的组合物中所含式Ⅰ化合物的量可方便地在0.01至10%重量百分数范围内,典型地是0.05至5%,优选的是0.05至3%,更优选的范围是0.05至2%。组合物可包含一种或多种式Ⅰ化合物的组份并且重量百分数是基于所说化合物的总量。计算时是基于没有式Ⅰ化合物存在时有机物的总重量。
掺入有机物中的操作可通过本专业通常使用的方法来完成,即把它们与式Ⅰ化合物及进一步可供选择的添加剂掺和在一起,或者把式Ⅰ化合物施用到有机物中去。如果有机物是高聚物,特别是合成高聚物。掺入操作可在成型商品成形操作之前或在操作过程中完成,或将溶解或分散好的化合物施用到高聚物中去,然后蒸发掉溶剂,或不蒸发溶剂。在高弹体的情况下,这些也可作为胶乳而稳定化。把式Ⅰ化合物掺入高聚物中的另一种方法是,在相应的单体聚合过程中或刚聚合完的时候,或在交联之前把所说的化合物加进去。式Ⅰ化合物也可以用胶囊包起来的形式(例如包在蜡,油脂或高聚物中)加入。如果式Ⅰ化合物是在聚合前或聚合过程中加入,它也可以用作高聚物链长的调节剂(链终止剂)。
式Ⅰ化合物或它的混合物也可以包含的这些化合物的母料的形式加入,欲被稳定的高聚物,其浓度典型的值是2.5至25%重量百分数。
式Ⅰ化合物可通过以下的技术方便地掺入:
-作为乳液或分散液(例如往胶乳或乳液高聚物中)
-作为干混合物同时掺入别的组份或高聚物混合物。
-直接加入加工装置中(例如挤压机,密闭式混合机以及类似的装置)
-作为溶液或熔化物。
本发明的高聚物组合物可以不同的形式应用,並加工成不同的产物,包括板片,丝,螺条,模制件,模型,或用作涂料、清漆,粘合剂或腻子的掺合剂。
如已经说过的那样,欲保护的有机物最好是天然的,半合成的或更好是合成的高聚物。它对于保护热塑性高聚物,特别是聚烯烃,是特别有用的。在这方面,式Ⅰ化合物作为加工稳定剂(热稳定剂)的优良作用特别值得一提。为此目的,式Ⅰ化合物可在高聚物加工前或加工过程中方便地加入。
但是它也可稳定别的高聚物(例如高弹体)或润滑剂和液压流体使免于遭受降解反应,诸如光诱导和/或热氧化降解。高弹体的实例可在以上列出的可能的有机物中找到。
适当的润滑剂和液压流体可基于矿物或合成的油脂或它们的混合物,润滑剂对于技术熟练的人员是已知的,並在有关的技术文献中叙述过,例如可参看Dieter klamann所著的“Schmierstoff(“润滑剂和有关产物”)一书,Verlag Chemie,Weinheim,1982;Schewe-Kobek所著的“Das Schmiermittel-Taschenbuch”(“润滑剂手册”),Dr.Alfred Hüthig-Verlag,Heidelberg,1974;以及“Ullmanns Enzyklop
die der technischen Chemie”(“Ullmann工业化学大全”)第13卷第85-94页(Verlag Chemie,Weimheim,1977)。
本发明还涉及保护有机物免遭氧化,热和/或光诱导的降解反应的方法,它包括往所说的有机物中掺入或施用至少一种式Ⅰ化合物作为稳定剂。
除含有这些新化合物以外,本发明的组合物中还可包含其它通常使用的添加剂,特别是当组合物中包含有机的、最好是合成的高聚物时。
这类进一步的添加剂的作为说明性的实例有:
1.抗氧剂
1.1.烷基化的一元酚,例如2,6-二叔丁基-4-甲基酚、2-叔丁基-4,6-二甲基酚、2,6-二叔丁基-4-乙基酚、2,6-二叔丁基-4-丁基酚、2,6-二叔丁基-4-异丁基酚、2,6-二环戊基-4-甲基酚、2-(α-甲基环己基)-4,6-二甲基酚、2,6-双一十八烷基-4-甲基酚、2,4,6-三环己基酚、2,6-二叔丁基-4-甲氧基甲基酚、2,6-二壬基-4-甲基酚、2,4-二甲基-6-(1′-甲基-十一-1′-基)酚、2,4-二甲基-6-(1′-甲基十七-1′-基)酚、2,4-二甲基-6-(1′-甲基十三-1′-基)酚以及它们组成的混合物。
1.2.烷基硫甲基酚,例如2,4-二辛基-硫甲基-6-叔丁基酚、2,4-二辛基-硫甲基-6-甲基酚、2,4-二辛基硫甲基-6-乙基酚、2,6-双十二烷基硫甲基-4-壬基酚。
1.3.氢醌和烷基化的氢醌,例如2,6-二叔丁基-4-甲氧基酚、2,5-二叔丁基-氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基酚、2,6-叔丁基氢醌、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。
1.4.羟基化的硫代二苯基醚,例如2,2′-硫代双(6-叔丁基-4-甲基酚)、2,2′-硫代双(4-辛基酚)、4,4′-硫代双(6-叔丁基-3-甲基酚)、4,4′-硫代双(6-叔丁基-2-甲基酚)、4,4′-硫代双-(3,6-二-第二戊基酚)、4,4′-双-(2,6-二甲基-4-羟基苯基)二硫化物。
1.5.亚烷基双酚,例如2,2′-亚甲基双(6-叔丁基-4-甲基酚)、2,2′-亚甲基双(6-叔丁基-4-乙基酚)、2,2′-亚甲基双[4-甲基-6-(α-甲基环己基)酚]、2,2′-亚甲基双(4-甲基-6-环己基酚)、2,2′-亚甲基双(6-壬基-4-甲基酚)、2,2′-亚甲基双(4,6-二叔丁基酚)、2,2′-亚乙基双(4,6-二叔丁基酚)、2,2′-亚乙基双(6-叔丁基-4-异丁基酚)、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(2,6-二叔丁基酚)、4,4′-亚甲基双(6-叔丁基-2-甲基酚)、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。
