CN102137890A - 用于脂族聚酯的稳定剂共混物 - Google Patents
用于脂族聚酯的稳定剂共混物 Download PDFInfo
- Publication number
- CN102137890A CN102137890A CN2009801338116A CN200980133811A CN102137890A CN 102137890 A CN102137890 A CN 102137890A CN 2009801338116 A CN2009801338116 A CN 2009801338116A CN 200980133811 A CN200980133811 A CN 200980133811A CN 102137890 A CN102137890 A CN 102137890A
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- Prior art keywords
- butyl
- phenyl
- tert
- ester
- methyl
- Prior art date
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 21
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- 239000010457 zeolite Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种组合物,其含有:a)脂族聚酯,b)酚类抗氧化剂,c)亚磷酸酯或亚膦酸酯,和d)硫代协同剂。
Description
本发明涉及一种组合物,其含有a)脂族聚酯,优选基于乳酸的聚酯;b)酚类抗氧化剂;c)亚磷酸酯或亚膦酸酯;和d)硫代协同剂,以及涉及所述稳定剂共混物用于稳定脂族聚酯以抵抗氧化降解、热降解或光诱导降解的用途。
JP-A-2006-176613公开了热塑性聚酯树脂,其含有次膦酸酯和二次膦酸酯作为阻燃剂、氟化合物、抗静电剂以及抗氧化剂。
公知的稳定剂不能在每个方面都满足稳定剂混合物所需的高要求,尤其是储存期、吸水性、水解敏感性、工艺中的稳定性、着色性能、挥发性、迁移行为、相容性和耐光方面的改进。所以,仍然需要有效地用于脂族聚酯的稳定剂混合物,其对氧化降解、热降解和/或光诱导降解是敏感的。
现在发现了一种稳定剂混合物尤其适合用做脂族聚酯的稳定剂。
因此,本发明涉及一种组合物,其含有:
a)脂族聚酯,
b)酚类抗氧化剂,
c)亚磷酸酯或亚膦酸酯,和
d)硫代协同剂。
感兴趣的组合物包括包含下式I化合物作为组分(b)的那些组合物:
其中:
R1是C1-C4烷基,
n是1、2、3或4,
X是亚甲基,
Y是氧或-NH-;和
如果n是1,则:
R2是C1-C25烷基;和
如果n是2,则:
X是其中Y与R2连接,和
R2是C2-C12亚烷基,被氧或硫间隔的C4-C12亚烷基;或如果Y是-NH-,则R2另外是直接键;和,
如果n是3,则:
如果n是4,则:
R2是C4-C10链烷四基。
具有最多25个碳原子的烷基是支化或非支化的基团,例如是甲基,乙基,丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,2-乙基丁基,正戊基,异戊基,1-甲基戊基,1,3-二甲基丁基,正己基,1-甲基己基,正庚基,异庚基,1,1,3,3-四甲基丁基,1-甲基庚基,3-甲基庚基,正辛基,2-乙基己基,1,1,3-三甲基己基,1,1,3,3-四甲基戊基,壬基,癸基,十一烷基,1-甲基十一烷基,十二烷基,1,1,3,3,5,5-六甲基己基,十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,二十烷基或二十二烷基。优选的R1是甲基和叔丁基。特别优选的R2是C1-C20烷基,尤其是C1-C18烷基,例如C4-C18烷基。尤其优选的R2是C8-C18烷基,尤其是C14-C18烷基,例如C18烷基。
C2-C12亚烷基是支化或非支化的基团,例如是亚乙基、亚丙基、四亚甲基、五亚甲基、六亚甲基、七亚甲基、八亚甲基、十亚甲基或十二亚甲基。优选的R2例如是C2-C10亚烷基,尤其是C2-C8亚烷基。尤其优选的R2例如是C4-C8亚烷基,尤其是C4-C6亚烷基,例如六亚甲基。
被氧或硫间隔的C4-C12亚烷基可以被间隔一次或多次,例如是-CH2-O-CH2CH2-O-CH2-,-CH2-(O-CH2CH2-)2O-CH2-,-CH2-(O-CH2CH2-)3O-CH2-,-CH2-(O-CH2CH2-)4O-CH2-,-CH2CH2-O-CH2CH2-O-CH2CH2-,或-CH2CH2-S-CH2CH2-。优选的R2例如是被氧或硫间隔的C4-C10亚烷基,尤其是被氧或硫间隔的C4-C8亚烷基,例如被氧或硫间隔的C4-C6亚烷基。尤其优选的R2是-CH2CH2-O-CH2CH2-O-CH2CH2-或-CH2CH2-S-CH2CH2-。
组分(b)也可以含有不同的式I位阻酚的混合物。
感兴趣的组合物包括含有至少一种式I化合物作为组分(b)的那些组合物,其中如果n是1,则R2是C1-C20烷基。
优选含有至少一种式I化合物作为组分(b)的那些组合物,其中如果n是2,则R2是C2-C8亚烷基、被氧或硫间隔的C4-C8亚烷基;或如果Y是-NH-,则R2另外是直接键;和如果n是4,则R2是C4-C8链烷四基。
也优选含有至少一种式I化合物作为组分(b)的那些组合物,其中:
R1是甲基或叔丁基,
n是1、2或4,
Y是氧或-NH-;和
如果n是1,则:
R2是C14-C18烷基;和
如果n是2,则:
R2是C4-C6亚烷基,或是被氧间隔的C4-C6亚烷基;和
如果n是4,则:
R2是C4-C6链烷四基。
也感兴趣的是这样的组合物,其中组分(b)选自:季戊四基-四[3-(3′,5′-二叔丁基-4-羟基苯基)]丙酸酯,十八烷基3-(3′,5′-二叔丁基-4-羟基苯基)丙酸酯,亚乙基二(氧亚乙基)二-(3-(5-叔丁基-4-羟基-间-甲苯基)-丙酸酯),α-生育酚,2,3-二[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙酰肼,2-丙烯酸,2-(1,1-二甲基乙基)-6-[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]甲基-4-甲基苯基酯,3,3′,3″,5,5′,5″-六叔丁基-α,α’,α”-(基-2,4,6-三基)三-对-甲酚,N,N’-己烷-1,6-二基二[3-(3,5-二叔丁基-4-羟基苯基丙酰胺)],二乙基((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)膦酸酯,六亚甲基二(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯),二((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)-乙基膦酸)钙,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲苯基)甲基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮,1,3,5-三(3,5-二叔丁基-4-羟基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮,(2,4,6-三氧-1,3,5-三嗪-1,3,5(2H,4H,6H)-三基)三亚乙基三(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯),与1,3,5-三(2-羟基乙基)-s-三嗪-2,4,6(1H,3H,5H)-三酮的3,5-二叔丁基-4-羟基氢化肉桂酸三酯,2,6-二叔丁基-4-(4,6-二(辛基硫代)-1,3,5-三嗪-2-基氨基)苯酚,苯丙酸3,5-二(1,1-二