CN101155866A - 防止环状烯烃共聚物光分解的组合物和方法 - Google Patents
防止环状烯烃共聚物光分解的组合物和方法 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
本发明揭示一种稳定的环状共聚物组合物和对环状共聚物制品,如挤出或模塑制品或双轴取向带或膜进行稳定,以防止制品因暴露于UV光而发生分解的方法以及稳定的环状烯烃共聚物制品。该制品采用下述方法形成:将环状烯烃共聚物材料与约50-2000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约250-5000ppm至少一种分子量小于约500的低分子量HALS以及任选的约250-5000ppm低聚HALS混合,其中,HALS与三嗪光吸收剂的重量比值约为7∶1至20∶1,形成稳定的环状烯烃共聚物组合物,并由该稳定的环状烯烃共聚物组合物形成挤出或模塑的制品或膜。
Description
技术领域
本发明涉及在保护环状烯烃共聚材料免受紫外辐射或紫外光(“UV光”)中的组合物及其应用。具体地,本发明涉及包含至少一种邻羟基三芳基三嗪UV光吸收剂和至少一种低分子量位阻胺光稳定剂(“HALS”)的协同组合的组合物。该组合物还可以包含至少一种低聚HALS。
背景技术
近来,一些公司已经引进有乙烯的环状烯烃共聚物(COP)的生产线。这些材料具有优良的光性质、大于丙烯酸类或聚碳酸酯的UV透射率、良好的尺寸稳定性、良好的热挠曲以及良好的阻氧性和防水性。这些COP材料的可能的应用中,有用于数据存储/检索系统的透镜、用于LCD的光漫射器和光导以及用于HID灯的壳体。然而,COP因为光稳定性差而在这些应用中的许多应用受到限制。
众所周知,特别是来自阳光的紫外(UV)光或辐射能使聚合物如COP降解,经常导致脆化,泛黄或起雾。然而,这种降解现象可以通过在由聚合物制成的制品内或制品上加入紫外光稳定剂和紫外光吸收剂得到抑制。
例如,单独或组合使用HALS和UV光吸收剂(“UVA”)来稳定聚合物材料为本领域公知。具体地,最初使用UV光吸收剂如苯并三唑和二苯甲酮来稳定聚合物材料,并防止这类材料暴露于UV光时发生降解。后来发现,HALS能清除聚合物材料暴露于UV光时形成的自由基,比UV光吸收剂更有效,因此,目前,在大多数常规应用中UV光吸收剂与至少一种HALS组合使用。
美国专利第4,619,956号揭示一种使聚烯烃聚合物膜、涂层或模塑制品稳定,能抗光、湿气和氧的作用的方法。该方法包括在聚合物中加入HALS和三芳基-2-三嗪UV光吸收剂。
UV光吸收剂和HALS各自的用量约为0.01-5重量%,但是只列举了UV光吸收剂和HALS的量相等的配方。据说该组合物能有效稳定聚合物材料,聚合物材料在暴露于UV光约1,000至2,400小时后才开始失去光泽或变黄。
美国专利第4,331,586号(Hardy)揭示用作光稳定剂的低聚物。虽然提供了对聚合物材料如聚丙烯的保护,但是含揭示的低聚HALS的聚合物膜在暴露于UV光约1,700小时后仍会成为脆性。
因此,仍需要能稳定聚合物材料,尤其环状烯烃共聚物并能长时期提供暴露于UV光时的保护的组合物及其使用方法。本发明提供了这类方法和组合物。
发明内容
本发明涉及UV稳定的环状烯烃聚合物和由这种聚合物制成的制品,如数据存储/检索系统、用于LCD的光漫射器和光导以及用于HID灯的壳体。本发明的制品包含环状烯烃聚合物材料,约50-5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约500ppm-1.25%的至少一种分子量小于约500的低分子量HALS,其中,HALS与三嗪的重量比值约为3∶1至20∶1,优选约5∶1至10∶1,最优选约6∶1至7.5∶1。该聚合物制品优选是厚度不小于约1mm的模塑制品或挤出制品。
用于本发明的低分子量HALS是数均分子量小于约500的单官能或双官能HALS,包括但不限于以下:
二(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯,以及琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇(piperidineethanol)的聚合物。
用于本发明的第三任选组分的低聚HALS包括但不限于通式(I)的低聚物:
通式(I)
式中,R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己基胺,X和X1可以相同或不同,是氢、C1-C20烷基,或通式(II)的基团:
通式(II)
