CN1615335B - 协同性稳定剂混合物的制备方法 - Google Patents
协同性稳定剂混合物的制备方法 Download PDFInfo
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- CN1615335B CN1615335B CN038021994A CN03802199A CN1615335B CN 1615335 B CN1615335 B CN 1615335B CN 038021994 A CN038021994 A CN 038021994A CN 03802199 A CN03802199 A CN 03802199A CN 1615335 B CN1615335 B CN 1615335B
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- Prior art keywords
- tert
- bis
- compound
- butyl
- weight
- Prior art date
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- 150000001875 compounds Chemical class 0.000 claims abstract description 46
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- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
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- YEWBOZCFGXOUQW-UHFFFAOYSA-N 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-ylmethanol Chemical compound C1OP2OCC1(CO)CO2 YEWBOZCFGXOUQW-UHFFFAOYSA-N 0.000 description 5
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
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Abstract
本发明描述一种用于制备含有如下通式(I)、(II)和(III)组分的协同性稳定剂混合物的方法,所述混合物包含分数为65-95重量%的化合物(I),分数为5至35重量%的化合物(II),以及分数为0至10重量%的化合物(III),其特征为,在相转移反应中,将式(V)的化合物与式(VI)的表卤代醇反应
Description
技术领域
本发明涉及一种用于制备基于多烷基-1-氧杂二氮杂螺癸烷化合物的协同性稳定剂混合物的方法。
众所周知有机材料会由于光、辐射、热或氧而损坏。
目前已有许多文献公开了用于将有机材料相对光与热效应稳定化的化合物。其中有些文献涉及基于2,2,6,6-四烷基哌啶的化合物。为了提供有效的保护,这些稳定剂必须以足够浓度存在,特别是在有机材料的暴露部位。
2,2,6,6-四烷基哌啶类的低分子量代表具有快速迁移到特别遭受损坏性影响的部位的优点,在此部位它们展现其保护性作用。然而,它们也有缺点,即其挥发性太高且很容易从有机材料中萃取出。
虽然此类化合物的较高分子量代表并不易于萃取,但却有迁移较慢的缺点。在本领域内,此问题经常通过使用一种由低(快速迁移)分子量稳定剂与高(缓慢迁移)分子量稳定剂组成的混合物而加以解决。
因此,已知有相当大量的基于空间位阻胺的稳定剂混合物,它们在很大程度上没有或完全没有上述的缺点。
作为代表性例子,可提及例如下列文献中所述的混合物:US4,692,486、US4,863,981、US4,957,953、US5,980,783、WO92/12201、WO94/22946、EP449685A、EP623092A、GB2267499A,以及Research Disclosure No.34549(1993年1月)。
尽管如此,对能给予有机材料提高的光稳定性或使用性能的新型、更有效力的稳定剂混合物一直有很高的需求。
US6,174,940公开了基于多烷基-1-氧杂二氮杂螺癸烷化合物的如下通式(I)、(II)和(III)的协同性稳定剂混合物,其中化合物(I)是以分数65-95重量%存在,优选为75至94重量%,特别是85至94重量%,化合物(II)的分数是5至35重量%,优选为5至20重量%,特别是5至12重量%,而化合物(III)的分数则为0至10重量%,优选为1至5重量%,特别是1至3重量%,
其中
n和m互相独立地表示0至100的数,但两者不能都为0,
R1表示氢、C5-C7环烷基或C1-C12烷基,
R2和R3互相独立地表示氢原子,C1-C18烷基,或是与连接它们的碳原子一起构成一个5至13元环,或者与将它们接合在一起的碳原子一起构成式(IV)的基团
R4和R5互相独立地表示氢或C1-C22烷基,氧自由基O*、-OH、-NO、 -CH2CN、苄基、烯丙基、C1-C30烷氧基、C5-C12环烷氧基、C6-C10芳氧基(其中芳基也可进一步被取代)、C7-C20芳基烷氧基(其中芳基也可进一步被取代)、C3-C10链烯基、C3-C6炔基、C1-C10酰基、卤素或是未经取代的苯基或经C1-C4烷基取代的苯基。
同样地,该混合物的各个组分的制备也已公开于US6,174,940,或者就此可参考出版物EP705 836 A、EP690 060 A和EP 057 885A。
在US6,174,940中,所公开的混合物是通过将组分(I)、(II)和适当情况下还有(III)按所需的比例组合而制备。
例如,此操作可在粉末混合器中进行,在此混合器中这些物质是以干燥形式混合。额外地或可选择地,此粉末混合物可通过熔融而均化,必要时在氮气下进行。该混合操作也可借助于溶剂来进行,此溶剂在这些组分已均化而形成溶液后再通过蒸发除去。
这种用于制备组分(I)、(II)和(III)的混合物的步骤有其决定性的缺点,即费时、复杂且昂贵,因为每一个别的组分必须首先单独制备,然后,在另一个物理过程的操作中必须以准确的协同性的比例混合。
目前已令人惊奇地发现,前述的组分(I)、(II)和(III)的混合物可通过巧妙的反应方式原位制备,也就是说,无另外的物理过程操作。
因此,本发明提供一种用于制备含有前述的通式(I)、(II)和(III)组分的协同性混合物的新型方法,其中,该混合物包含分数为65-95重量%,优选为75至94重量%,特别是85至94重量%的化合物(I),分数为5至35重量%,优选为5至20重量%,特别是5至12重量%的化合物(II),以及分数为0至10重量%,优选为1至5重量%,特别是1至3重量%的化合物(III),
其中
n和m互相独立地表示0至100的数,但两者不能都为0,
R1表示氢、C5-C7环烷基或C1-C12烷基,
R2和R3互相独立地表示氢原子,C1-C18烷基,或是与连接它们的碳原子一起构成一个5至13元环,或者与将它们接合在一起的碳原子一起构成如式(IV)的基团,
以及其中
R4和R5互相独立地表示氢或C1-C22烷基,氧自由基O*、-OH、-NO、-CH2CN、苄基、烯丙基、C1-C30烷氧基、C5-C12环烷氧基、C6-C10芳氧基(其中芳基也可进一步被取代)、C7-C20芳基烷氧基(其中芳基也可进一步被取代)、C3-C10链烯基、C3-C6炔基、C1-C10酰基、卤素或是未经取代的苯基或经C1-C4烷基取代的苯基。
优选的混合物中
n和m互相独立地表示0至10的数,但两者不能都为0,
R1表示氢、C6环烷基或C1-C4烷基,
R2和R3互相独立地表示氢原子,C1-C18烷基,或是与连接它们的碳原子一起构成一个6至12元环,或者与将它们接合在一起的碳原子一起构成如式(IV)的基团,