1.6.O-,N,和S-苄基化合物,例如3,5,3′,5′-四叔丁基-4,4′-二羟基二苄醚、十八烷基-4-羟基-3,5-二甲基苄基巯基醋酸酯、三-(3,5-二叔丁基-4-羟基苯基)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、异辛基-3,5-二叔丁基-4-羟基苄基巯基醋酸酯。
1.7.羟基苄基化的丙二酸酯,例如双十八烷基-2.2-双-(3,5-二叔丁基-2-羟基苄基)-丙二酸酯、双十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)-丙二酸酯、双十二烷基巯基乙基-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。
1.8.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)酚。
1.9.三嗪类化合物,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-羟基苯乙基)-1,3,5-三嗪、1,3,5-三-(3,5-二叔丁基-4-羟基苯丙基)-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。
1.10.苄基膦酸酯,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、双十八烷基-3,5-二叔丁基-4-羟基苄基膦酸酯、双十八烷基-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。
1.11.酰胺基酚类,例如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。
1.12.β-(3,5-二叔丁基-4-羟基苯基)丙酸与一元和多元醇所形成的酯,例如与甲醇、乙醇、十八碳烷醇、1,6-己二醇、1,9壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷等所形成的酯。
1.13.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、十八碳烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、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-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷等所形成的酯。
1.14.β-(3,5-二环己基-4-羟基苯基)丙酸与一元或多元醇形成的酯,例如与甲醇、乙醇、十八碳烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、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-羟甲基-1-磷杂-2,6,7-三氧杂-双环[2.2.2]辛烷等所形成的酯。
1.15.3,5-二叔丁基-4-羟基苯乙酸与一元或多元醇形成的酯,例如和甲醇、乙醇、十八碳烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N′-双(羟乙基)草酰胺、3-硫代十一醇、3-硫代十五烷醇、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]辛烷等所形成的酯。
1.16,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-双叔丁基-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。
2.紫外光吸收剂和光稳定剂
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′-第二丁基-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-辛氧羰乙基)苯基)-5-氯-苯并三唑、2-(3′-叔丁基-5′[2-(2-乙基己氧)-羰乙基]-2′-羟基苯基-5-氯苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧羰乙基)苯基-5-氯-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-甲氧羰乙基)苯基)-苯并三唑、2-(3′-叔丁基-2′-羟基-5′-(2-辛氧羰乙基)苯基)苯并三唑、2-(3′-叔丁基-5′-[2-(2-乙基己氧)羰乙基]-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、以及2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧羰乙基)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]所组成的混合物;2-[3′-叔丁基-5′-(2-甲氧基羰乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300进行酯交换反应的产物;[R-CH2CH2-COO(CH2)3]2,其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基苯基。