式中,R1表示氢、C2-C3羟基烷基、C1-C8烷基、酰基、烷氧基、羟基或烃氧基(oxyl);R2表示氢、C1-C8烷基或苄基;R3和R4可以相同或不同,是C1-C8烷基、苄基或苯乙基,或来自C5-C10环烷基;Z是直链或支链的C2-C20亚烷基或者被至少一个氧代、硫代或中断的直链或支链的C2-C20亚烷基,中的R5是氢、C1-C20烷基,或者是通式(II)的基团;C5-C10亚环烷基,
C6-C12亚芳基或者C8-C14芳基亚烷基;n是大于1的整数;Y是卤原子、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基、吗啉代、环己基胺或
式中,X、X1和Z按照前面定义;条件是X和X1中至少一个是通式(II)的基团。最优选X和X1是相同或不同的,是通式(II)的基团,其中R是吗啉代或辛基胺,R1是H或CH3,R2是H,R3和R4是CH3,Z是C6H12,Y是吗啉代、辛基胺或其中,X、X1和Z按照前面定义。
能用于本发明的其它HALS包括但是不限于以下:
通常,三嗪光吸收剂为通式(III)的化合物
式中,A、B和C中2个或3个是芳族,A、B和C中至少一个被连接于三嗪的点的邻位羟基取代,R1至R9各自选自下组:氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基。该三嗪光吸收剂优选是通式(IV)的化合物:
式中,R10、R11、R12和R13可以相同或不同,各自独立地选自下组:氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基,R14是氢或C1-C18烷基。最优选,R10、R11、R12和R13是H或CH3,R14是氢、C6H13或C8H17。
其它有用的三嗪光吸收剂包括但不限于:
2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-(己基)氧-苯酚,
2-(4-((2-羟基-3-十二烷氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,
2-(4-((2-羟基-3-十三烷氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,
2-(4-((2-羟基-3-十三烷氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,和
2-(4-((2-羟基-3-异辛氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,以及它们的混合物。
光稳定的聚合物制品优选由共聚物形成,最优选由环状烯烃的共聚物形成,并且可以是以下的聚合反应的产物:
式中,R1、R2、R3是H。
能用于本发明的环状烯烃聚合物包括但不限于:
A-系列 C-系列 D-系列
B-系列
本发明还涉及光稳定的添加剂组合物,该组合物包含至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量小于约500的低分子量HALS,以及任选的至少一种低聚HALS,其中HALS与三嗪光吸收剂的重量比值约为3∶1至20∶1,更优选约7∶1至20∶1,还涉及光稳定的添加剂母料,其包含约30-98重量%,优选约50-95重量%的环状烯烃聚合物树脂、至少一种邻羟基三芳基三嗪光吸收剂和至少一种分子量小于约500的低分子量HALS,以及任选的至少一种低聚HALS,其中,HALS与三嗪光吸收剂的重量比值约为3∶1至20∶1,更优选约7∶1至20∶1,所述母料可以是粒料、颗粒或锭剂。添加剂组合物可以采用喷雾光吸收剂和HALS的溶液、熔融混合、挤出,或者采用物理压实的方法形成。
本发明还涉及形成稳定的聚合物制品的方法。该方法包括:将聚合物材料与约50-5,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约500ppm至约1.25%的至少一种低聚的、聚合物的或者分子量至少约为500高分子量的HALS混合,其中HALS与三嗪光吸收剂的重量比值约为3∶1至20∶1,形成稳定的聚合物组合物,然后由该稳定的聚合物组合物形成挤出或模塑的制品,或者双轴取向带或膜。
具体实施方式
本发明涉及用来稳定聚合物材料,如模塑或挤出的制品、双轴取向带或膜以及涂层的组合物,防止聚合物材料暴露于UV光时发生降解。已出乎意料地发现当约50-5,000ppm(每百万份的份数)邻羟基三芳基三嗪和约500ppm至约1.25%的低分子量HALS与环状烯烃聚合物材料混合,HALS与三嗪的重量比值约为1∶1至20∶1,优选约7∶1至10∶1时,环状烯烃聚合物材料暴露于UV光时受到保护的时间明显大于由包含HALS、UV光吸收剂或它们的组合的任何现有技术光稳定剂组合物提供的保护时间。