R4和R5互相独立地表示氢或C1-C5烷基,氧自由基O*、-OH、-NO、-CH2CN、苄基、烯丙基、C1-C10烷氧基、C5-C6环烷氧基、C6-C7芳氧基(其中芳基也可进一步被取代)、C7-C10芳烷氧基(其中芳基也可进一步被取代)、C3-C6链烯基、C3-C6炔基、C1-C4酰基、卤素或是未经取代的苯基或经C1-C2烷基取代的苯基。
特别优选的混合物中
n和m互相独立地表示0至5的数,但两者不能都为0,
R1表示甲基,
R2和R3与连接它们的碳原子一起构成一个12元环,或者与将它们接合在一起的碳原子一起构成如式(IV)的基团,以及
R4和R5互相独立地表示氢、甲基、乙酰基、辛氧基或环己氧基。
组分(I)、(II)和(III)的协同性混合物通过将通式(V)的化合物
(其中R1、R2、R3和R4如上所定义,而R6 -表示元素周期表(PTE)中第(V)、(VI)或(VII)主族的质子酸的阴离子,优选衍生自PTE的第(VII)主族),与下式(VI)的表卤代醇反应而制得,
其中X表示卤素原子,特别是氯、溴或碘原子。
例如,衍生自PTE中第(V)和(VI)主族的质子酸的阴离子是含氧酸的阴离子,例如硫酸氢根、硫酸根、硝酸根、磷酸氢根和磷酸根。衍生自PTE中第(VII)主族的质子酸的阴离子例如有氟离子、氯离子、溴离子和碘离子,特别优选氯阴离子。
将化合物(V)和(VI)在相转移催化剂存在下在惰性有机溶剂中以1∶1至1∶2.9的摩尔比预混合。然后,在4至20倍摩尔量(相对于式(V)化合物的摩尔量)的碱金属氢氧化物存在下,在有机溶剂中,使用相转移催化剂将该预混合物反应生成所需的组分(I)、(II)和(III)的协同性混合物。
碱金属氢氧化物可以固体形式使用或作为具有重量比为9∶1至1∶9(水的份数对碱金属氢氧化物的份数)的水溶液形式使用。
合适的式(V)的化合物有:
2-异丙基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-丁基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异丁基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-戊基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-己基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-庚基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异庚基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异辛基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-壬基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异壬基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5] 癸烷,
2-苯基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-(4-氯苯基)-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2,2-二甲基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-乙基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-丙基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异丙基-6,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-丁基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-异丁基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-戊基-6,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-己基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-壬基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2,2-二乙基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2,2-二丙基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2,2-二丁基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2-乙基-2-戊基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺 [4.5]癸烷,
2,2-二苄基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧代螺[4.5]癸烷,
2,2,4,4-四甲基-7-氧杂-3,12-二氮杂-14-氧代二螺[5.1.4.2]十四烷,
2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代二螺[5.1.11.2]二十一烷,
2,2,4,4-四甲基-7-氧杂-3,14-二氮杂-15-氧代二螺[5.5.5.2]十五烷,
2,2,4,4,10,10,12,12-八甲基-7-氧杂-3,11,14-三氮杂-15-氧代二螺[5.1.5.2]十五烷,
2-乙基-2,7,7,9,9-五甲基-1-氧杂-3,8-二氮杂-4-氧代-8-烃氧基螺[4.5]癸烷。
阴离子R6 -如上文所定义,是衍生自PTE中第(V)、(VI)或(VII)主族的质子酸的阴离子,优选衍生自PTE的第(VII)主族,特别优选为氯离子。
用作起始产品的多烷基氧杂二氧杂螺癸烷原则上是已知的,并可根据US4,110,334和US4,107,139中给出的指示而获得。
在化合物(V)中特别优选2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代二螺[5.1.11.2]二十一烷盐酸盐。
优选的式(VI)的表卤代醇是表氯醇。
式(V)与式(VI)的化合物以摩尔比1∶1至1∶2.9,优选1∶1至1∶2.7,特别是1∶2至1∶2.5反应。
该反应在4-20倍摩尔量(相对于式(V)的化合物)的碱金属氢氧化物存在下,在惰性有机溶剂中进行,该碱金属氢氧化物以固体碱金属氢氧化物形式,或以相应量的碱金属氢氧化物水溶液形式,该水溶液的重量比为9∶1至1∶9,优选2∶3至4∶1,特别是1∶1至7∶3(碱金属氢氧化物的份数对水的份数)。
反应温度在20至220℃范围内,优选为40至120℃,特别是60至90℃。
例如,优选的惰性有机溶剂是脂族或芳族烃,例如石油醚、己烷、庚烷、石油馏份、甲苯、环己烷、1,3,5-三甲基苯或二甲苯。特别优选芳族烃,特别是二甲苯。
惰性有机溶剂优选以重量比2∶1至1∶5,更优选2∶1至1∶3,特别是2∶1至1∶2,相对于化合物(V),而使用。
所用的相转移催化剂是聚乙二醇,优选具有平均低聚程度的聚乙二醇,特别是聚乙二醇200,而其定量比例为1.5至10重量%,优选3至7重量%,特别是4-6重量%,相对于所用式(V)的化合物的量。
反应一般在30至60分钟后结束。
反应后,过量的表卤代醇优选通过蒸馏而从反应混合物中除去。在除去表卤代醇期间,一些或全部的惰性有机溶剂也可能被除去,在此情况下,在相分离前必须以适当量补足惰性有机溶剂。