2.2.2-羟基二苯酮类,例如4-羟基、4-甲氧基一、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.取代和未取代的苯甲酸酯类,例如水杨酸4-叔丁基-苯基酯、水杨酸苯基酯、水杨酸辛基苯基酯、二苯甲酰基间苯二酚、双(4-叔丁基苯甲酰基)间苯二酚、苯甲酰间苯二酚、3,5-二叔丁基-4-羟基苯甲酸2,4,-二叔丁基苯基酯、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-叔丁基苯基酯。
2.4.丙烯酸酯类,例如α-氰-β,β-二苯基丙烯酸乙酯、α-氰-β,β-二苯基丙烯酸异辛酯、α-羰甲氧基肉桂酸甲酯、α-氰-β-甲基-对-甲氧基-肉桂酸甲酯、α-氰-β-甲基-对-甲氧基肉桂酸丁酯、α-羰甲氧基-对-甲氧基肉桂酸甲酯和N-(β-羰甲氧基-β-氰乙烯基)-2-甲基二氢吲哚。
2.5.镍化合物,例如2,2′-硫代-双-[4-(1,1,3,3-四甲基丁基)苯酚的镍络合物,诸如1∶1或1∶2的络合物,带有或没有另外的配体,诸如正丁胺、三乙醇胺或N-环己基二乙醇胺、二丁基二硫代氨基甲酸酯镍、单烷基酯的镍盐,例如4-羟基-3,5-二叔丁基苄基磷酸甲酯或乙酯的镍盐,酮肟的镍络合物,例如2-羟基-4-甲基苯基十一烷基酮肟的镍络合物、1-苯基-4-月桂酰基-5-羟基吡唑的镍络合物,带有或没有另外的配体。
2.6.空间阻碍胺类,例如双(2,2,6,6-四甲基哌啶基)癸二酸酯、双(2,2,6,6-四甲基-哌啶基)丁二酸酯、双(1,2,2,6,6-五甲基哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基哌啶基)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-羟基哌啶和丁二酸的缩合物、N,N′-双(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺和4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三醋酸酯、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-硬脂酰氧-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)丁二酸酯、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-1,3,5-三嗪的缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶)-1,3,5-三嗪和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)-1,3,5-三嗪和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-2,4-二酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)四氢吡咯-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)四氢吡咯-2,5-二酮。
2.7.草酰胺类,例如4,4′-二辛氧基草酰苯胺,2,2′-二辛氧基-5,5′-二叔丁氧草酰苯胺、2,2′-双十二烷氧基-5,5′-二叔丁氧草酰苯胺、2-乙氧基-2′-乙氧草酰苯胺、N,N′-双(3-二甲氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2′-乙氧草酰苯胺以及它和2-乙氧基-2′乙基-5,4′-二叔丁氧草酰苯胺、邻位和对位甲氧基-二取代的草酰苯胺的混合物和邻位和对位乙氧基-二取代的草酰苯胺的混合物。
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-(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。
3.金属减活化剂,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-羟基苯丙酰基)肼、3-水杨酰氨基-1,2,4-三唑、双(亚苄基)草酰基-二酰肼、草酰苯胺、间苯二甲酰二酰肼、癸二酰双苯酰肼,N,N′-二缩乙醛己二酰二酰肼、N,N′-双(水杨酰)草酰基-二酰肼、N,N′-双(水杨酰)-硫代丙酰基-二酰肼。