适合用作所述任选第三组分的低聚HALS是在美国专利第4,331,586号中揭示的类型的低聚物,该专利内容全文引用结合于此。
能用于本发明的低聚HALS包括但不限于通式(I)的低聚物:
式中,R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己基氨基,优选是吗啉代或辛基胺,X和X1可以相同或不同,表示氢、C1-C20烷基或者下式(II)的基团:
式中,R1表示氢、C2-C3羟烷基、C1-C8烷基、羟基或烃氧基(oxyl);R2表示氢、C1-C8烷基或苄基;R3和R4可以相同或不同,表示C1-C8烷基、苄基或苯乙基,或者与它们连接的碳一起形成一个C5-C10环烷基;Z表示C2-C20直链或支链的亚烷基,其中,亚烷基(alkaline)链被氧代、硫代或的基团中断,该式中R5表示氢、C1-C20烷基或(II)的基团;C5-C10亚环烷基,
C6-C12亚芳基或C8-C14芳基亚烷基;n是大于1的整数;Y表示卤原子、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基、吗啉代,或该式中,X、X1和Z按照前面的定义;条件是通式(II)中至少一个哌啶基部分存在于重复单元中。
通式(I)的优选组合物是其中的X和X1都是通式(II)的部分的那些。通式(I)的特别优选的组合物是其中的X和X1都是2,2,6,6-四甲基-4-哌啶基,而Z是1,6-亚己基的那些。
能用于本发明作为UV光吸收剂的邻羟基三芳基三嗪是美国专利4,619,956中揭示的类型,该专利的内容全文引用结合于此。一般而言,本发明的三嗪光吸收剂是通式(III)的化合物:
式中,A、B和C中的2个或3个各自是芳族,A、B和C中的至少一个被连接于三嗪环的点的邻位羟基取代,R1至R9各自选自下组:氢、羟基、烷基、烷氧基、磺基、羧基、卤素、卤代烷基和酰氨基。
优选三嗪光吸收剂是通式(IV)的化合物:
式中,R10、R11、R12和R13按照上面对R1至R9所述,最优选是H或CH3,R14是氢或C1至C18烷基,最优选是氢、C6烷基和C8烷基。
通常,COP制品如模塑或挤出的制品、双轴取向带或膜可以通过本发明得到稳定,即,以环状烯烃材料的重量为基准,将约50-2,000ppm的本发明的三嗪光吸收剂和约250-5000ppm的本发明的低分子量HALS与用来形成制品的环状烯烃聚合物材料混合。任选地,可以加入约250-5000ppm低聚HALS。总HALS与三嗪光吸收剂的比值通常约为20∶1至10∶1,优选约10∶1至1∶1,最优选约20∶1至7∶1。
虽然本发明的低分子量HALS、任选的低聚HALS和三嗪光吸收剂可以在采用本领域已知的任何方法来加工COP材料期间逐一加入到COP材料中,但是,可以在进行加工前形成两种组分的混合物。通常,本发明的添加剂组合物成形为本发明的含HALS和UV光吸收剂的粒料、颗粒或锭剂。这可以采用以下方法完成,将HALS和三嗪熔融在一起,挤出该混合物,喷雾两种组分在一起的溶液,蒸发溶剂后,或者通过物理压实形成该混合物的粒料或颗粒。
本发明的光稳定的添加剂组合物还可以以母料的形式提供,该母料包含约2-70%,优选约5-50%的添加剂组合物,余量包含COP树脂,其中HALS与三嗪光吸收剂的比值通常约为20∶1至1∶1,优选约10∶1至7∶1。
任选地,组合物可以含有其它添加剂,尤其是如抗氧化剂、辅助光稳定剂、增塑剂、阻燃剂、抗静电剂和防滑剂、填料、染料、颜料等的添加剂。
合适的抗氧化剂包括:位阻酚类,如
2,6-二-叔丁基-对-甲酚;
4,4′-二(2,6-二-叔丁基苯酚);
四[亚甲基(3,5-二叔丁基)4-羟基-氢化肉桂酸酯]]甲烷;
1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)-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)-s-三嗪-2,4,6-(1H,3H,5H)-三酮;
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;
2[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧杂phosphepin-6-基]氧]-N,N-二[2[[2,4,8,10-四(1,1-二甲基乙基)二苯并[d,f][1,3,2]二氧杂phosphepin-6-基]氧]乙胺;
氧化的二(牛油烷基)胺;
4,4′-二(2,6-二异丙基苯酚);
2,4,6-三-叔丁基苯酚;
2,2′-硫代二(4-甲基-6-叔丁基苯酚);
2(3′,5′-二-叔丁基-4-′羟基苯基)-丙酸十八烷酯,等;