甲基乙基)-4-羟基-,C7-C9-支化和直链烷基酯,6,6′-二叔丁基-2,2′-硫代二-对-甲酚,2,2′-硫代二亚乙基-二(3,5-二叔丁基-4-羟基苯基)丙酸酯,2,6-二叔丁基-4-甲基-苯酚,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯基)苯,二(3,3-二(4′-羟基-3′-叔丁基苯基)丁酸)二醇酯,4,4′硫代二(2-叔丁基-5-甲基苯酚),2,2′-亚甲基-二(6-(1-甲基-环己基)-对-甲酚),1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷,3,9-二[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺杂[5.5]十一烷,2,6-二叔丁基苯酚,2,6-二叔丁基-4-壬基苯酚,4,4′-亚丁基二(6-叔丁基-3-甲基苯酚),2,2′-亚甲基二(4-甲基-6-叔丁基苯酚),2,2′-亚甲基二(4-乙基-6-叔丁基苯酚),2,2′-亚乙基二(4,6-二叔丁基苯酚),1,1-二(2-甲基-4-羟基-5-叔丁基苯基)丁烷,2,5-二叔戊基氢醌,4,6-二(辛基硫代甲基)-邻-甲酚和4,6-二(十二烷基硫代甲基)-邻-甲酚,或它们的混合物。
也感兴趣的是这样的组合物,其中组分(b)选自:季戊四基-四[3-(3′,5′-二叔丁基-4-羟基苯基)]丙酸酯,十八烷基3-(3′,5′-二叔丁基-4-羟基苯基)丙酸酯,亚乙基二(氧亚乙基)-二(3-(5-叔丁基-4-羟基-间-甲苯基)-丙酸酯),α-生育酚,2,3-二[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙酰肼,2-丙烯酸,2-(1,1-二甲基乙基)-6-[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]甲基-4-甲基苯基酯,3,3′,3″,5,5′,5″-六-叔丁基-α,α’,α”-(基-2,4,6-三基)三-对-甲酚,N,N’-己烷-1,6-二基二[3-(3,5-二叔丁基-4-羟基苯基丙酰胺)],二乙基((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)膦酸酯,二((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)-乙基膦酸)钙,或它们的混合物。
感兴趣的组合物包括含有选自式1-7的有机亚磷酸酯或亚膦酸酯中的化合物作为组分(c)的那些组合物:
其中各指数是整数,并且
n’是2、3或4;p’是1或2;q’是2或3;r’是4-12;y’是1、2或3;z’是1-6;
或亚苯基;
如果n’是3,则A′是式-Cr′H2r′1-的基团;
如果n’是2,则A″具有A′的含义;
B′是直接键,-CH2-,-CHR′4-,-CR′1R′4-,硫或C5-C7亚环烷基,或是在3、4和/或5位上被1-4个C1-C4烷基取代的亚环己基;
如果 p’是1,则D′是甲基;如果p’是2,则D′是-CH2OCH2-;
如果y’是1,则E′是C1-C18烷基、-OR′1或卤素;
如果y’是2,则E′是-O-A″-O-,
如果y’是3,则E′是基团R′4C(CH2O-)3或N(CH2CH2O-)3;
Q′是至少z’价的醇或酚的基团,此基团经由氧原子连接到磷原子上;
R′1、R′2和R′3各自独立地是未取代的C1-C18烷基,或被卤素、-COOR4′、-CN-或-CONR4′R4′-取代的C1-C18烷基;被氧、硫或-NR′4-间隔的C2-C18烷基;C7-C9苯基烷基;C5-C12环烷基,苯基或萘基;被卤素、1-3个具有总共1-8个碳原子的烷基或烷氧基取代的或被C7-C9苯基烷基取代的萘基或苯基;或是基团其中m′是3-6范围内的整数;
R′4是氢、C1-C18烷基、C5-C12环烷基或C7-C9苯基烷基,
R′5和R′6各自独立地是氢、C1-C8烷基或C5-C6环烷基,
如果q’是2,则R′7和R′8各自独立地是C1-C4烷基,或一起是2,3-脱氢五亚甲基;和
如果q’是3,则R′7和R′8是甲基;
R′14是氢,C1-C9烷基或环己基,
R′15是氢或甲基,并且如果存在两个或多个基团R′14和R′15,则这些基团是相同或不同的,
X′和Y′各自是直接键或氧,
Z′是直接键,亚甲基,-C(R′16)2-或硫,和
R′16是C1-C8烷基。
特别感兴趣的是含有式1、2、5或6的亚磷酸酯或亚膦酸酯作为组分(c)的那些组合物,其中:
n′是2,y′是1、2或3;
A′是C2-C18亚烷基,对-亚苯基或对-亚联苯基,
如果y’是1,则E′是C1-C18烷基、-OR′1或氟;
如果y’是2,则E′是对-亚联苯基,
如果y’是3,则E′是N(CH2CH2O-)3,
R′1、R′2和R′3各自独立地是C1-C18烷基,C7-C9苯基烷基,环己基,苯基,或被1-3个具有总共1-18个碳原子的烷基取代的苯基;
R′14是氢或C1-C9烷基,
R′15是氢或甲基;
X′是直接键,
Y′是氧,
Z′是直接键或-CH(R′16)-,和
R′16是C1-C4烷基。
也感兴趣的是含有式1、2、5或6的亚磷酸酯或亚膦酸酯作为组分(c)的那些组合物,其中:
n′是2,y′是1或3;
A′是对-亚联苯基,
如果y’是1,则E′是C1-C18烷基或氟;
如果y’是3,则E′是N(CH2CH2O-)3,
R′1、R′2和R′3各自独立地是C1-C18烷基,或被2或3个具有总共2-12个碳原子的烷基取代的苯基;
R′14是甲基或叔丁基,
R′15是氢;
X′是直接键,
Y′是氧,
Z′是直接键、亚甲基或-CH(CH3)-。
特别优选的是含有式1、2或6的亚磷酸酯或亚膦酸酯作为组分(c)的那些组合物。
尤其优选的是这样的组合物,其中组分(c)是选自:三(2,4-二叔丁基苯基)亚磷酸酯,二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,四[(2,4-二叔丁基苯基)-4,4-亚联苯基二亚膦酸酯],三(壬基苯基)亚磷酸酯,二(2,4-二叔丁基-6-甲基苯基)-乙基-亚磷酸酯,2,2’2”-次氮基[三乙基-三[3,3’,5,5’-四-叔丁基-1,1’-二苯基-2,2’-二基]]亚磷酸酯,二-硬脂基-季戊四基-二亚磷酸酯,二(2,4-二枯基苯基)季戊四醇二亚磷酸酯,(2,4,6-三叔丁基苯酚)-2-丁基-2-乙基-1,3-丙二醇亚磷酸酯,二[2,6-二叔丁基-4-甲基苯基]-季戊四醇二亚磷酸酯,二[壬基苯基]季戊四醇二亚磷酸酯和2,2-亚甲基-二(4,6-二叔丁基苯基)-辛基亚磷酸酯,或它们的混合物。
尤其优选的是这样的组合物,其中组分(c)是选自:三(2,4-二叔丁基苯基)亚磷酸酯,二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,四[(2,4-二叔丁基苯基)-4,4-亚联苯基二亚膦酸酯],二-硬脂基-季戊四基-二亚磷酸酯,二(2,4-二枯基苯基)季戊四醇二亚磷酸酯,二[2,6-二叔丁基-4-甲基苯基]-季戊四醇二亚磷酸酯,二[壬基苯基]季戊四醇二亚磷酸酯,或它们的混合物。
感兴趣的包括这样的组合物,其中组分(d)是选自:双-十八烷基3,3′-硫代二丙酸酯,双-十二烷基3,3′-硫代二丙酸酯,混合的月桂基-硬脂基硫代二丙酸酯,双肉豆蔻基硫代二丙酸酯,双-棕榈基/硬脂基-硫代二丙酸酯,月桂基-硬脂基-硫代二丙酸酯,双-十三烷基-硫代二丙酸酯,双-十八烷基二硫化物,二叔十二烷基二硫化物,季戊四醇辛基硫代二丙酸酯,季戊四醇-四(3-月桂基硫代丙酸酯),或它们的混合物。
尤其感兴趣的是这样的组合物,其中组分(d)是选自:双-十八烷基3,3′-硫代二丙酸酯,双-十二烷基3,3′-硫代二丙酸酯,或它们的混合物。
组分(b)、(c)和(d)的混合物适用于稳定脂族聚酯以抵抗氧化降解、热降解或光诱导的降解。