4.其他的亚膦酸酯和膦酸酯,例如亚膦酸三苯酯、烷基亚膦酸二苯酯、二烷基亚膦酸苯酯、亚膦酸三(壬基苯基)酯、亚膦酸三月桂酯、亚膦酸三(十八烷基)酯、季戊四醇二亚膦酸二(十八烷基)酯、亚膦酸三(2,4-二叔丁基苯基)酯、季戊四醇二亚膦酸二异癸基酯、双(2,4-二叔丁基苯基)季戊四醇二亚膦酸酯、双(2,6-二叔丁基-4-甲基苯基)-季戊四醇二亚膦酸酯、二异癸氧基季戊四醇二亚膦酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚膦酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚膦酸酯、山梨醇三亚膦酸三(十八烷基)酯、四(2,4-二叔丁基苯基)4,4′-亚联苯基-二膦酸酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d.g]-1,3,2-二氧膦杂环己烷、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d.g]-1,3,2-二氧膦杂环己烷、双(2,4-二叔丁基-6-甲基苯基)甲基亚膦酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚膦酸酯。
5.过氧化物净化剂,例如β-硫代丙酸的酯类,如月桂酯、十八碳醇酯、十四碳醇酯、十三碳醇酯、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(十八碳烷基)二硫化物、季戊四醇四(β-十二烷基巯基)丙酸酯。
6.聚酰胺稳定剂,例如与碘化物结合一起的铜盐和/或磷化合物以及两价锰盐。
7.碱性助稳定剂,例如蜜胺、聚乙烯四氢吡咯烷酮、双氰胺、三烯丙基氰脲酸酯、尿素衍生物、肼衍生物、胺类、聚酰胺类、聚氨基甲酸酯类、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、山嵛酸镁、硬脂酸镁、蓖麻酸钠和软脂酸钾,焦性儿茶酸锑或焦性儿茶酸锌。
8.成核剂,例如,4-叔丁基苯甲酸、己二酸、二苯基醋酸。
9.填充剂和增强剂,例如,碳酸钙、硅酸盐、玻璃纤维、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。
10.其它添加剂,例如增塑剂、润滑剂、乳化剂、颜料、荧光增白剂、防火剂、抗静电剂和发泡剂。
11.苯并呋喃酮和二氢吲哚酮类,例如那些在美国专利US-A-4325863或US-A-4338244中公开过的这类化合物。
作为进一步的稳定剂,最好是用抗氧剂、光稳定剂和加工稳定剂。按此,本发明特别有关于那些包含抗氧剂、光稳定剂或加工稳定剂作为进一步的稳定剂的组合物。特别优选的组合物是那些含有酚类,阻碍胺类(HALS)和含硫增效剂和/或含磷化合物作为进一步稳定剂的那些组合物。
下面的实例更详细地说明了本发明,在权利要求和描述部分的主要正文中,除非另外指明,所用的百分数均为重量百分数。
实例1:把23.8克1,1-双(4-羟基-3-叔丁基苯基)环己烷和19.2毫升三乙胺溶解在360毫升甲苯中,在搅拌下以及冷却至10℃以后,往这溶液中慢慢滴加23.4克2-氯-5.5-二甲基-1,3-二氧膦杂环己烷,反应混合物在10℃保持搅拌1小时。然后过滤除去三乙胺盐酸盐,溶液蒸发浓缩,残余物在100℃溶解于100毫升石油醚中,进一步过滤并冷却到5℃,抽吸过滤出产物,在减压下于五氧化二磷的保干器中干燥,得到31.65克具有下式的化合物:
熔点140-145℃。
元素分析:%C %H %P
计算值:67.06 8.44 9.61
实验值:67.03 8.40 9.56
实例2-10:化合物2至5和7至10是按照实例1中所叙述的方法制备的。化合物6的制备方法基本与实例1的方法一致,除了用与酚羟基相同的化学计量比例的丁基锂作为碱。得到的这些化合物的结构式和特征值总结于表1中。
实例11:经多次挤压的聚丙烯的稳定化
把具有在230°/216公斤条件下测量并列于表2中的熔体指数的1.3公斤聚丙烯粉末(Propathene
HF24,Moplen
FL S20,Prcfax
6501)与0.05%的Irganox
1010(即四-[3-(3.5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯),0.05%的硬脂酸钙,表2中指出的那么多量的水滑石[DHT 4A
,Kyowa化学工业公司产品,成份为Mg4.5Al2(OH)13CO3·3.5H2O]以及0.05%的表1中所列的化合物掺和在一起。然后把这混合物在一台柱直径为20毫米,长度400毫米的挤压机中,于每分钟100转,三个加热区温度调节在260℃,270℃,280℃的条件下进行挤压。通过把压出物拉过水浴而使之冷却,然后成粒。这颗粒被重复挤压,在加工过程中联机测量它的熔体指数,并相应于可方便地在230℃/2.16公斤/10分钟条件下测量的值。熔体指数的大量增高指示显著的链降解,即稳定性很差,实验结果列于表2中。
Irganox
1076=3-[3,5-二叔丁基-4-羟苯基]丙酸正十八烷基酯