分离有机相和水相;用水洗涤有机相,再优选通过蒸馏除去惰性有机溶剂。
所得的粘稠预混合物无需进一步的纯化步骤,即可通过在100至240℃,优选在120-220℃,特别是150-200℃下加热,优选在减压下,转化成所需的式(I)、(II)和(III)的混合物。
通过改变所用的式(V)化合物的量、表卤代醇(VI)的量、所用的碱金属氢氧化物的量以及所用的聚乙二醇相转移催化剂的量,可以在宽范围内改变组分(I)、(II)和(III)的混合物的组成。
该混合物(组分(I)、(II)和(III))的组成可通过常规的光谱法(IR和13C-NMR光谱)来表明。
聚合后,该反应混合物可非必要地通过已知的方法在R4位置上被衍生。
通过本发明方法制备的式(I)、(II)和(III)的混合物适合用作如下面举例列出的有机材料中的光稳定剂。
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚异戊二烯或聚丁二烯,还有环烯烃的聚合物,如环戊烯或降冰片烯的聚合物;另外有聚乙烯(可非必要地被交 联),如高密度聚乙烯(HDPE)、高密度且高摩尔质量的聚乙烯(HDPE-HMW)、高密度且超高摩尔质量的聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、支化低密度聚乙烯(BLDPE)。
聚烯烃,即如前段所例举的单烯烃聚合物,特别是聚乙烯和聚丙烯,其可通过各种方法,尤其是通过下列的方法而制备:
a)自由基聚合反应(通常是在高压和高温下)
b)使用通常包含第IVb、Vb、VIb或VIII族的一种或多种金属的催化剂的催化聚合反应。这些金属通常具有一个或多个配体,如氧化物、卤化物、醇化物、酯、醚、胺、烷基、链烯基和/或芳基(其可以π-或σ-配位)。这些金属配合物可以游离形式或固定在基材(如活化的氯化镁、氯化钛(III)、氧化铝或二氧化硅)上。这些催化剂可以是可溶于或不溶于聚合介质中。这些催化剂可以如在聚合反应中那样为活性的,或者可以使用另外的活化剂,如金属烷基化物、金属氢化物、烷基金属卤化物、烷基金属氧化物或金属烷基噁烷,所述金属是周期表第Ia、IIa和/或IIIa族的元素。例如,活化剂可以用另外的酯、醚、胺或甲硅烷基醚基修饰。这些催化剂体系通常称为Phillips催化剂,Standard Oil Indiana催化剂,齐格勒(纳塔)催化剂,TNZ(杜邦)催化剂,茂金属催化剂或单活性中心催化剂(SSC)。
2.在1)中所提及的聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚乙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(如PP/PE-HD/PE-LD),以及不同类型的聚乙烯彼此间的混合物(如PE-LD/PE-HD)。
3.单烯烃与二烯烃彼此间的共聚物,或它们与其他乙烯基单体的共聚物,例如乙烯-丙烯共聚物,线性低密度聚乙烯(PE-LLD)和其与低密度聚乙烯(PE-LD)的混合物,丙烯-丁-1-烯共聚物、丙烯-异丁烯共聚物、乙烯-丁-1-烯共聚物、乙烯-己烯共聚物、乙烯-甲基戊烯共聚物、乙烯-庚烯共聚物、乙烯-辛烯共聚物、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-醋酸乙烯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),还有乙烯与丙烯以及二烯如己二烯、二环戊二烯或乙叉降冰片烯的三元共聚物;以及此类共聚物彼此间的混合物,和它们与1)中所提及的聚合物的混合物,例如聚丙烯-乙烯-丙烯共聚物、PE-LD-乙烯-醋酸乙烯酯共聚物、PE-LD-乙烯-丙烯酸共聚物、PE-LLD-乙烯-醋酸乙烯酯共聚物、PE-LLD-乙烯-丙烯酸共聚物,以及嵌段或无规的聚烷撑-一氧化碳共聚物以及它们与其他聚合物如聚酰胺的混合物。
4.烃树脂(如C5-C9),包括它们的氢化变体(如增粘剂树脂),以及聚烷撑与淀粉的混合物。
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-甲基苯乙烯与二烯或丙烯酸系衍生物的共聚物,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-甲基丙烯酸酯;高冲击强度苯乙烯共聚物与另一种聚合物(如聚丙烯酸酯、二烯聚合物或乙烯-丙烯-二烯三元共聚物)的混合物;以及苯乙烯的嵌段共聚物,如苯乙烯-丁二烯-苯乙烯、苯乙烯-异戊二烯-苯乙烯、苯乙烯-乙烯/丁烯-苯乙烯或苯乙烯-乙烯/丙烯-苯乙烯。
7.苯乙烯或α-甲基苯乙烯的接枝共聚物,例如苯乙烯接枝在聚丁二烯上、苯乙烯接枝在聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上、苯乙烯与丙烯腈(甲基丙烯腈)接枝在聚丁二烯上;苯乙烯、丙烯腈和甲基丙烯酸甲酯接枝在聚丁二烯上;苯乙烯和马来酸酐接枝在聚丁二烯上;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺接枝在聚丁二烯上;苯乙烯和马来酰亚胺接枝在聚丁二烯上;苯乙烯和丙烯酸烷基酯或甲基丙烯酸烷基酯接枝在聚丁二烯上,苯乙烯和丙烯腈接枝在乙烯-丙烯-二烯三元共聚物上,苯乙烯和丙烯腈接枝在聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上,苯乙烯和丙烯腈接枝在丙烯酸酯-丁二烯共聚物上,以及它们与6)中所提及的共聚物的混合物,如已知称为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素聚合物,如聚氯丁二烯、氯化橡胶、异丁烯-异戊二烯的氯化和溴化共聚物(卤代丁基橡胶)、氯化或磺基氯化聚乙烯、乙烯与氯化乙烯的共聚物、表氯醇均聚物和共聚物,特别是含卤素的乙烯基化合物的聚合物,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,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。
9.衍生自α,β-不饱和酸及其衍生物的聚合物,如聚丙烯酸酯和聚甲基丙烯酸酯、聚丙烯腈、聚丙烯酰胺和经丙烯酸丁酯抗冲改性的聚甲基丙烯酸甲酯。
10.在9)中所提及的单体彼此间或与其他不饱和单体的共聚物,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共聚物、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.衍生自不饱和醇和胺或酰基衍生物或是它们的缩醛的聚合物,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、聚乙烯醇缩丁醛、聚邻苯二甲酸烯丙酯或聚烯丙基三聚氰胺;以及它们与第1部分中提及的烯烃的共聚物。
12.环状醚的均聚物和共聚物,如聚烷撑二醇、聚氧化乙烯、聚氧化丙烯或它们与双缩水甘油醚的共聚物。
13.聚缩醛,如聚甲醛,以及那些含有共单体如氧化乙烯的聚甲醛;经热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
14.聚苯醚和聚苯硫醚,以及它们与苯乙烯聚合物或聚酰胺的混合物。
15.衍生自一方面是端羟基聚醚、聚酯和聚丁二烯和另一方面是脂族或芳族多异氰酸酯的聚氨酯,以及它们的前体。
16.衍生自二胺与二羧酸和/或衍生自氨基羧酸或相应的内酰胺的聚酰胺和共聚酰胺,例如聚酰胺4,6,6/6,6/10,6/9,6/12,4/6,12/12,11和12;起始于间-二甲苯、二胺和己二酸的芳族聚酰胺;从己二胺和间苯二甲酸和/或对苯二甲酸制备并具有或不具有弹性体作为改性剂的聚酰胺, 如聚-2,4,4-三甲基亚己基对苯二甲酰胺或聚间苯二甲酰间苯二胺。前述的聚酰胺与聚烯烃、烯烃共聚物、离聚物或是化学键合弹性体或接枝弹性体的嵌段共聚物;或者是前述的聚酰胺与聚醚如聚乙二醇、聚丙二醇或聚丁二醇的嵌段共聚物。另外,经用EPDM或ABS改性的聚酰胺或共聚酰胺;以及在加工(RIM聚酰胺体系)期间缩合的聚酰胺。