本发明的脂族聚酯是可商购的,或可以根据本领域现有技术人员已知的方法制备;例如通过脂族羟基羧酸的缩聚反应,开环聚合,或脂族二元酸和/或脂族二元酸的能形成酯键的化合物与脂族二醇进行的缩聚反应。
通过这些脂族羟基羧酸的缩聚反应获得的脂族聚酯树脂的例子包括聚乳酸、聚乙二醇酸、聚3-羟基丁酸、聚4-羟基丁酸以及聚4-羟基戊酸。
通过开环聚合获得的脂族聚酯树脂的例子包括聚乳酸、聚丙内酯、聚丁内酯、聚新戊内酯、聚戊内酯和聚己内酯。
通过脂族二元酸和/或脂族二元酸的能形成酯键的化合物与脂族二醇进行的缩聚反应获得的脂族聚酯树脂的例子包括聚亚乙基琥珀酸酯、聚亚丁基琥珀酸酯、聚六亚甲基琥珀酸酯、聚亚乙基己二酸酯、聚亚丁基己二酸酯、聚六亚甲基己二酸酯、聚亚乙基草酸酯、聚亚丁基草酸酯、聚六亚甲基草酸酯、聚亚乙基癸二酸酯和聚亚丁基癸二酸酯。
或者,聚乳酸树脂可以通过选择具有以下结构的原料获得:作为环状乳酸二聚体的交酯,作为环状二醇酸二聚体的乙交酯,己内酯等;然后使所述原料进行开环聚合。交酯可以是作为环状L-乳酸二聚体的L-交酯,作为环状D-乳酸二聚体的D-交酯,作为D-乳酸和L-乳酸的环状二聚体的内消旋-交酯,以及作为D-交酯和L-交酯的外消旋混合物的DL-交酯。在本发明中,可以使用任何交酯。但是,主要的原料优选是D-交酯或L-交酯。
如此获得的聚乳酸可以通过从L-乳酸衍生的单体单元或从D-乳酸衍生的单体单元形成,或可以是这两种单元的共聚物。此外,如果聚乳酸是从L-乳酸衍生的单体单元和从D-乳酸衍生的单体单元形成的共聚物,则这些单体单元之一的含量优选是约85-100摩尔%,更优选约90-100摩尔%,进一步优选约95-100摩尔%,最优选约98-100摩尔%。特别合适的聚乳酸例如参见US-A-2006/142,505。
希望脂族聚酯尤其不含剩余的单体。因此,优选的是剩余单体含量为5000ppm或更少的脂族聚酯树脂,更优选剩余单体含量为2000ppm或更少的脂族聚酯树脂,再更优选剩余单体含量为1000ppm或更少的脂族聚酯树脂,进一步更优选剩余单体含量为500ppm或更少的脂族聚酯树脂。
本发明的脂族聚酯的平均分子量没有特别限制。但是,优选重均分子量为50,000-400,000g/mol的聚酯树脂,更优选重均分子量为80,000-400,000g/mol的聚酯树脂,再更优选重均分子量为100,000-400,000g/mol的聚酯树脂。聚合物的重均分子量是通常通过光散射法按照ASTM D4001-93(2006)检测的。
在这里使用的脂族聚酯树脂包括通过使用仅仅一种能形成脂族酯的化合物作为原料所获得的均聚物,以及通过使用一种或多种能形成脂族酯的化合物作为原料所获得的共聚物,以及这些均聚物和共聚物的混合物。在排列方面,这些共聚物可以是无规共聚物、交替共聚物、嵌段共聚物或接枝共聚物。
脂族聚酯优选是基于乳酸的脂族聚酯,尤其是聚乳酸。术语“聚乳酸(PLA)”表示乳酸或内酯的均聚物,优选聚L-乳酸,或者乳酸或内酯与其它单体形成的共聚物,以及它们的任何共混物或与其它聚合物形成的合金。其它单体是例如羟基羧酸,例如乙醇酸、3-羟基丁酸、4-羟基丁酸、4-羟基戊酸、5-羟基戊酸、6-羟基己酸和它们的环状形式;术语“乳酸”或“内酯”包括L-乳酸,D-乳酸,以及它们的混合物和二聚体,即L-内酯、D-酯、内消旋-内酯以及它们的任何混合物。
在本发明的组合物中,也可以使用上述脂族聚酯基树脂和其它合适聚合物的按照例如重量比1∶100至100∶1的共混物。
所述聚合物的例子是:
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚-1-丁烯、聚4-甲基-1-丁烯、聚乙烯基环己烷、聚异戊二烯或聚丁二烯,以及环烯烃例如环戊烯或降冰片烯的聚合物;以及聚乙烯(任选地被交联),例如高密度聚乙烯(HDPE)、具有高分子量的高密度聚乙烯(HDPE-HMW)、具有超高分子量的高密度聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、线型低密度聚乙烯(LLDPE)、(VLDPE)和(ULDPE)。
聚烯烃,即在上段中所列的单烯烃的聚合物,优选聚乙烯和聚丙烯,可以通过不同的方法制备,尤其是以下方法:
a)自由基聚合(通常在高压和高温下进行)。
b)催化聚合,使用一般含有一种或多于一种元素周期表IVb、Vb、VIb或VIII族的金属的催化剂。这些金属通常具有一种或多于一种的配体,通常是氧化物、卤化物、醇盐、酯、醚、胺、烷基化物、烯基化物和/或芳基化物,它们可以是π-或σ-配位的。这些金属配合物可以是游离形式或固体在基材上,通常固定在活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些催化剂可以是能溶于或不溶于聚合介质中。催化剂可以本身在聚合中使用,或可以使用其它活化剂,一般是金属烷基化物、金属氢化物、金属烷基卤化物、金属烷基氧化物或金属烷基氧丙环,所述金属是元素周期表Ia、IIa和/或IIIa族的元素。活化剂可以方便地用其它酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系一般称为Phillips、Standard OilIndiana,Ziegler(-Natta),TNZ(DuPont)、金属茂或单点催化剂(SSC)。
2.在1)中所述聚合物的混合物,例如聚丙烯与聚异丁烯的混合物,聚丙烯与聚乙烯的混合物(例如PP/HDPE、PP/LDPE),以及不同类型聚乙烯的混合物(例如LDPE/HDPE)。
3.单烯烃和二烯烃彼此之间或与其它乙烯基单体之间的共聚物,例如乙烯/丙烯共聚物,线性低密度聚乙烯(LLDPE)和它们与低密度聚乙烯(LDPE)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,乙烯/乙烯基环己烷共聚物,乙烯/环烯烃共聚物(例如乙烯/降冰片烯,如COC),乙烯/1-烯烃共聚物,其中1-烯烃一般是原地产生的;丙烯/丁二烯共聚物,异丁烯/异戊二烯共聚物,乙烯/乙烯基环己烯共聚物,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/乙酸乙烯酯共聚物或乙烯/丙烯酸共聚物以及它们的盐(离聚物),以及乙烯与丙烯和二烯例如己二烯、二环戊二烯或亚乙基降冰片烯的三元共聚物;以及这些共聚物彼此之间和与上述1)中所述聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物,LDPE/乙烯-乙酸乙烯酯共聚物(EVA),LDPE/乙烯-丙烯酸共聚物(EAA),LLDPE/EVA,LLDPE/EAA,以及交替或无规的聚烯/一氧化碳共聚物,以及它们与其它聚合物的混合物,例如聚酰胺。
4.烃树脂(例如C5-C9),包括其氢化改性形式(例如增粘剂)和聚烯与淀粉的混合物。
1.)-4.)中的均聚物和共聚物可以具有任何立体结构,包括间规立构、等规立构、半等规立构或无规立构;其中优选无规立构聚合物。立体嵌段聚合物也包括在内。
5.聚苯乙烯,聚(p-甲基苯乙烯),聚(α-甲基苯乙烯).
6.衍生自乙烯基芳族单体的芳族均聚物和共聚物,包括苯乙烯,α-甲基苯乙烯,乙烯基甲苯的所有异构体,尤其是对-乙烯基甲苯,乙基苯的所有异构体,丙基苯乙烯,乙烯基联苯,乙烯基萘,以及乙烯基蒽,以及它们的混合物。均聚物和共聚物可以具有任何立体结构,包括间规立构、等规立构、半等规立构或无规立构;其中优选无规立构聚合物。立体嵌段聚合物也包括在内。
6a.包括上述乙烯基芳族单体和选自以下的共聚单体的共聚物:乙烯,丙烯,二烯,腈,酸,马来酸酐,马来酰亚胺,乙酸乙烯酯和氯乙烯或丙烯酸衍生物以及它们的混合物,例如苯乙烯/丁二烯,苯乙烯/丙烯腈,苯乙烯/乙烯(三元共聚物),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/丙烯酸甲基酯;高抗冲强度的苯乙烯共聚物与其它聚合物的混合物,例如聚丙烯酸酯,二烯聚合物,或乙烯/丙烯/二烯三元共聚物;以及苯乙烯的嵌段共聚物,例如苯乙烯/丁二烯/苯乙烯,苯乙烯/异戊二烯/苯乙烯,苯乙烯/乙烯/丁烯/苯乙烯或者苯乙烯/乙烯/丙烯/苯乙烯.