实例12:试验加工过程中聚缩醛类对泛黄作用的稳定性
把100份聚缩醛粉末(Hostaform
C)与0.3份硬脂酸钙,表3中指出的那么多量的Irganox
1010(即四-[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯)以及表1中所列的化合物1掺合在一起,混合物在190℃/30rpm条件下在一台Brabender塑度表中捏和7分钟,然后把经捏和的物料压缩成1毫米的板,板块的泛黄指数(YI)被用作稳定作用的参考值(按照ASTM D-1925-70的方法测量),低的YI值指示没有明显的泛黄作用,高的YI值指示强的泛黄作用。泛黄作用愈小表示稳定剂愈有效。结果报告于表3中。
表3:加工过程中聚缩醛对泛黄作用的稳定性
每100份聚缩醛 每100份聚缩醛中化合物1 泛黄指数
中Irganox (表1)的份数 (YI)
1010的份数
0.3 - 7.25
- 0.3 2.25
0.25 0.05 3.3
Claims (20)
1、一种式Ⅰ化合物:
其中n是0、1或2,
R和R1可彼此独立地是C1-C4烷基,或者它们在一起组成2,3-去氢-1,5-亚戊基,
R2和R3可彼此独立地是氢,C1-C4烷基或C5-C6环烷基,并且
如果n=1,R4,R5,R6,R7可彼此独立地是氢或C1-C4烷基,或者,如果n=0以及如果n=2,则它们都是氢。
2、一种权利要求1的化合物,其中的n是1或2。
3、一种权利要求1的化合物,其中R2和R3彼此独立地是氢,C1-C4烷基或环己基。
4、一种权利要求1中的化合物,其中n=1。
5、一种权利要求1中的化合物,其中n=1,R4是氢,R5,R6,R7彼此独立地是氢或甲基。
6、一种权利要求1中的化合物,其中R2和R3彼此独立地是氢、甲基、丁基或环己基。
7、一种权利要求1的化合物,其中R2和R3彼此独立地是氢、甲基或叔丁基。
8、一种权利要求1的化合物,其中R5,R6,R7是氢,R4是氢或叔丁基。
9、一种权利要求1的化合物,其中R4,R5,R6和R7是氢。
10、一种权利要求1的化合物,其中R和R1彼此独立地是甲基或丁基,或它们在一起组成一个2,3-去氢-1,5-亚戊基。
11、一种组合物,它包含(a):一种对氧化,热或光诱导的降解敏感的有机物,(b):至少一种本发明的式Ⅰ化合物。
12、一种权利要求11的组合物,其中的组份(a)是一种天然的、半合成的或合成的高聚物。
13、一种权利要求11的组合物,其中的组份(a)是一种热塑性高聚物。
14、一种权利要求11的组合物,其中的组份(a)是一种聚烯烃或聚氧乙烯。
15、一种权利要求11的组合物,其中的组份(a)是聚乙烯或聚丙烯。
16、一种权利要求11的组合物,其中除组份(a)和(b)以外还含有一种抗氧剂,一种光稳定剂和一种加工稳定剂。
17、应用权利要求1的化合物作为使有机物防止氧化、热降解或光降解的稳定剂。
18、应用权利要求1的化合物作为热塑性高聚物,尤其是聚烯烃的加工稳定剂。
19、一种防止有机物氧化,热降解或光降解的方法,它包括往所说的有机物中掺入或施用至少一种式Ⅰ化合物作为稳定剂。
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CH14992 | 1992-01-21 | ||
CH149/92-0 | 1992-01-21 |
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CN1075968A true CN1075968A (zh) | 1993-09-08 |
Family
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CN93100816A Pending CN1075968A (zh) | 1992-01-21 | 1993-01-20 | 新型亚膦酸环亚烷基双酚酯 |
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US (1) | US5280057A (zh) |
EP (1) | EP0553059B1 (zh) |
JP (1) | JPH0625271A (zh) |
KR (1) | KR930016432A (zh) |
CN (1) | CN1075968A (zh) |
AT (1) | ATE143966T1 (zh) |
AU (1) | AU656255B2 (zh) |
BR (1) | BR9300218A (zh) |
CA (1) | CA2087582A1 (zh) |
CZ (1) | CZ5093A3 (zh) |
DE (1) | DE59304064D1 (zh) |
ES (1) | ES2095025T3 (zh) |
MX (1) | MX9207621A (zh) |
SK (1) | SK1393A3 (zh) |
TW (1) | TW260688B (zh) |
ZA (1) | ZA93380B (zh) |
Families Citing this family (6)