17.聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰胺、聚乙内酰脲和聚苯并咪唑。
18.衍生自二羧酸和二元醇和/或羟基羧酸或相应的内酯的聚酯,如聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚-1,4-二羟甲基环己烷对苯二甲酸酯、聚羟基苯甲酸酯,以及衍生自端羟基聚醚的嵌段聚醚-酯;还有经用聚碳酸酯或MBS改性的聚酯。
19.聚碳酸酯和聚酯碳酸酯。
20.聚砜、聚醚砜和聚醚酮。
21.衍生自一方面是醛,且另一方面是酚、脲或三聚氰胺的交联聚合物,例如酚/甲醛树脂、脲/甲醛树脂和三聚氰胺/甲醛树脂。
22.干燥和未干燥的醇酸树脂。
23.衍生自饱和和不饱和二羧酸与多元醇以及乙烯基化合物做为交联剂的不饱和聚酯树脂,以及它们的具有低可燃性的含卤素的变体。
24.衍生自经取代的丙烯酸酯如环氧丙烯酸酯、氨基甲酸酯丙烯酸酯或聚酯丙烯酸酯的交联性丙烯酸系树脂。
25.用三聚氰胺树脂、尿素树脂、异氰酸酯、异氰脲酸酯、多异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸系树脂。
26.衍生自脂族、环脂族、杂环系或芳族缩水甘油基化合物的交联环氧树脂,例如双酚A二缩水甘油醚、双酚F二缩水甘油醚的产物,例如,它们是借助常规的硬化剂如酸酐或胺,并使用或不使用促进剂而交联。
27.天然聚合物,如纤维素、天然橡胶、明胶,及其经聚合物系方式加以化学改性的衍生物,例如纤维素醋酸酯、纤维素丙酸酯和纤维素丁酸酯,或是纤维素醚如甲基纤维素;以及松香及其衍生物。
28.上述聚合物的混合物(聚合物共混物),例如PP/EPDM、聚酰胺 /EPDM或ABS、PVC/EVA、PVC/ABS、PVC/MBS、PC/ABS、PBTP/ABS、PC/ASA、PC/BT、PVC/CPE、PVC/丙酸酯系、POM/热塑性PUR、PC/热塑性PUR、POM/丙酸酯、POM/MBS、PPO/MBS、PPO/HIPS、PPO/PA6.6和共聚物、PA/PE-HD、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
29.构成纯单体配混物的天然和合成的有机物质或其混合物,例子有矿物油,动物或植物脂、油和蜡,或者是基于合成酯(如邻苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)的油、蜡和脂,以及以任意所需重量比例混合的合成酯与矿物油的共混物,例如作为旋涂面漆使用的那些,及其水乳液。
30.天然或合成橡胶的水乳液,如天然橡胶胶乳或羧化苯乙烯-丁二烯共聚物的胶乳。
通过本发明方法制得的式(I)、(II)和(III)的混合物可直接用来稳定上述的有机材料,或者以与其他添加剂,例如抗氧化剂、光稳定剂、金属减活剂、抗静电剂、阻燃剂、润滑剂、成核剂、酸清除剂(碱性共稳定剂)、颜料和填料的合适的组合的形式。
例如,可额外地用于本发明所制备的(I)、(II)和(III)的混合物的配混物的抗氧化剂和光稳定剂是基于空间位阻胺或空间位阻酚或是含硫或磷的共稳定剂的化合物。可组合应用的合适的添加剂的例子如下文所列:
1.抗氧化剂
1.1烷基化一元酚,例如2,6-二叔丁基-4-甲基苯酚、2-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、直链或支链的壬基苯酚,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,以及它们的混合物。
1.2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。
1.3氢醌和烷基化氢醌,例如2,6-二叔丁基-4-甲氧基苯酚、2,5-二叔丁基氢醌、2,5-二叔戊基氢醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、硬脂酸-3,5-二叔丁基-4-羟基苯酯、己二酸双(3,5-二叔丁基-4-羟基苯)酯。
1.4羟基化二苯硫醚,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)二硫化物。
1.5烷叉双酚,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’-乙叉双(4,6-二叔丁基苯酚)、2,2’-乙叉双(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、双(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯、对苯二甲酸双[2-(3’-叔丁基-2’-羟基-5’-甲基苄基)-6-叔丁基-4-甲基苯基]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、乙二醇双[3,3-双(3’-叔丁基-4’-羟基苯基)丁酸酯]。
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 基二苄基醚、4-羟基-3,5-二甲基苄基巯基醋酸十八烷基酯、三(3,5-二叔丁基-4-羟基苄基)胺、二硫代对苯二甲酸双(4-叔丁基-3-羟基-2,6-二甲基苄基)酯、双(3,5-二叔丁基-4-羟基苄基)硫化物、3,5-二叔丁基-4-羟基苄基巯基醋酸异辛酯、4-羟基-3,5-二叔丁基苄基巯基醋酸十三烷基酯。
1.7羟苄基化的丙二酸酯,例如2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸二(十八烷基)酯、2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸二(十八烷基)酯、巯基乙基-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸二(十二烷基)酯、2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸二[4-(1,1,3,3-四甲基丁基)苯基]酯。
1.8芳族羟苄基化合物,例如1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)苯酚。
1.9三嗪化合物,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、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-羟苄基)异氰脲酸酯。
1.10苄基膦酸酯,例如2,5-二叔丁基-4-羟苄基膦酸二甲酯、3,5-二叔丁基-4-羟苄基膦酸二乙酯、3,5-二叔丁基-4-羟苄基膦酸二(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-羟苄基膦酸的单乙酯的钙盐。
1.11酰基氨基苯酚,例如4-羟基-N-月桂酰苯胺、4-羟基-N-硬脂酰苯胺、N-(3,5-二叔丁基-4-羟基苯基)氨基甲酸辛酯。
1.12β-(3,5-二叔丁基-4-羟苯基)丙酸与一元醇或多元醇形成的酯,所述一元醇或多元醇例如有甲醇、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-2,6,7-三氧杂二环[2.2.2]辛烷。