6b.衍生自在6)中所述聚合物的氢化反应的氢化芳族聚合物,尤其包括通过氢化无规立构聚苯乙烯制备的聚环己基乙烯(PCHE),通常称为聚乙烯基环己烷(PVCH)。
6c.衍生自在6a)中所述聚合物的氢化反应的氢化芳族聚合物。
均聚物和共聚物可以具有任何立体结构,包括间规立构、等规立构、半等规立构或无规立构;其中优选无规立构聚合物。立体嵌段聚合物也包括在内。
7.乙烯基芳族单体的接枝共聚物,例如苯乙烯或α-甲基苯乙烯,例如苯乙烯在聚丁二烯上的接枝共聚物,苯乙烯在聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上的接枝共聚物;苯乙烯和丙烯腈(或甲基丙烯腈)在聚丁二烯上的接枝共聚物;苯乙烯、丙烯腈和甲基丙烯酸甲酯在聚丁二烯上的接枝共聚物;苯乙烯和马来酸酐在聚丁二烯上的接枝共聚物;苯乙烯、丙烯腈和马来酸酐或马来酰亚胺在聚丁二烯上的接枝共聚物;苯乙烯和马来酰亚胺在聚丁二烯上的接枝共聚物;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的接枝共聚物;苯乙烯和丙烯腈在乙烯/丙烯/二烯三元共聚物上的接枝共聚物;苯乙烯和丙烯腈在聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上的接枝共聚物,苯乙烯和丙烯腈在丙烯酸酯/丁二烯共聚物上的接枝共聚物,以及它们与6)中所述共聚物的混合物,例如公知为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素的聚合物,例如聚氯丁二烯、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),氯化或磺基氯化的聚乙烯,乙烯和氯化乙烯的共聚物,表氯醇均聚物和共聚物,尤其是含卤素的乙烯基化合物的聚合物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯,聚偏二氟乙烯,它们的共聚物,例如氯乙烯/偏二氯乙烯、氯乙烯/乙酸乙烯酯或偏二氯乙烯/乙酸乙烯酯共聚物。
9.衍生自α,β-不饱和酸和其衍生物的聚合物,例如聚丙烯酸酯和聚甲基丙烯酸酯;聚甲基丙烯酸甲酯,聚丙烯酰胺和聚丙烯腈,用丙烯酸丁酯进行冲击改性。
10.在9)中所述单体彼此之间或与其它不饱和单体之间的共聚物,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/乙烯基卤共聚物或丙烯腈/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其酰基衍生物或缩醛的聚合物,例如聚乙烯基醇、聚乙酸乙烯酯、聚硬脂酸乙烯基酯、聚苯甲酸乙烯基酯、聚马来酸乙烯基酯、聚乙烯基丁缩醛、聚邻苯二甲酸烯丙酯或聚烯丙基蜜胺;以及它们与1)中所述烯烃的共聚物。
12.环醚的均聚物和共聚物,例如聚亚烷基二醇,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,例如聚甲醛,以及含有环氧乙烷作为共聚单体的聚甲醛;用热塑性聚氨酯、丙烯酸酯或MBS改性的聚缩醛。
14.聚苯醚和聚苯硫醚,以及聚苯醚与苯乙烯聚合物或聚酰胺的混合物。
15.从羟基封端的聚醚、聚酯或聚丁二烯以及脂族或芳族多异氰酸酯及其前体衍生的聚氨酯。
16.衍生自二胺和二羧酸和/或衍生自氨基羧酸或相应内酰胺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,来自间二甲苯二胺和己二酸的芳族聚酰胺;从六亚甲基二胺和间苯二甲酸和/或对苯二甲酸并且在存在或不存在作为改性剂的弹性体情况下制备的聚酰胺,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;以及上述聚酰胺与聚烯烃、烯烃共聚物、离聚体或化学键合或接枝弹性体的嵌段共聚物;或与聚醚的共聚物,例如聚乙二醇、聚丙二醇或聚四亚甲基二醇;以及用EPDM或ABS改性的聚酰胺或共聚酰胺,以及在加工期间缩合的聚酰胺(RIM聚酰胺体系)。
17.聚脲、聚酰亚胺、聚酰胺-酰亚胺、聚醚酰亚胺、聚酯酰亚胺、聚乙内酰脲和聚苯并咪唑。
18.衍生自二羧酸和二醇和/或衍生自羟基羧酸或相应内酯或交酯的聚酯,例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、聚萘甲酸亚烷基酯(PAN)和聚羟基苯甲酸酯,以及衍生自羟基封端的聚醚的共聚醚酯,以及用聚碳酸酯或MBS改性的聚酯。共聚酯可以包括例如(但不限于):聚亚丁基琥珀酸酯/对苯二甲酸酯、聚亚丁基己二酸酯/对苯二甲酸酯、聚四亚甲基己二酸酯/对苯二甲酸酯、聚亚丁基琥珀酸酯/己二酸酯、聚亚丁基琥珀酸酯/碳酸酯、聚-3-羟基丁酸酯/辛酸酯共聚物、聚-3-羟基丁酸酯/己酸酯/癸酸酯三元共聚物。此外,脂族聚酯可以包括例如(但不限于)聚羟基链烷酸酯,尤其是聚丙内酯、聚丁内酯、聚新戊内酯、聚戊内酯和聚己内酯,聚亚乙基琥珀酸酯,聚亚丙基琥珀酸酯,聚亚丁基琥珀酸酯,聚六亚甲基琥珀酸酯,聚亚乙基己二酸酯,聚亚丙基己二酸酯,聚亚丁基己二酸酯,聚六亚甲基己二酸酯,聚亚乙基草酸酯,聚亚丙基草酸酯,聚亚丁基草酸酯,聚六亚甲基草酸酯,聚亚乙基癸二酸酯,聚亚丙基癸二酸酯和聚亚丁基癸二酸酯,以及用聚碳酸酯或MBS改性的相应聚酯。
19.聚碳酸酯和聚酯碳酸酯。
20.聚烯酮。
21.聚砜、聚醚砜和聚醚酮。
22.从酚、脲和蜜胺之一以及醛衍生的交联聚合物,例如苯酚/甲醛树脂、脲/甲醛树脂,以及蜜胺/甲醛树脂。
23.干燥和非干燥的醇酸树脂。
24.从饱和和不饱和羧酸与多元醇以及作为交联剂的二乙烯基化合物衍生的不饱和聚酯树脂,以及具有低可燃性的含卤素的改性形式。
25.从被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、聚氨酯丙烯酸酯或聚酯丙烯酸酯。
26.用蜜胺树脂、脲树脂、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、聚酯树脂以及丙烯酸酯树脂。
27.从脂族、脂环族、杂环或芳族的缩水甘油基化合物衍生的交联的环氧树脂,例如双酚A和双酚F的二缩水甘油醚的产物,其被常规硬化剂例如酸酐或胺交联,其中使用或不使用加速剂。
28.天然聚合物,例如纤维素、橡胶、明胶和它们的化学改性的同系衍生物,例如乙酸纤维素、丙酸纤维素和丁酸纤维素,或纤维素醚,例如甲基纤维素;以及松香和它们的衍生物。
29.上述聚合物的共混物(聚合共混物),例如PP/EPDM,聚酰胺/EPDM或ABS,PVC/EVA,PVC/ABS,PVC/MBS,PC/ABS,PBTP/ABS,PC/ASA,PC/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/PA 6.6和共聚物,PA/HDPE,PA/PP,PA/PPO,PBT/PC/ABS或PBT/PET/PC。
30.天然和合成的有机材料,其是纯的单体化合物或这些化合物的混合物,例如矿物油、动物和植物脂肪、油和蜡,或基于合成酯的油、脂肪和蜡(例如邻苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯),以及合成酯与矿物油按照任何重量比例的混合物,通常用做纺丝组合物,以及这些材料的水乳液。
31.天然或合成橡胶的水乳液,例如天然胶乳或羧基化苯乙烯/丁二烯共聚物的胶乳。
组分(b)优选按照0.01-0.80%的浓度加入要稳定的脂族聚酯中,优选0.05-0.30%,基于所述材料[组分(a)]的重量计。
组分(c)优选按照0.01-0.60%的浓度加入要稳定的脂族聚酯中,优选0.05-0.20%,基于所述材料[组分(a)]的重量计。
组分(d)优选按照0.01-0.40%的浓度加入要稳定的脂族聚酯中,优选0.10-0.20%,基于所述材料[组分(a)]的重量计。
除了组分(a)、(b)、(c)和(d)之外,新组合物可以含有其它助稳定剂(添加剂),通常是以下:
1.胺类抗氧剂,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’-二(1,4-二甲基戊基)-对-亚苯基二胺、N,N’-二(1-乙基-3-甲基戊基)-对-亚苯基二胺、N,N’-二(1-甲基庚基)-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’-二(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-甲苯氨磺酰基)二苯基胺、N,N’-二甲基-N,N’-二仲丁基-对-亚苯基二胺、二苯基胺、N-烯丙基二苯基胺、4-异丙氧基-二苯基胺、N-苯基-1-萘基胺、N-(4-叔辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化的二苯基胺(例如对,对’-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、二(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、1,2-二[(2-甲基苯基)氨基]乙烷、1,2-二(苯基氨基)丙烷、邻-甲苯基双胍、二[4-(1’,3’-二甲基丁基)苯基]胺、叔辛基化的N-苯基-1-萘基胺、单和双烷基化的叔丁基/叔辛基二苯基胺的混合物、单和双烷基化的壬基二