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US6124230A (en) * | 1995-07-13 | 2000-09-26 | Exxon Chemical Patents, Inc. | Polymerization catalyst systems, their production and use |
US6140432A (en) * | 1995-07-13 | 2000-10-31 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
TW338046B (en) * | 1995-06-29 | 1998-08-11 | Ciba Sc Holding Ag | Process for the preparation of stabilized olefin polymers |
US5594053A (en) * | 1996-01-22 | 1997-01-14 | General Electric Company | Aromatic cyclic bisphosphite esters and polymeric compositions thereof |
US8142864B2 (en) * | 2007-01-25 | 2012-03-27 | Konica Minolta Opto, Inc. | Cellulose ester pellets, cellulose ester film, manufacturing method of cellulose ester film, polarizing plate, and liquid crystal display |
US8466096B2 (en) * | 2007-04-26 | 2013-06-18 | Afton Chemical Corporation | 1,3,2-dioxaphosphorinane, 2-sulfide derivatives for use as anti-wear additives in lubricant compositions |
Family Cites Families (15)
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US2883365A (en) * | 1955-03-01 | 1959-04-21 | Goodrich Co B F | Sulfur vulcanizable rubber and 1,1-bis(4-hydroxy phenyl) cycloalkane |
US2894004A (en) * | 1956-08-13 | 1959-07-07 | Dow Chemical Co | Bisphenols |
US3039993A (en) * | 1960-05-10 | 1962-06-19 | Weston Chemical Corp | Polyethylene stabilizers |
DE1237312B (de) * | 1961-06-27 | 1967-03-23 | Pure Chem Ltd | Formmassen aus Polymerisaten von Olefinen |
FR1384809A (fr) * | 1963-11-28 | 1965-01-08 | Kuhlmann Ets | Nouveaux esters phosphoreux, procédé pour leur fabrication et applications desdits esters |
US3467733A (en) * | 1965-11-26 | 1969-09-16 | Hooker Chemical Corp | Cyclic esters of phosphorus and a process for the preparation thereof |
US3441633A (en) * | 1965-12-03 | 1969-04-29 | Weston Chemical Corp | Cyclic phosphites |
US3491157A (en) * | 1968-01-11 | 1970-01-20 | Dow Chemical Co | Cycloalkylidenebis(cycloalkylphenols) |
US3655832A (en) * | 1969-02-18 | 1972-04-11 | Argus Chem | Polycarbocyclic phenolic phosphites |
US3856728A (en) * | 1971-04-26 | 1974-12-24 | Argus Chem | Acrylonitrile-butadiene-styrene polymers having improved resistance to discoloration |
US4206111A (en) * | 1977-05-06 | 1980-06-03 | Borg-Warner Corporation | Stabilized polyolefins |