1.13β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元醇或多元醇形成的酯,所述一元醇或多元醇例如有甲醇、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-2,6,7-三氧杂二环[2.2.2]辛烷。
1.14β-(3,5-二环己基-4-羟苯基)丙酸与一元醇或多元醇形成的酯,所述一元醇或多元醇例如有甲醇、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-2,6,7-三氧杂二环[2.2.2]辛烷。
1.15 3,5-二叔丁基-4-羟苯基醋酸与一元醇或多元醇形成的酯,所述一元醇或多元醇例如有甲醇、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-2,6,7-三氧杂二环[2.2.2]辛烷。
1.16 3,3-双(3’-叔丁基-4’-羟苯基)丁酸与一元醇或多元醇形成的酯,所述一元醇或多元醇例如有甲醇、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-2,6,7-三氧杂二环[2.2.2]辛烷。
1.17β-(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)己二胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)丙二胺、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)肼。
1.18生育酚,如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚、以及它们的混合物(维生素E)。
1.19羟苄基芳族化合物,如1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)苯酚。
1.20抗坏血酸(维生素C)。
1.21胺抗氧化剂,例如N,N’-二异丙基-对苯二胺、N,N’-二仲丁基-对苯二胺、N,N’-双(1,4-二甲基戊基)-对苯二胺、N,N’-双(1-乙基-3-甲基戊基)-对苯二胺、N,N’-双(1-甲基庚基)-对苯二胺、N,N’-二环己基-对苯二胺、N,N’-二苯基-对苯二胺、N,N’-二(萘基-2-)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、辛基化二苯胺(例如对,对’-二叔辛基二苯胺)、4-正丁氨基苯酚、4-丁酰胺基苯酚、4-壬酰胺基苯酚、4-十二烷酰胺基苯酚、4-十八烷酰胺基苯酚、二(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲氨基甲基苯酚、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、1,2-二[(2-甲苯基)-氨基]乙烷、1,2-二(苯氨基)丙烷、(邻甲苯基)双胍、二[4-(1’,3’-二甲基丁基)-苯基]胺、叔辛基化N-苯基-1-萘胺、单烷基化与二烷基化叔丁基/叔辛基二苯胺的混合物、单烷基化与二烷基化壬基二苯胺的混合物、单烷基化与二烷基化十二烷基二苯胺的混合物、单烷基化与二烷基化异丙基/异己基-二苯胺的混合物、单烷基化与二烷基化叔丁基二苯胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单烷基化与二烷基化叔丁基/叔辛基-吩噻嗪的混合物,单烷基化与二烷基化叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N’,N’-四苯基-1,4- 二氨基-丁-2-烯、N,N-双(2,2,6,6-四甲基哌啶-4-基)己二胺、双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、2,2,6,6-四甲基哌啶-4-醇。
2.UV吸收剂和光稳定剂
2.12-(2’-羟苯基)苯并三唑,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)羰乙基]-2’-羟基苯基)-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧羰基乙基)-苯基-5-氯苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-甲氧羰基乙基)-苯基)苯并三唑、2-(3’-叔丁基-2’-羟基-5’-(2-辛氧羰基乙基)苯基)苯并三唑、2-(3’-叔丁基-5’-[2-(2-乙基己氧基)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)苯并三唑与2-(3’-叔丁基-2’-羟基-5’-(2-异辛氧羰基乙基)苯基苯并三唑的混合物、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-甲氧羰基乙基)-2’-羟基苯基]苯并三唑与聚乙二醇300的酯交换产物;[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-羟基二苯甲酮,例如4-羟基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苄氧基、4,2’,4’-三羟基和2’-羟基-4,4’-二甲氧基衍生物。
2.3经取代或未经取代的苯甲酸的酯,例如水杨酸-4-叔丁基-苯酯、水杨酸苯酯、水杨酸辛基苯酯、二苯甲酰基间苯二酚、双(4-叔丁基苯甲酰基)间苯二酚、苯甲酰基间苯二酚、3,5-二叔丁基-4-羟基苯甲酸-2, 4-二叔丁基苯酯、3,5-二叔丁基-4-羟基苯甲酸十六烷基酯、3,5-二叔丁基-4-羟基苯甲酸十八烷基酯、3,5-二叔丁基-4-羟基苯甲酸-2-甲基-4,6-二叔丁基苯酯。
2.4丙烯酸酯,例如α-氰基-β,β-二苯基丙烯酸乙酯或异辛酯、α-甲氧羰基肉桂酸甲酯、α-氰基-β-甲基-对甲氧基-肉桂酸甲酯或丁酯、α-甲氧羰基-对甲氧基肉桂酸甲酯、N-(β-甲氧羰基-β-氰乙烯基)-2-甲基二氢吲哚。
2.5镍化合物,例如具有或不具有额外配体如正丁胺、三乙醇胺或N-环己基二乙醇胺的2,2’-硫代双[4-(1,1,3,3-四甲基丁基)苯酚]的镍配合物,例如1∶1或1∶2配合物,二丁基二硫代氨基甲酸镍,单烷基酯如4-羟基-3,5-二叔丁基苄基膦酸甲酯或乙酯的镍盐,酮肟如2-羟基-4-甲基苯基十一烷基酮肟的镍配合物,具有或不具有额外配体的1-苯基-4-月桂酰基-5-羟基吡唑的镍配合物。
2.6空间位阻胺,例如癸二酸双(2,2,6,6-四甲基哌啶-4-基)酯、戊二酸双(2,2,6,6-四甲基哌啶-4-基)酯、琥珀酸双(2,2,6,6-四甲基哌啶-4-基)酯、癸二酸双(1,2,2,6,6-五甲基哌啶-4-基)酯、戊二酸双(1,2,2,6,6-五甲基哌啶-4-基)酯、正丁基-3,5-二叔丁基-4-羟基苄基-马来酸-双(1,2,2,6,6-五甲基-哌啶基)酯、山嵛酸-2,2,6,6-四甲基哌啶基酯、山嵛酸-1,2,2,6,6-五甲基哌啶基酯、1-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-叔辛氨基-2,6-二氯-1,3,5-s-三嗪的缩合产物、氮川三醋酸三(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁四酸四(2,2,6,6-四甲基-4-哌啶基)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-硬脂氧基-2,2,6,6-四甲基哌啶、4-硬脂酰氧基-2,2,6,6-四甲基哌啶、4-硬脂氧基-1,2,2,6,6-五甲基哌啶、4-硬脂酰氧基-1,2,2,6,6-五甲基哌啶、2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯、2-正丁基-2-(4-羟基-3,5-二叔丁基苄基)丙二酸双(1,2,2,6,6-五甲基哌啶基)酯、3-正辛基 -7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、癸二酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、琥珀酸双(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、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-1,3,5-三嗪的缩合产物、N,N’-双(2,2,6,6-四甲基-4-哌啶基)己二胺与4-环己氨基-2,6-二氯-1,3,5-三嗪的缩合产物、2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙氨基)乙烷的缩合产物、2-氯-4,6-二(4-甲氧丙氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙氨基)乙烷的缩合产物、2-氯-4,6-二(4-甲氧基丙氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙氨基)乙烷的缩合产物、2-氯-4,6-二(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪与1,2-双(3-氨基丙基氨基)乙烷的缩合产物,2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷的反应产物,2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基-1,3,5-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷的反应产物,2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和4-叔辛氨基-2,6-二氯-1,3,5-s-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷的反应产物,2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和4-叔辛氨基-2,6-二氯-1,3,5-s-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷取代)的反应产物,2-氯-4,6-二(4-正丁氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和4-(4-正丁氨基-2,2,6,6-四甲基哌啶基)-2,6-二氯-1,3,5-s-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙 二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷的反应产物,2-氯-4,6-二(4-正丁氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和4-(4-正丁氨基-2,2,6,6-四甲基哌啶基)-2,6-二氯-1,3,5-s-三嗪与单官能或多官能胺(其中胺上的一个至全部活泼氢原子被取代),例如与乙二胺、二亚乙基三胺、三亚乙基四胺、己二胺、1,2-双(3-氨基丙氨基)乙烷的反应产物,1,2-双(3-氨基丙氨基)乙烷与2,4,6-三氯-1,3,5-三嗪以及4-丁氨基-2,2,6,6-四甲基哌啶的缩合产物,N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基琥珀酰亚胺、8-乙酰基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮杂螺[4.5]癸烷-2,4-二酮、低聚的2,2,4,4-四甲基-20-(环氧乙烷基甲基)-7-氧杂-3,20-二氮杂-二螺[5.1.11.2]二十一烷-21-酮、低聚的1,2,2,4,4-五甲基-20-(环氧乙烷基甲基)-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮、低聚的1-乙酰基-2,2,4,4-四甲基-20-(环氧乙烷基甲基)-7-氧杂-3,20-二氮杂-二螺[5.1.11.2]二十一烷-21-酮、3-十二烷基-1-(2,2,6,6-四甲基-4-哌啶基)吡咯烷-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯烷-2,5-二酮、2,2,4,4-四甲基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮、2,2,4,4-四甲基-7-氧杂-21-氧代-3,20-二氮杂二螺[5.1.11.2]二十一烷-3-丙酸十二烷基酯、2,2,4,4-四甲基-7-氧杂-2 1-氧代-3,20-二氮杂二螺[5.1.11.2]二十一烷-3-丙酸十四烷基酯、2,2,3,4,4-五甲基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮、2,2,3,4,4-五甲基-7-氧杂-21-氧代-3,20-二氮杂-二螺[5.1.11.2]二十一烷-3-丙酸十二烷基酯、2,2,3,4,4-五甲基-7-氧杂-21-氧代-3,20-二氮杂-二螺[5.1.11.2]二十一烷-3-丙酸十四烷基酯、3-乙酰基-2,2,4,4-四甲基-7-氧杂-3,20-二氮杂二螺[5.1.11.2]二十一烷-21-酮、3-乙酰基-2,2,4,4-四甲基-7-氧杂-21-氧代-3,20-二氮杂二螺[5.1.11.2]二十一烷-3-丙酸十二烷基酯、3-乙酰基-2,2,4,4-四甲基-7-氧杂-21-氧代-3,20-二氮杂二螺[5.1.11.2]二十一烷-3-丙酸十四烷基酯、1,1’,3,3’,5, 5’-六氢-2,2’,4,4’,6,6’-六氮杂-2,2’,6,6’-双桥亚甲基-7,8-二氧代-4,4’-双(1,2,2,6,6-五甲基-4-哌啶基)联苯、聚-N,N’-双(2,2,6,6-四甲基-4-哌啶基)-1,8-二氮杂癸烯,2,2,6,6-四甲基-4-烯丙氧基哌啶与聚甲基氢硅氧烷(摩尔质量最高至4000)的加合物、1,2,2,6,6-五甲基-4-烯丙氧基哌啶与聚甲基氢硅氧烷(摩尔质量最高至4000)的加合物、N,N’-二甲酰基-N,N’-双(2,2,6,6-四甲基-4-哌啶基)己二胺、N,N’-二甲酰基-N,N’-双(1,2,2,6,6-五甲基-4-哌啶基)己二胺、5,11-双(2,2,6,6-四甲基-4-哌啶基)-3,5,7,9,11,13-六氮杂四环[7.4.0.02,7.13,13]十四烷-8,14-二酮、5,11-双(1,2,2,6,6-五甲基-4-哌啶基)-3,5,7,9,11,13-六氮杂四环[7.4.0.02,7.13,13]十四烷-8,14-二酮、[(4-甲氧基苯基)亚甲基]丙二酸双(2,2,6,6-四甲基-4-哌啶基)酯、[(4-甲氧基苯基)亚甲基]丙二酸双(1,2,2,6,6-五甲基-4-哌啶基)酯、2,4,6-三(N-环己基-N-[2-(3,3,4,5,5-五甲基哌嗪酮-1-基)-乙基]氨基)-1,3,5-三嗪,具有α-甲基苯乙烯的苯乙烯和马来酸酐与4-氨基-2,2,6,6-四甲基哌啶和十八胺的共聚物,具有α-甲基苯乙烯的苯乙烯和马来酸酐与4-氨基-1,2,2,6,6-五甲基哌啶和十八胺的共聚物,具有2,2’-[(2,2,6,6-四甲基-4-哌啶基)亚胺基]双[乙醇]作为二醇组分的聚碳酸酯,含有2,2’-[(1,2,2,6,6-五甲基-4-哌啶基)亚胺基]双[乙醇]作为二醇组分的聚碳酸酯,马来酸酐和最高至C30的α-烯烃与4-氨基-2,2,6,6-四甲基哌啶的共聚物,马来酸酐和最高至C30的α-烯烃与1-乙酰基-4-氨基-2,2,6,6-四甲基哌啶的共聚物,马来酸酐和最高至C30的α-烯烃与4-氨基-1,2,2,6,6-五甲基哌啶的共聚物,以及哌啶上具有游离NH基的上述化合物的N-烷氧基和N-芳氧基衍生物,特别是α-甲基苄氧基和C1至C18烷氧基。