苯基胺的混合物、单和双烷基化的十二烷基二苯基胺的混合物、单和双烷基化的异丙基/异己基二苯基胺的混合物、单和双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、单和双烷基化的叔丁基/叔辛基吩噻嗪的混合物、单和双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,N,N-二(2,2,6,6-四甲基哌啶-4-基)-六亚甲基二胺,二(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′-羟基苯基)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′-二(α,α-二甲基苄基)-2′-羟基苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)-5-氯苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基己氧基)羰基乙基]-2′-羟基苯基)-5-氯苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)-5-氯苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-甲氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-辛氧基羰基乙基)苯基)苯并三唑,2-(3′-叔丁基-5′-[2-(2-乙基-己氧基)羰基乙基]-2′-羟基苯基)苯并三唑,2-(3′-十二烷基-2′-羟基-5′-甲基-苯基)苯并三唑,2-(3′-叔丁基-2′-羟基-5′-(2-异辛氧基羰基乙基)苯基-苯并三唑,2,2′-亚甲基-二[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基-苯酚];2-[3′-叔丁基-5′-(2-甲氧基羰基乙基)-2′-羟基苯基]-2H-苯并三唑与聚乙二醇300的酯交换产物;[R-CH2CH2-COO-CH2CH2-]2-,其中R=3′-叔丁基-4′-羟基-5′-2H-苯并三唑-2-基-苯基;2-[2′-羟基-3′-(α,α-二甲基苄基)-5′-(1,1,3,3-四甲基丁基)苯基]-苯并三唑;2-[2′-羟基-3′-(1,1,3,3-四甲基丁基)-5′-(α,α-二甲基苄基)苯基]-苯并三唑。
2.2.2-羟基二苯酮,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.未取代或取代的苯甲酸的酯,例如4-叔丁基苯基水杨酸酯,水杨酸苯基酯,辛基苯基水杨酸酯,二苯甲酰基间苯二酚,二(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,例如α-氰基-β,β-二苯基丙烯酸乙基酯,α-氰基-β,β-二苯基丙烯酸异辛基酯,α-甲氧基羰基肉桂酸甲基酯,α-氰基-β-甲基-p-甲氧基肉桂酸甲基酯或丁基酯,α-甲氧基羰基-p-甲氧基肉桂酸甲基酯,以及N-(β-甲氧基羰基-β-氰基乙烯基)-2-甲基吲哚。
2.5.镍化合物,例如:2,2’-硫代二[4-(1,1,3,3-四甲基丁基)苯酚]的镍络合物,如1∶1或1∶2络合物,任选地使用其它配体,如正丁胺、三乙醇胺或N-环己基二乙醇胺,二硫代氨基甲酸二丁酯镍、4-羟基-3,5-二叔丁基苄基膦酸单烷基酯(例如甲酯或乙酯)的镍盐、酮肟(例如2-羟基-4-甲基苯基十一烷基酮肟)的镍络合物、和1-苯基-4-十二烷酰基-5-羟基吡唑的镍络合物,任选地使用其它配体。
2.6.位阻胺,例如:癸二酸二(2,2,6,6-四甲基-4-哌啶基)酯、琥珀酸二(2,2,6,6-四甲基-4-哌啶基)酯、癸二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯、癸二酸二(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)酯、正丁基-3,5-二叔丁基-4-羟基苄基丙二酸二(1,2,2,6,6-五甲基-4-哌啶基)酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶与琥珀酸的缩合产物,N,N’-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-叔辛基氨基-2,6-二氯-1,3,5-三嗪的线性或环状缩合产物,次氮基三乙酸三(2,2,6,6-四甲基-4-哌啶基)酯、1,2,3,4-丁烷四羧酸四(2,2,6,6-四甲基-4-哌啶基)酯、1,1’-(1,2-乙烷二基)二(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-硬脂酰基-2,2,6,6-四甲基哌啶、2-正丁基-2-(2-羟基-3,5-二叔丁基苄基)丙二酸二(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-2,4-二酮、癸二酸二(1-辛氧基-2,2,6,6-四甲基哌啶基)酯、琥珀酸二(1-辛氧基-2,2,6,6-四甲基哌啶基)酯,N,N’-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-吗啉基-2,6-二氯-1,3,5-三嗪的线性或环状缩合产物,2-氯-4,6-二(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪与1,2-二(3-氨基丙基氨基)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1,2-二(3-氨基丙基氨基)乙烷的缩合产物,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)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,4-十六烷氧基-和4-硬脂酰氧基-2,2,6,6-四甲基哌啶的混合物,N,N’-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺与4-环己基氨基-2,6-二氯-1,3,5-三嗪的缩合产物,1,2-二(3-氨基丙基氨基)乙烷与2,4,6-三氯-1,3,5-三嗪以及4-丁基氨基-2,2,6,6-四甲基哌啶的缩合产物(CAS登记序号[136504-96-6]);1,6-二氨基己烷与2,4,6-三氯-1,3,5-三嗪以及N,N-二丁基胺与4-丁基氨基-2,2,6,6-四甲基哌啶的缩合物(CAS登记序号[192268-64-7]);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、2-十一烷基-7,7,9,9-四甲基-1-氧杂-3,8-二氮杂-4-氧螺[4.5]癸烷,7,7,9,9-四甲基-2-环十一烷基-1-氧杂-3,8-二氮杂-4-氧螺[4.5]癸烷和表氯醇的反应产物、1,1-二(1,2,2,6,6-五甲基-4-哌啶氧基羰基)-2-(4-甲氧基苯基)乙烯、N,N’-二甲酰基-N,N’-二(2,2,6,6-四甲基-4-哌啶基)六亚甲基二胺,4-甲氧基亚甲基丙二酸与1,2,2,6,6-五甲基-4-羟基哌啶的二酯,聚[甲基丙基-3-氧-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷,马来酸酐/α-烯烃共聚物和2,2,6,6-四甲基-4-氨基哌啶或1,2,2,6,6-五甲基-4-氨基哌啶的反应产物。
2.7.草酸二酰胺,例如4,4′-二辛氧基-N,N’-草酰二苯胺,2,2′-二乙氧基-N,N’-草酰二苯胺,2,2′-二辛氧基-5,5′-二叔丁基-N,N’-草酰二苯胺,2,2′-双十二烷氧基-5,5′-二叔丁基-N,N’-草酰二苯胺,2-乙氧基-2′-乙基-N,N’-草酰二苯胺,N,N′-二(3-二甲基氨基丙基)-N,N’-草酰二苯胺,2-乙氧基-5-叔丁基-2′-乙基-N,N’-草酰二苯胺以及它们与2-乙氧基-2′-乙基-5,4′-二叔丁基-N,N’-草酰二苯胺的混合物,o-和p-甲氧基-以及o-和p-乙氧基-二取代的-N,N’-草酰二苯胺的混合物。