GB2044272B (en) * | 1979-02-05 | 1983-03-16 | Sandoz Ltd | Stabilising polymers |
US4312803A (en) * | 1979-03-16 | 1982-01-26 | General Electric Company | Thermally stable polycarbonate compositions |
JPS5692934A (en) * | 1979-12-26 | 1981-07-28 | Adeka Argus Chem Co Ltd | Synthetic resin composition |
US4463112A (en) * | 1980-02-13 | 1984-07-31 | Leistner William E | Phenylethylidene-substituted phenyl polyphosphites |
-
1992
- 1992-12-30 MX MX9207621A patent/MX9207621A/es unknown
-
1993
- 1993-01-12 ES ES93810013T patent/ES2095025T3/es not_active Expired - Lifetime
- 1993-01-12 DE DE59304064T patent/DE59304064D1/de not_active Expired - Fee Related
- 1993-01-12 AT AT93810013T patent/ATE143966T1/de not_active IP Right Cessation
- 1993-01-12 EP EP93810013A patent/EP0553059B1/de not_active Expired - Lifetime
- 1993-01-13 TW TW082100164A patent/TW260688B/zh active
- 1993-01-13 US US08/004,147 patent/US5280057A/en not_active Expired - Fee Related
- 1993-01-15 AU AU31841/93A patent/AU656255B2/en not_active Ceased
- 1993-01-18 SK SK1393A patent/SK1393A3/sk unknown
- 1993-01-19 CA CA002087582A patent/CA2087582A1/en not_active Abandoned
- 1993-01-19 BR BR9300218A patent/BR9300218A/pt not_active Application Discontinuation
- 1993-01-20 CN CN93100816A patent/CN1075968A/zh active Pending
- 1993-01-20 CZ CZ9350A patent/CZ5093A3/cs unknown
- 1993-01-20 ZA ZA93380A patent/ZA93380B/xx unknown
- 1993-01-21 KR KR1019930000853A patent/KR930016432A/ko not_active Application Discontinuation
- 1993-01-21 JP JP5026090A patent/JPH0625271A/ja active Pending
Also Published As
Publication number | Publication date |
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AU656255B2 (en) | 1995-01-27 |
ATE143966T1 (de) | 1996-10-15 |
KR930016432A (ko) | 1993-08-26 |
BR9300218A (pt) | 1993-07-27 |
SK1393A3 (en) | 1993-09-09 |
AU3184193A (en) | 1993-07-22 |
TW260688B (zh) | 1995-10-21 |
MX9207621A (es) | 1993-07-01 |
EP0553059A1 (de) | 1993-07-28 |
JPH0625271A (ja) | 1994-02-01 |
ZA93380B (en) | 1993-07-21 |
EP0553059B1 (de) | 1996-10-09 |
CA2087582A1 (en) | 1993-07-22 |
US5280057A (en) | 1994-01-18 |
CZ5093A3 (en) | 1993-10-13 |
ES2095025T3 (es) | 1997-02-01 |
DE59304064D1 (de) | 1996-11-14 |
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