2.7草酰胺,例如4,4’-二辛氧基-N-草酰苯胺、2,2’-二乙氧基-N-草酰苯胺、2,2’-二辛氧基-5,5’-二叔丁基-N-草酰苯胺、2,2’-二(十二烷氧基)-5,5’-二叔丁基-N-草酰苯胺、2-乙氧基-2’-乙基-N-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’-乙基-N-草酰苯胺及其与2-乙氧基-2’-乙基-5,4’-二叔丁基-N-草酰苯胺的混合物,以及 邻甲氧基-和对甲氧基-二取代-N-草酰苯胺的混合物与邻乙氧基-和对乙氧基-二取代-N-草酰苯胺的混合物。
2.8 2-(2-羟基苯基)-1,3,5-三嗪,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(2,4-二甲基苯基)-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-[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。
3.金属减活剂,例如N,N’-二苯基草酰胺、N-水杨醛-N’-水杨酰基肼、N,N’-双(水杨酰基)肼、N,N’-双(3,5-二叔丁基-4-羟苯基丙酰基)肼、3-水杨酰胺基-1,2,4-三唑、双(苄叉)草酰基二肼、N-草酰苯胺、间苯二甲酰基二肼、癸二酰基双苯基肼、N,N’-二乙酰基己二酰基二肼、N,N’-双(水杨酰基)草酰基二肼、N,N’-双(水杨酰基)硫代丙酰基二肼。
4.亚磷酸酯和亚膦酸酯,例如亚磷酸三苯酯、亚磷酸二苯基烷基酯、亚磷酸苯基二烷基酯、亚磷酸三(壬基苯)酯、亚磷酸三月桂酯、亚磷酸三(十八烷基)酯、二硬脂基季戊四醇二亚磷酸酯、亚磷酸三(2,4-二叔丁基苯)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(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、双 异癸氧基季戊四醇二亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯、三硬脂基山梨糖醇三亚磷酸酯、4,4’-联苯撑二亚膦酸四(2,4-二叔丁基苯基)酯、6-异辛氧基-2,4,8,10-四叔丁基-12H-二苯并[d,g]-1,3,2-二氧杂环亚磷酸酯(phosphocin)、6-氟-2,4,8,10-四叔丁基-12-甲基-二苯并[d,g]-1,3,2-二氧杂环亚磷酸酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)甲酯、亚磷酸双(2,4-二叔丁基-6-甲基苯基)乙酯、亚磷酸三(2-叔丁基-4-硫代-(2’-次甲基-4’-羟基-5’-叔丁基)苯基-5-次甲基)苯酯2,2’,2”-氮川[三(3,3’,5,5’-四叔丁基-1,1’-联苯-2,2’-二基)亚磷酸三乙酯]、双[2-甲基-4,6-双(1,1-二甲基乙基)苯酚]亚磷酸乙酯。
5.羟基胺,例如N,N-二苄基羟基胺、N,N-二乙基羟基胺、N,N-二辛基羟基胺、N,N-二月桂基羟基胺、N,N-二(十四烷基)羟基胺、N,N-二(十六烷基)羟基胺、N,N-二(十八烷基)羟基胺、N-十六烷基-N-十八烷基羟基胺、N-十七烷基-N-十八烷基羟基胺、由氢化牛油脂肪胺制得的N,N-二烷基羟基胺。
6.硝酮,例如N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-十八烷基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十六烷基硝酮、衍生自由氢化牛油脂肪胺所制得的N,N-二烷基羟基胺的硝酮。
此类水滑石可用下式描述
[(M2+)1-x(M3+)x(OH)2(An-)x/nyH2O],
其中
(M2+)表示Mg,Ca,Sr,Ba,Zn,Pb,Sn,Ni
(M3+)表示Al,B,Bi
An-表示化合价为n的阴离子
n表示1-4的整数
x表示0到0.5的值
y表示0到2的值
A表示OH-、Cl-、Br-、I-、ClO4-、CH3COO-、C6H5COO-、CO3 2-、SO4 2-、(OOC-COO)2-、(CHOHCOO)2 2-、(CHOH)4CH2OHCOO-、C2H4(COO)2 2-、(CH2COO)2 2-、CH3CHOHCOO-、SiO3 2-、SiO4 4-、Fe(CN)6 3-、Fe(CN)6 4-、BO3 3-、PO3 3-、HPO4 2-。
优选使用其中(M2+)表示(Ca2+),(Mg2+),或(Mg2+)与(Zn2+)的混合物;(An-)表示CO3 2-、BO3 3-、PO3 3-;x具有0至0.5的值且y具有0至2的值的水滑石。也可以使用用下式描述的水滑石
[(M2+)x(Al3+)2(OH)2x+6nz(An-)2yH2O],
此处,(M2+)表示Mg2+、Zn2+,但更优选为Mg2+。(An-)表示阴离子,特别是选自CO3 2-、(OOC-COO)2-、OH-和S2-,其中n描述离子的化合价。y是一个正数,更优选地是0到5,尤其是0.5到5。x和z都具有正值,其中x优选地是2至6,而z应小于2。下式的水滑石应视为特别优选的:
Al2O3×6MgO×CO2×12H2O,
Mg4.5Al2(OH)13×CO3×3.5H2O,
4MgO×Al2O3×CO2×9H2O,
4MgO×Al2O3×CO2×6H2O,
ZnO×3MgO×Al2O3×CO2×8-9H2O,
ZnO×3MgO×Al2O3×CO2×5-6H2O,
Mg4.5Al2(OH)13×CO3。
优选地,水滑石在聚合物中的使用浓度为0.01至5重量%,特别是0.2至3重量%,基于整个聚合物调方。
8.硫代协合剂,例如硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯。
9.过氧化物清除剂,例如β-硫代二丙酸的酯(如月桂酯、硬脂酯、肉豆蔻酯或十三烷基酯)、巯基苯并咪唑、2-巯基苯并咪唑的锌盐、烷基二硫代氨基甲酸锌、二丁基二硫代氨基甲酸锌、二(十八烷基)一硫化物、二(十八烷基)二硫化物、季戊四醇四(β-十二烷基巯基)丙酸酯。
10.聚酰胺稳定剂,例如铜盐与碘化物和/或磷化合物以及二价锰的 盐的组合。
11.碱性共稳定剂,例如三聚氰胺、聚乙烯基吡咯烷酮、双氰胺、氰脲酸三烯丙酯、脲衍生物、肼衍生物、胺、聚酰胺、聚氨酯、高级脂肪酸的碱金属盐和碱土金属盐,例如硬脂酸钙、硬脂酸锌、山嵛酸镁、硬脂酸镁、蓖麻醇酸钠、棕榈酸钾,焦儿茶酚锑或焦儿茶酚锡。
12.成核剂,例如无机物质,例如滑石,金属氧化物,如二氧化钛或氧化镁,磷酸盐、碳酸盐或硫酸盐(优选地是碱土金属盐),有机化合物,如一元或多元羧酸及其盐,例如4-叔丁基苯甲酸、己二酸;二苯基醋酸;琥珀酸钠或苯甲酸钠;芳族醛与多官能醇如山梨糖醇的缩醛,该山梨糖醇例如有1,3-2,4-二(苄叉)-D-山梨糖醇、1,3-2,4-二(4-甲苯叉)-D-山梨糖醇、1,3-2,4-二(4-乙基苄叉)-D-山梨糖醇;聚合化合物,如离子共聚物(离聚物)。
13.填料和增强剂,例如碳酸钙、硅酸盐、玻璃纤维、石棉、滑石、高岭土、云母、硫酸钡、金属氧化物和金属氢氧化物、炭黑、石墨、木粉和其他粉类或其他天然产品的纤维、合成纤维。
14.其他添加剂,例如增塑剂、润滑剂、乳化剂、颜料、流变添加剂、催化剂、流平助剂、荧光增白剂、阻燃剂、抗静电剂、发泡剂。