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)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2,4-二羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2,4-二(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)-4,6-二(4-甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-十二烷氧基苯基)-4,6-二(2,4-二甲基-苯基)-1,3,5-三嗪,2-(2-羟基-4-十三烷氧基苯基)-4,6-二(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]-4,6-二(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]-4,6-二(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]-4,6-二(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]-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,2-(2-羟基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪,2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪,2,4,6-三[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-1,3,5-三嗪,2-(2-羟基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪,2-{2-羟基-4-[3-(2-乙基己基-1-氧基)-2-羟基丙氧基]苯基}-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪。
3.金属钝化剂,例如:N,N’-二苯基草酰胺、N-水杨醛-N’-水杨酰肼、N,N’-二(水杨酰)肼、N,N’-二(3,5-二叔丁基-4-羟基苯基丙酰基)肼、3-水杨酰氨基-1,2,4-三唑、二(亚苄基)草酰二酰肼、N,N’-草酰二苯胺、间苯二甲酰二酰肼、癸二酰二苯基酰肼、N,N’-二乙酰基己二酸二酰肼、N,N’-二(水杨酰)草酸二酰肼、N,N’-二(水杨酰)硫代丙酸二酰肼。
4.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-双十四烷基羟基胺、N,N-双十六烷基羟基胺、N,N-双十八烷基羟基胺、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、衍生自氢化牛油胺的N,N-二烷基羟基胺。
5.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、从衍生自氢化牛油胺的N,N-二烷基羟基胺制备的硝酮。
6.过氧化物清除剂,例如:β-硫代二丙酸的酯,例如月桂基、硬脂基、十四烷基或十三烷基酯,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,双十八烷基二硫化物,四(β-十二烷基巯基)丙酸季戊四醇酯。
7.碱性助稳定剂,例如:三聚氰胺、聚乙烯基吡咯烷酮、二氰基二酰胺、氰脲酸三烯丙基酯、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,邻苯二酚锑或邻苯二酚锌。
8.成核剂,例如无机物质,例如滑石,金属氧化物,例如二氧化钛或氧化镁,磷酸盐,优选含有二氧杂磷结构部分的有机磷酸盐,最优选是它们的锂、钠和[Al(OH)]2+盐的形式,优选碱金属、碱土金属的碳酸盐或硫酸盐;单碱铝[Al(OH)]2+;有机化合物,例如单羧酸或多羧酸以及它们的衍生物,例如4-叔丁基苯甲酸,2,6-萘二甲酸,庚二酸,辛二酸,琥珀酸,己二酸,二苯基乙酸,偏苯三酸,苯甲酸,以及它们的任何碱金属盐或碱土金属盐或任何酰胺,例如琥珀酸钠或苯甲酸钠;或聚合化合物,例如离子共聚物(离聚物),另外是多元醇的二缩醛,例如1,3:2,4-二(3’,4’-二甲基亚苄基)山梨醇,1,3:2,4-二(五甲基二亚苄基)山梨醇,1,3:2,4-二(亚苄基)山梨醇,以及Irgaclear XT386(RTM,Ciba Inc)。
9.填料和增强剂,例如碳酸钙,硅酸盐,玻璃纤维,玻璃珠,石棉,滑石,高岭土,云母,硫酸钡,金属氧化物和氢氧化物,碳黑,石墨,木粉,以及其它天然产物的粉末或纤维,合成纤维;所谓的纳米材料,极细分散或剥离的层结构是特别有用的,例如蒙脱土、膨润土等,以及天然或合成的纳米管填料,例如多水高岭土、沸石或基于碳的纳米管,或石墨或氮化硼类型的层材料。
10.其它添加剂,例如增塑剂、润滑剂、乳化剂、颜料、流变添加剂、催化剂、流动控制剂、荧光增白剂、阻燃剂、抗静电剂和发泡剂。
11.苯并呋喃酮和吲哚满酮,例如:US4,325,863、US4,338,244、US5,175,312、US5,216,052、US 5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839、EP-A-0591102、EP-A-1291384中所描述的那些,或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’-二[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-甲氧基苯基)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-乙酰氧基-3,5-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-新戊酰氧基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2,3二甲基苯基)-5,7-二叔丁基苯并呋喃-2-酮、3-(2-乙酰基-5-异辛基苯基)-5-异辛基苯并呋喃-2-酮。
助稳定剂例如按照0.01-10%的浓度添加,基于要稳定的脂族聚酯的总重量计。
组分(a)、(c)、(c)和(d)的混合物可以尤其与UV吸收剂、光稳定剂和/或加工稳定剂一起使用。
填料和增强剂(在列表中的第9点)例如滑石、碳酸钙、云母或高岭土按照例如0.01-40%的浓度添加到聚烯烃中,基于要稳定的脂族聚酯的总重量计。
除了组分(a)、(b)、(c)和(d),其它优选的组合物还含有其它添加剂,尤其是高级脂肪酸的碱土金属盐,例如硬脂酸钙、乳酸钙和/或硬脂酰基-2-乳酸钙。
根据已知方法将组分(b)、(c)和(d)以及其它任选添加剂的混合物引入脂族聚酯中,例如在成型之前或期间引入模制品中,或通过用组分(b)、(c)和(d)的溶液或分散体涂覆脂族聚酯并随后蒸发溶剂。也可以将组分(b)、(c)和(d)以及其它任选添加剂的混合物以母料的形式加入要稳定的脂族聚酯中,所述母料通常以例如1.5-25重量%的浓度含有这些化合物。
组分(b)、(c)和(d)以及其它任选添加剂的混合物也可以在聚合之前或期间或者在交联之前加入。
组分(b)、(c)和(d)以及其它任选添加剂的混合物可以以纯形式或被包封在蜡、油或聚合物中的形式引入要稳定的材料中。
组分(b)、(c)和(d)以及其它任选添加剂的混合物也可以被喷到要稳定的脂族聚酯上。它们能用于稀释其它添加剂(例如上述常规的添加剂)或其熔体,使得它们也可以与这些添加剂一起喷到要稳定的聚合物上。在聚合催化剂的钝化期间通过喷涂施用是尤其有利的,在这种情况下喷涂方便地用那些用于钝化的蒸气进行。
按照此方式稳定的脂族聚酯可以以各种形式使用,例如作为膜、纤维、带、模塑组合物、型材,或作为用于涂料的粘合剂,尤其是粉末涂料、粘合剂或腻子。
本发明的一个优选实施方案也是一种稳定脂族聚酯以抵抗氧化降解、热降解或光诱导降解的方法,包括向脂族聚酯中引入或向脂族聚酯施用至少组分(b)、(c)和(d)以及其它任选添加剂的混合物。
本发明的另一个优选实施方案是组分(b)、(c)和(d)以及其它任选添加剂的混合物用做脂族聚酯的稳定剂以抵抗氧化降解、热降解或光诱导降解的用途。
优选用于此方法的组分(b)、(c)和(d)以及其它任选添加剂的混合物及其用途与上述对于脂族聚酯的组合物所述那些相同。
本发明的组合物可以有利地用于生产各种成型制品。例子是:
I-1)漂浮设备,海洋应用,浮桥,浮标,用于甲板的塑料管,管道,船,皮划艇,船桨,以及海岸增强材料。
I-2)汽车应用,尤其是保险杠,仪表盘,电池,后衬和前衬,在引擎罩下的模塑部件,衣帽架,卡车衬里,内衬,空气袋盖子,用于装备的电子模塑件(照明),用于仪表盘的镶板,头灯玻璃,仪器板,外衬,坐垫,汽车灯,头灯,停车灯,后灯,停止灯,内部和外部装饰;门板,气罐;发光前侧;后窗;座椅背,外板,电线绝缘,用于密封的型材挤出件,包层,中柱,底盘配件,消耗系统,燃料过滤器,燃料泵,燃料罐,车体侧模塑配件,可转式顶部,外镜,外部装饰,固定件/固定器,前端模件,玻璃,合叶,锁系统,行李箱/车顶行李架,压制/冲压件,密封件,侧面冲击保护,静音器/绝缘器和阳光车顶。
I-3)道路交通设施,尤其是标志牌,用于路标记的牌子,汽车附件,警示三角件,医疗箱,头盔,轮胎。
I-4)用于飞机、铁路、车辆(汽车、摩托车、卡车)的设备,包括家具。
I-5)用于航天应用的设备,尤其是火箭和卫星,例如重返罩。
I-6)用于建筑和设计、采矿应用,静音系统,街头保护区和庇护所的设备。
II-1)在一般和电子/电器设备中的设施、箱体和覆盖物(个人电脑、电话、手机、打印机、电视、音响设备),花盆,卫星TV接受器,以及表盘设备。
II-2)用于其它材料的夹套,例如不锈钢或织物。
II-3)用于电子工业的设备,尤其是用于插座的绝缘材料,尤其是电脑插座,用于电子和电器部件的外壳,印刷电路板,以及用于电子疏浚存储的材料,例如芯片、现金卡或信用卡。
II-4)电器,尤其是洗衣机,玻璃杯,炉子(微波炉),洗碟机,混合器,以及熨斗。
II-5)用于光的罩子(例如路灯、灯罩)。
II-6)用于电线和电缆中的装置(半导体、绝缘和电缆夹套)。