硫代二丙酸的酯,如硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯等;
亚磷酸烃基酯,如亚磷酸三苯酯、亚磷酸三壬酯、二亚磷酸二异癸基季戊四醇酯、亚磷酸二苯基癸酯,等;以及它们的组合。
合适的辅助光稳定剂包括苯并三唑类,如2-(2′-羟基-5-叔辛基苯基)苯并三唑;2(2′-羟基-3=-5=-二-叔丁基苯基)-5-氯苯并三唑;羟基二苯甲酮类,如2-羟基-4-甲氧基二苯甲酮;2-羟基-4-辛氧基二苯甲酮;2,2′-二羟基-4,4′-二-甲氧基二苯甲酮;位阻酚酯,如3,5-二-叔丁基-4-羟基苯甲酸正十六烷酯和3,5-二-丁基-4-羟基苯甲酸2′4′-二-叔丁基苯酯;2,2′-硫代二(4-叔辛基苯酚)的金属配合物;二(4-叔辛基苯基)砜的镍配合物;二丁基二硫代氨基甲酸镍;4-羟基-3-二-叔丁基苄基磷酸单烷基酯的镍盐,其中的烷基是甲基、乙基、丙基、丁基等;2-羟基-4-甲基苯基十一烷基酮肟的镍配合物等。
可以由本发明保护免受UV光的COP制品包括但不限于:模塑或挤出制品、涂层、带和膜。所述制品可以通过挤出、片材挤出、注塑、吹塑、注坯吹塑、旋转模塑或滚塑、压延、热成形、压塑、真空模塑、压力成型、反应注塑和本领域已知的其它类似方法形成。此外,涂层可以采用以下方法施加:粉末涂装、挤出涂装、电泳涂漆、喷雾、浸涂以及本领域已知的其它类似的方法。
实施例
下面的非限制性实施例仅用来说明本发明的优选实施方式,不构成对本发明的限制,本发明的范围由所附权利要求书限定。
实施例
TOPAS 5013(Ticona)树脂与下表列出的添加剂进行干混。然后,将这些干混合物直接加入注塑机(Arburg,location)。简体温度向着喷嘴逐渐升高,为240℃、255℃、265℃和275℃。模具温度为121℃。
下面实施例中添加剂的浓度
UV-3346 | UV-3853 | UV-1194 | |
A | 2670ppm | 330ppm | |
B | 2655ppm | 345ppm | |
C | 1778ppm | 1000ppm | 222ppm |
D |
评价注塑板的复制样品的最初颜色(L,a,b色标)和雾度(按照%雾度测定)。然后将这些样品置于按ASTM G155(AZ-干)条件操作的氙弧老化试验机(Ci65,Atlas老化试验机)。按时从该老化试验机取样,测定颜色和雾度。结果示于下表。
表1.随氙弧老化试验机曝光而变的总色位移(ΔE)
400h | 800h | 1200h | 1600h | 2000h | |
UV-3346+UV-1164 | 0.23 | 0.61 | 1.16 | 2.02 | 3.2 |
UV-3853+UV-1164 | 0.23 | 0.34 | 0.6 | 0.89 | 1.35 |
UV-3346+UV-3853+UV-1164 | 0.23 | 0.29 | 0.34 | 0.51 | 0.79 |
无UV | 0.95 | 3.22 | 6.09 |
表2.随氙弧老化试验机曝光而变的黄度指数(Y1)
400h | 800h | 1200h | 1600h | 2000h | |
UV-3346+UV-1164 | 3.22 | 3.7 | 4.36 | 5.19 | 5.94 |
UV-3853+UV-1164 | 3.17 | 3.38 | 3.66 | 3.95 | 4.36 |
UV-3346+UV-3853+UV-1164 | 3.01 | 3.11 | 3.35 | 3.54 | 3.77 |
无UV | 3.94 | 6.34 | 9.75 |
表3.随氙弧老化试验机曝光而变的板透明度(%雾度)
0h | 800h | 1600h | 2000h | |
UV-3346+UV-1164 | 2.57 | 3.62 | 5.31 | 8.11 |
UV-3853+UV-1164 | 1.71 | 1.86 | 3.17 | 4.39 |
UV-3346+UV-3853+UV-1164 | 1.36 | 2.05 | 2.8 | 3.72 |
无UV | 2.51 | 8.51 |
虽然很明显,可以认为在此揭示的本发明满足了上述的目的,但是,应理解,本领域的技术人员可以作出各种变动和实施方式。因此,所附权利要求书覆盖了在本发明的真正精神和范围之内的所有这类变动和实施方式。
Claims (11)
1.一种聚合物制品,该制品包含环状烯烃聚合物材料、约50-2,000ppm的至少一种邻羟基三芳基三嗪光吸收剂和约250-2000ppm的至少一种数均分子量小于约500的低分子量HALS,其中,HALS与三嗪的重量比约为1∶1至20∶1。
2.如权利要求1所述的环状烯烃聚合物制品,其特征在于,该制品还包含约20-5000ppm的低聚HALS。