15.苯并呋喃酮和二氢吲哚,例如描述于US-A-4325863、US-A-4338244、US-A-5175312、US-A-5216052、US-A-5252643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839或EP-A-0591102,或者是3-[4-(2-乙酰氧基乙氧基)苯基]-5,7-二叔丁基苯并呋喃-2-酮、5,7-二叔丁基-3-[4-(2-硬脂酰氧基乙氧基)苯基]-苯并呋喃-2-酮、3,3’-双[5,7-二叔丁基-3-(4-[2-羟基乙氧基]苯基)苯并呋喃-2-酮、5,7-二叔丁基-3-(4-乙氧基苯基苯并呋喃-2-酮、3-(4-乙酰氧-3,5-二甲基苯基)-5,7-二叔丁基-苯并呋喃-2-酮、3-(3,5-二乙基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮。
将上文第1至12组以及第15组的各种加入的添加剂可以0.01至10重量%,优选地0.01至5重量%,基于待稳定的有机材料的总重量的量加入到该待稳定的聚合物中。第13组和第14组的添加物的比例则是0.1 至80重量%,优选地0.1至50重量%,其于待稳定的有机材料。
使用常用且公知的方法将这些添加剂掺入待稳定的有机材料中。例如,掺入的进行可通过混合入刚聚合好的聚合物中或是成形之前或期间的熔体中,或者是将本发明的混合物与必非要另外的添加剂一起施用入或到刚聚合好的聚合物或成形之前或期间的熔体中。
掺入的进行也可通过将经溶解或分散的化合物直接施用到聚合物中,或通过将它们混合成聚合物的溶液、悬浮液或乳液,合适的情况下,随后蒸发掉溶剂。
这些化合物如果随后在单独的加工步骤中掺入已造粒的聚合物中,也是有效的。
根据本发明所制备的化合物也可以含有这些化合物的母料形式,例如以浓度为1至75重量%,优选地2.5至60重量%,加入待稳定的聚合物中。
本发明的方法提供的重要的优点是,组分(I)、(II)和(III)的混合物可以不通过费时、复杂且昂贵地将各个制得的组分混合而制备,取而代之地,有利地且令人惊奇地是以灵巧的反应方式原位制备。
下列的实施例用于举例说明本发明的主题。
实施例1-6
关于所述的变量x和y的值,参见表1。
向x克二甲苯中相继掺入200.3克(0.50摩尔)的2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代二螺[5.1.11.2]二十一烷盐酸盐、10克聚乙二醇200和y克表氯醇以及164.0克浓度为50%的氢氧化钠水溶液(2.05摩尔)。
在70℃下搅拌此混合物40分钟。当已蒸发掉过量的表氯醇和二甲苯溶剂后,向反应混合物中加入220g二甲苯和220g水并且分相。每次用110克水洗涤有机相,洗两次。在减压下蒸馏除去溶剂,得到黄色油状物,其无需进一步纯化即在220℃下在全真空下反应而获得所需的混合物。产物是一种脆的、几乎无色的树脂,其产量、熔程和溶液粘度概括于表1中。
表1
实施例 编号 | x(克) (二甲苯) | y(克) (表氯醇) | 产量 (克) | 熔程(℃) | 溶液粘度 (mm2/s)1 |
1 | 345.0 | 115.6 | 98.5 | 158-210 | 1.83 |
2 | 114.9 | 115.6 | 98.1 | 166-216 | 2.23 |
3 | 172.5 | 115.6 | 98.2 | 163-216 | 2.09 |
4 | 241.5 | 115.6 | 98.7 | 160-210 | 2.00 |
5 | 345.0 | 92.5 | 96.0 | 153-202 | 1.64 |
6 | 345.0 | 104.1 | 99.0 | 146-197 | 1.75 |
1)根据DIN 51562,在25℃下,20%浓度的甲苯溶液
实施例1、5和6是比较实施例。
Claims (16)
1.一种用于制备含有如下通式(I)、(II)和(III)组分的协同性稳定剂混合物的方法,所述混合物包含分数为65-95重量%的化合物(I),分数为5至35重量%的化合物(II),以及分数为0至10重量%的化合物(III),
其中
n和m互相独立地表示0至100的数,但两者不能都为0,
R1表示氢、C5-C7环烷基或C1-C12烷基,
R2和R3互相独立地表示氢原子,C1-C18烷基,或是与连接它们的碳原子一起构成一个5至13元环,或者与将它们接合在一起的碳原子一起构成式(IV)的基团,
R4和R5互相独立地表示氢或C1-C22烷基,氧自由基O*、-OH、-NO、-CH2CN、苄基、烯丙基、C1-C30烷氧基、C5-C12环烷氧基、C6-C10芳氧基、C7-C20芳基烷氧基、C3-C10链烯基、C3-C6炔基、C1-C10酰基、卤素或是未经取代的苯基或经C1-C4烷基取代的苯基,
其特征为,在相转移反应中,将式(V)的化合物
,其中R1、R2、R3和R4如上所定义,和R6 -表示质子酸的阴离子,与式(VI)的表卤代醇反应
,其中X表示氯、溴或碘原子,然后再进行聚合反应,
其中以2∶1-1∶5的比率使用惰性有机溶剂,相对于化合物(VI)。
2.根据权利要求1的方法,其特征为如下步骤:在有机溶剂中预混合化合物(V)、(VI)和相转移催化剂,加入相对于化合物(V)4-20倍摩尔量的固体碱金属氢氧化物或碱金属氢氧化物水溶液,在20-220℃的温度下进行反应,除去过量的表卤代醇(VI),分离出有机相并除去有机溶剂,以及在100至240℃的温度下进行聚合反应。
3.根据权利要求1的方法,其特征为,所述化合物(V)和(VI)以1∶1至1∶2.9的摩尔比预混合。
4.根据权利要求1的方法,其特征为,所述相转移催化剂是聚乙二醇。
5.根据权利要求1的方法,其特征为,所用的惰性有机溶剂是二甲苯。
6.根据权利要求1的方法,其特征为,所述惰性有机溶剂以2∶1至1∶3的比率使用,相对于化合物(VI)。
7.根据权利要求5的方法,其特征为,所述惰性有机溶剂以2∶1至1∶2的比率使用,相对于化合物(VI)。
8.根据权利要求1的方法,其特征为,所述碱金属氢氧化物是氢氧化钠,且是以固体形式或以水溶液形式使用。
9.根据权利要求1的方法,其特征为,在所述水溶液中碱金属氢氧化物对水的比是在9∶1至1∶9的范围内。
10.根据权利要求9的方法,其特征为,在所述水溶液中碱金属氢氧化物对水的比为2∶3至4∶1。
11.根据权利要求1的方法,其特征为,所述反应是在40至120℃的温度下进行。
12.根据权利要求1的方法,其特征为,过量的表卤代醇(VI)和惰性有机溶剂通过蒸馏除去。
13.根据权利要求1的方法,其特征为,所述聚合反应在120至220℃的温度下进行。
14.根据权利要求1的方法,其特征为,所述聚合反应在减压下进行。
15.根据权利要求1的方法,其特征为,式(V)的化合物是2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代二螺[5.1.11.2]二十一烷盐酸盐。
16.根据权利要求1的方法,其特征为,式(VI)的化合物是表氯醇。
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ES2262967T3 (es) | 2006-12-01 |
DE60305003D1 (de) | 2006-06-08 |
US20050228086A1 (en) | 2005-10-13 |
TW200302863A (en) | 2003-08-16 |
ATE325159T1 (de) | 2006-06-15 |
JP2005517065A (ja) | 2005-06-09 |
KR100944297B1 (ko) | 2010-02-24 |
AU2003201747A1 (en) | 2003-09-02 |
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