II-7)用于以下物品的箔:冷凝器,冰箱,加热设备,空调,电器的包封,半导体,咖啡机,以及真空清洁机。
III-1)技术制品,例如钝齿轮(齿轮),滑动配件,垫片,螺丝,螺栓,把手,以及扶手。
III-2)旋转叶片,换风机和风力发动机,太阳能设备,游泳池,游泳池覆盖物,池塘衬材,池塘衬垫,壁橱,衣柜,间隔壁,滑槽壁,折叠壁,屋顶,快门(例如自动瞄准干扰发射机快门),配件,管道件的连接件,套筒,以及传送带。
III-3)卫生间制品,尤其是淋浴间、马桶,覆盖物和水池。
III-4)卫生制品,尤其是尿布(婴儿,成人行动不便者),妇女卫生制品,浴帘,刷子,垫子,桶,活动厕所,牙刷,以及床垫。
III-5)用于水、废水和化学品的管道(交联或未交联),用于电线和电缆保护的管道,用于气体、油和下水道的管道,细石屑,下水管道,和排水系统。
III-6)具有任何几何形状的型材(窗框)和挡板。
III-7)玻璃替代品,尤其是挤出或共挤出的板,用于建筑物、航天、学校的玻璃窗(整料,双壁或多层壁),挤出的片材,用于建筑物玻璃窗、火车、运输、卫生制品和温室的窗膜。
III-8)板材(墙壁,切割板),挤出涂料(相片纸,纸张和管道涂层),筒仓,木材替代品,塑料木材,木材复合材料,墙壁,表面,家具,装饰箔,地面覆盖物(室内和室外应用),地板,甲板,以及瓷砖。
III-9)入口和出口岐管。
III-10)水泥、砖和复合材料的应用和覆盖物、档板和包层,硬轨,楼梯扶手,厨房台面面板,屋顶,屋顶片材,瓦,以及油布。
IV-1)板材(墙壁和切割板),塔板,人工玻璃,得富草皮,用于体育场的人造覆盖物(体育),用于体育场的人造地面(体育),以及塞子。
IV-2)连续和常产纤维的织造织物(地毯/卫生制品/土工织物/单丝;过滤器;擦布/幕帘(遮光物)/医疗应用),散纤维(应用例如是袍子/保护服),网,绳子,电缆,绳子,线,纱线,安全坐带,外衣,内衣,手套;靴子;橡胶靴,内衣,衣物,游泳衣,运动服,伞(遮阳伞,遮阳),降落伞,滑翔伞,帆,“气球绸”,野营制品,帐篷,充气床,阳光浴床,集装袋以及袋子。非织造织物,例如医用织物以及相关服装,工作服装,户外织物,室内家具以及结构织物。
IV-3)用于以下的膜、绝缘材料、覆盖材料和密封材料:屋顶、隧道、堆放场、池塘、仓库、墙壁封顶膜,农用膜,游泳池,帘子(遮光物)/防晒罩,雨篷,华盖,壁纸,食品包装(柔软和实心),医用包装(柔软和实心),空气囊/安全带,手垫和头垫,地毯,中心控制台,仪表盘,座舱,门,头顶控制模件,门内饰板,车顶内衬,内部照明,内部镜,置物板,后行李箱罩,坐椅,转向柱,方向盘,织物,以及舱室饰板。
V)膜(包装,仓库,层压,农牧业,温室,护盖物,隧道,青贮),托盘缠绕物,游泳池,垃圾袋,壁纸,拉伸膜,酒椰纤维,脱盐膜,电池,以及连接器。
VI-1)食品包装(柔软和实心),瓶子。
VI-2)储存系统,例如盒子(板条箱),行李箱,匣子,家用盒子,托盘,架子,导轨,螺丝盒,包,以及罐子。
VI-3)卡带,弹簧,医疗设备,用于任何运输的容器,垃圾筐和垃圾筒,垃圾袋,桶,垃圾桶,桶衬垫,轮式桶,常规容器,用于水/废水/化学品/气体/油/汽油/柴油的罐子;罐子衬垫,盒子,板条箱,电池外壳,槽,医疗设备例如活塞、眼科设备、诊断设备以及用于药物的吸塑包装。
VII-1)挤出物涂层(相纸,纸张,管道涂层),任何种类的家用制品(例如电池、热水瓶/衣架),固定系统例如塞子、电线和电缆端子,拉锁,闭塞物,锁,以及吸式闭合件。
VII-2)支持设备,用于休闲时间的制品,例如运动健身设备,体操垫,滑雪靴,轮滑鞋,滑雪板,脚蹼,运动表面(例如羽毛球场地);螺旋盖,瓶盖和瓶塞,以及罐子。
VII-3)常用家具,发泡制品(垫子,冲击吸收器),泡沫材料,海绵,洗碗布,垫子,花园座椅,体育场座椅,桌子,躺椅,玩具,建筑用针织物(板/图形/球),游乐室,滑盖,以及游戏设备。
VII-4)用于光学和磁力数据储存的材料。
VII-5)厨房器皿(餐具,饮用,烹饪,储存)。
VII-6)用于CD、磁带和录像带的盒子;DVD电子制品,任何类型的办公用品(圆珠笔,印台,鼠标,架子,导轨),任何体积和内容物的瓶子(饮料,洗涤剂,化妆品,包括香水),以及胶粘带。
VII-7)鞋子(鞋/鞋底),鞋垫,鞋罩,粘合剂,结构粘合剂,食品盒(水果,蔬菜,肉,鱼),合成纸,用于瓶子的标签,榻,人工关节(人),印刷板(胶版),印刷电路板,以及显示技术。
VII-8)填充聚合物的设备(滑石,白垩,粘土(高岭土),硅灰石,颜料,碳黑,TiO2,云母,纳米复合材料,白云石,硅酸盐,玻璃,石棉)。
因此,本发明的另一个实施方案涉及含有上述组合物的成型制品,尤其是膜、管道、型材、瓶、罐或容器,以及纤维。
本发明的另一个实施方案涉及含有上述组合物的模制品。模制品尤其通过注塑、吹塑、压塑、旋转模塑或沥铸成型或挤出获得。
以下实施例更详细地说明本发明。份数和百分比是按重量计。
粘度:
将基于聚乳酸的化合物溶解在氯仿中达到0.5g/dl的浓度。粘度是在乌氏粘度计(毛细管编号oC,0.36mm直径)中于25℃根据ISO 3105检测的。实验一次用仅仅含有聚合物的溶液进行,另一次用含有聚合物和稳定剂的溶液进行。对于每次检测,检测比粘度,这等于溶液的粘度减去溶剂的粘度,再除以溶剂的粘度,如下所示。
ηspec=(η溶液-η溶剂)/η溶剂
然后,计算含有稳定剂的溶液的比粘度与仅仅含有聚合物的溶液的比粘度之比,并用百分比表示。
比粘度之差=100*(ηspec化合物/ηspec聚合物)
比粘度之差越高,聚合物被稳定得越好。
亮度:
作为第二种方法,使用CIELAB色的亮度L*,这提供了对降解的目测评价的最接近标准。亮度L*表示以下含义:如果L*=0,则样品是黑色的;L*=100,则样品扩散白色。此检测在Dr.Lange的Micro Color II上进行,其中使用椭圆板进行预先校准,光源D65,角度8度。结果用未稳定的聚合物与被稳定的聚合物之间的亮度百分比之差表示。亮度L*的增加越多,聚合物的不利脱色越少。
热稳定性
聚合物的热稳定性用来自Metrohm的Thermomat 763评价。在此检测中,载气(空气流量7L/小时)经过被加热到230℃的3g探针,并将聚合物的挥发性物质输送到水池;检测水的电导率。实验持续6小时或直到水电导率达到200μS/cm。结果用未稳定的聚合物与被稳定的聚合物之间的电导率百分比之差表示。电导率的降低越多,聚合物被稳定得越好。
实施例1:聚乳酸的稳定
熔融温度为153℃(DSC检测,10K/min)的聚乳酸[来自美国NatureWorks的工业级]在16小时内于80℃在真空烘箱中干燥,然后与本发明的稳定剂于190℃在实验室级双螺杆挤出机中在氮气保护下混合。不含稳定剂的由聚乳酸组成的配料也进行预干燥并在相同条件下挤出。圆柱形挤出物在挤出后直接冷却到环境空气中。挤出的样品如上所述在6小时内进行热稳定性实验。然后如上所述检测粘度和亮度。结果列在表1中。
表1:
脚注的解释参见表3结尾处。
实施例2:聚乳酸的稳定。
先将熔融温度为150℃(DSC检测,10K/min)的聚乳酸[来自美国NatureWorks的工业级]在低温条件下研磨,然后加入添加剂(都是粉末形式)并用高速混合器混合。干混物然后在16小时内在真空烘箱中于80℃干燥,并在Berstorff双螺杆挤出机(L/D 32,D=25mm)上于190℃在氮气保护下挤出,并在水下立即冷却挤出物。不含稳定剂的由已研磨的聚乳酸组成的配料也进行预干燥并在相同条件下挤出。结果列在表2中。
表2:
脚注的解释参见表3结尾处。
实施例3:聚乳酸的稳定
先将熔融温度为150℃(DSC检测,10K/min)的聚乳酸[来自美国NatureWorks的工业级]在低温条件下研磨,然后加入添加剂(都是粉末形式)并用高速混合器混合。干混物然后在16小时内在真空烘箱中于80℃干燥,并在Haake双螺杆挤出机(L/D 25,D=16mm)上于190℃在氮气保护下挤出,并在水下立即冷却挤出物。不含稳定剂的由已研磨的聚乳酸组成的配料也进行预干燥并在相同条件下挤出。结果列在表3中。
表3:
a)对比实施例
b)本发明的实施例
c)Irganox 1076(RTM)(Ciba Inc.)是3-(3′,5′-二叔丁基-4-羟基苯基)丙酸
十八烷基酯
d)Irgafos 126(RTM)(Ciba Inc.)是二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯。
e)Irganox 3052(RTM)(Ciba Inc.)是2-丙烯酸,2-(1,1-二甲基乙基)-6-[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]甲基-4-甲基苯基酯。
f)Irganox PS802(RTM)(Ciba Inc.)是双十八烷基3,3′-硫代二丙酸酯。
g)Irganox 245(RTM)(Ciba Inc.)是亚乙基二(氧亚乙基)二(3-(5-叔丁基甲基-4-羟基-间-甲苯基)-丙酸酯)。
此结果显示,同样在所有总浓度相同(0.4%)的情况下,本发明的三组分组合物显示出比单个组分更好的效果,即证明了具有协同效果。
Claims (13)
1.一种组合物,其含有:
a)脂族聚酯,
b)酚类抗氧化剂,
c)亚磷酸酯或亚膦酸酯,和
d)硫代协同剂。
2.权利要求1的组合物,其中组分a)是基于乳酸的聚酯。
3.权利要求1或2的组合物,其中组分a)是聚乳酸。
4.权利要求1-3的组合物,其中组分b)选自:季戊四基-四[3-(3′,5′-二叔丁基-4-羟基苯基)]丙酸酯,十八烷基3-(3′,5′-二叔丁基-4-羟基苯基)丙酸酯,亚乙基二(氧亚乙基)二-(3-(5-叔丁基-4-羟基-间-甲苯基)-丙酸酯),α-生育酚,2,3-二[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]丙酰肼,2-丙烯酸,2-(1,1-二甲基乙基)-6-[3-(1,1-二甲基乙基)-2-羟基-5-甲基苯基]甲基-4-甲基苯基酯,3,3′,3″,5,5′,5″-六叔丁基-α,α’,α”-(基-2,4,6-三基)三-对-甲酚,N,N’-己烷-1,6-二基二[3-(3,5-二叔丁基-4-羟基苯基丙酰胺)],二乙基((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)膦酸酯,六亚甲基二(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯),二((3,5-二(1,1-二甲基乙基)-4-羟基苯基)甲基)-乙基膦酸)钙,1,3,5-三(4-叔丁基-3-羟基-2,6-二甲苯基)甲基)-1,3,5-三嗪-2,4,6-(1H,3H,5H)-三酮,1,3,5-三(3,5-二叔丁基-4-羟基苄基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮,(2,4,6-三氧-1,3,5-三嗪-1,3,5(2H,4H,6H)-三基)三亚乙基三(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯),与1,3,5-三(2-羟基乙基)-s-三嗪-2,4,6(1H,3H,5H)-三酮的3,5-二叔丁基-4-羟基氢化肉桂酸三酯,2,6-二叔丁基-4-(4,6-二(辛基硫代)-1,3,5-三嗪-2-基氨基)苯酚,苯丙酸3,5-二(1,1-二甲基乙基)-4-羟基-,C7-C9-支化和直链烷基酯,6,6′-二叔丁基-2,2′-硫代二-对-甲酚,2,2′-硫代二亚乙基-二(3,5-二叔丁基-4-羟基苯基)丙酸酯,2,6-二叔丁基-4-甲基-苯酚,1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯基)苯,二(3,3-二(4′-羟基-3′-叔丁基苯基)丁酸)二醇酯,4,4′-硫代二(2-叔丁基-5-甲基苯酚),2,2′-亚甲基-二(6-(1-甲基-环己基)-对-甲酚),1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷,3,9-二[1,1-二甲基-2-[(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基]-2,4,8,10-四氧杂螺杂[5.5]十一烷,2,6-二叔丁基苯酚,2,6-二叔丁基-4-壬基苯酚,4,4′-亚丁基二(6-叔丁基-3-甲基苯酚),2,2′-亚甲基二(4-甲基-6-叔丁基苯酚),2,2′-亚甲基二(4-乙基-6-叔丁基苯酚),2,2′-亚乙基二(4,6-二叔丁基苯酚),1,1-二(2-甲基-4-羟基-5-叔丁基苯基)丁烷,2,5-二叔戊基氢醌,4,6-二(辛基硫代甲基)-邻-甲酚和4,6-二(十二烷基硫代甲基)-邻-甲酚,或它们的混合物。
5.权利要求1-4的组合物,其中组分c)是选自:三(2,4-二叔丁基苯基)亚磷酸酯,二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯,四[(2,4-二叔丁基苯基)-4,4-亚联苯基二亚膦酸酯],三(壬基苯基)亚磷酸酯,二(2,4-二叔丁基-6-甲基苯基)-乙基-亚磷酸酯,2,2’2”-次氮基[三乙基-三[3,3’,5,5’-四-叔丁基-1,1’-二苯基-2,2’-二基]]亚磷酸酯,二-硬脂基-季戊四基-二亚磷酸酯,二(2,4-二枯基苯基)季戊四醇二亚磷酸酯,(2,4,6-三叔丁基苯酚)-2-丁基-2-乙基-1,3-丙二醇亚磷酸酯,二[2,6-二叔丁基-4-甲基苯基]-季戊四醇二亚磷酸酯,二[壬基苯基]季戊四醇二亚磷酸酯和2,2-亚甲基-二(4,6-二叔丁基苯基)-辛基亚磷酸酯,或它们的混合物。
6.权利要求1-5的组合物,其中组分d)是选自:双-十八烷基3,3′-硫代二丙酸酯,双-十二烷基3,3′-硫代二丙酸酯,混合的月桂基-硬脂基硫代二丙酸酯,双肉豆蔻基硫代二丙酸酯,双-棕榈基/硬脂基-硫代二丙酸酯,月桂基-硬脂基-硫代二丙酸酯,双-十三烷基-硫代二丙酸酯,双-十八烷基二硫化物,二叔十二烷基二硫化物,季戊四醇辛基硫代二丙酸酯,季戊四醇-四(3-月桂基硫代丙酸酯),或它们的混合物。
7.权利要求1-6的组合物,其中组分(b)的存在量是0.01-0.80%,基于组分(a)的重量计。
8.权利要求1-7的组合物,其中组分(c)的存在量是0.01-0.60%,基于组分(a)的重量计。
9.权利要求1-8的组合物,其中组分(d)的存在量是0.01-0.40%,基于组分(a)的重量计。
10.权利要求1-9的组合物,其中除了组分(a)、(b)、(c)和(d)之外还含有其它添加剂。
11.权利要求10的组合物,其含有作为其它添加剂的UV吸收剂、光稳定剂和/或加工稳定剂。
12.一种稳定脂族聚酯以抵抗氧化降解、热降解或光诱导降解的方法,包括向脂族聚酯中引入或向脂族聚酯施用根据权利要求1的至少一种组分(b)、(c)和(d)。
13.根据权利要求1的组分(b)、(c)和(d)的混合物用做脂族聚酯的稳定剂以抵抗氧化降解、热降解或光诱导降解的用途。
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EP (1) | EP2297239A1 (zh) |
JP (1) | JP2011526317A (zh) |
KR (1) | KR20110038042A (zh) |
CN (1) | CN102137890A (zh) |
WO (1) | WO2010000638A1 (zh) |
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2009
- 2009-06-23 EP EP09772338A patent/EP2297239A1/en not_active Withdrawn
- 2009-06-23 CN CN2009801338116A patent/CN102137890A/zh active Pending
- 2009-06-23 US US13/000,134 patent/US20110144246A1/en not_active Abandoned
- 2009-06-23 WO PCT/EP2009/057766 patent/WO2010000638A1/en active Application Filing
- 2009-06-23 KR KR1020117001336A patent/KR20110038042A/ko not_active Application Discontinuation
- 2009-06-23 JP JP2011515341A patent/JP2011526317A/ja not_active Withdrawn
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CN102617842A (zh) * | 2012-03-29 | 2012-08-01 | 金发科技股份有限公司 | 一种锑/钛复合催化剂及其用于制备pet共聚酯的方法 |
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CN104164060A (zh) * | 2014-07-22 | 2014-11-26 | 江南大学 | 一种可生物堆肥聚酯材料组合物及其制备方法 |
CN104164060B (zh) * | 2014-07-22 | 2016-04-06 | 江南大学 | 一种可生物堆肥聚酯材料组合物及其制备方法 |
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CN112912442A (zh) * | 2018-08-30 | 2021-06-04 | 杜邦聚合物公司 | 具有改善的热稳定性的共聚醚酯配制品 |
CN112912442B (zh) * | 2018-08-30 | 2023-06-20 | 杜邦聚合物公司 | 具有改善的热稳定性的共聚醚酯配制品 |
CN109796752A (zh) * | 2019-01-22 | 2019-05-24 | 重庆鑫翎创福光电科技股份有限公司 | 一种抗老化聚酰胺组合物及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US20110144246A1 (en) | 2011-06-16 |
KR20110038042A (ko) | 2011-04-13 |
EP2297239A1 (en) | 2011-03-23 |
WO2010000638A1 (en) | 2010-01-07 |
JP2011526317A (ja) | 2011-10-06 |
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