3.环状烯烃聚合物制品,其特征在于,HALS与三嗪光吸收剂之比约为7∶1至10∶1。
4.如权利要求2所述的聚合物制品,其特征在于,所述低聚HALS是通式(I)的低聚物:
式中,R是吗啉代、C1-C8烷基胺、二(C1-C8)烷基胺、吡咯烷基或环己基胺,X和X1相同或不同,是氢、C1-C20烷基或通式(II)的基团:
式中,R1表示氢、C2-C3羟烷基、C1-C8烷基、羟基或烃氧基;R2表示氢、C1-C8烷基或苄基;R3和R4相同或不同,是C1-C8烷基、苄基或苯乙基,或形成C5-C10环烷基;Z是直链或支链的C2-C20亚烷基,或被至少一个氧代、硫代或基团中断的直链或支链的C2-C20亚烷基链,该式中R5是氢、C1-C20烷基或通式(II)的基团;C5-C10亚环烷基,
5.如权利要求4所述的环状烯烃聚合物制品,其特征在于,X和X1相同或不同,是通式(II)的基团,其中R是吗啉代或辛基胺,R1是H或CH3,R2是H,R3和R4是CH3,Z是C6H12,Y是吗啉代、辛基胺、或该式中X、X1和Z按前述定义。
6.如权利要求2所述的环状烯烃聚合物制品,其特征在于,所述低聚HALS选自下组:
二(1-辛氧基-2,2,6,6,四甲基-4-哌啶基)癸二酸酯,琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物,琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物及N,N=-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-戊胺的聚合物的混合物,
1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-乙二基二[[[(4,6-二[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基)亚氨基]-3,1-丙二基]]-二[N=N==-二丁基-N=,N==-二(1,2,2,6,6-五甲基-4-哌啶基),
1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-乙二基二[[[(4,6-二[丁基(1-环己氧基-2,2,6,6-四甲基-4-哌啶基)氨基]-1,3,5-三嗪-2-基)亚氨基]-3,1-丙二基]]-二[N=N==-二丁基-N=,N==-二(1,2,2,6,6-五甲基-4-哌啶基),
1,3,5-三嗪-2,4,6-三胺,N,N===[1,2-乙二基二[[[(4,6-二[丁基(1,2,2,6,6-五甲基-4-哌啶基)氨基]-2-基)亚氨基]-3,1丙二基]]-二[N=N==-二丁基-N=,N==-二(1,2,2,6,6-五甲基-4-哌啶基),
N,N=-二(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺与2,4,6-三氯-1,3,5-三嗪和2,4,4-三甲基-1,2-戊胺的聚合物,
聚甲基丙基-3-氧-(4(2.2.6.6-四甲基)哌啶基)硅氧烷,
聚甲基丙基-3-氧-(4(1,2.2.6.6-五甲基)哌啶基)硅氧烷,
四甲基-7-氧杂-3,20-二氮杂-21-氧杂-二螺(5.1.11.12)二十一烷与表氯醇反应的聚烷基-1-氧杂-二氮杂螺癸烷产物,
1,3-丙二胺,N,N==-1,2-乙二基二-,与2,4,6-三氯-1.3.5-三嗪的聚合物,与N-丁基-2,2,6,6-四甲基-4-哌啶胺的反应产物。
7.如权利要求1所述的环状烯烃聚合物制品,其特征在于,所述低分子量HALS包括:
二(1-辛氧基-2,2,6,6,四甲基-4-哌啶基)癸二酸酯,以及琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物。
10.如权利要求8所述的聚合物制品,其特征在于,R10、R11、R12和R13是H或CH3,R14是氢,C6H13或C8H17。
11.如权利要求7所述的聚合物制品,其特征在于,所述三嗪光吸收剂选自下组:
2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-(己基)氧-苯酚,
2-(4-((2-羟基-3-十二烷氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,
2-(4-((2-羟基-3-十三烷氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪,和
2-(4-((2-羟基-3-异辛氧基丙基)-氧基-2-羟基苯基)-4,6-二(2,4-二甲基苯基)-1,3,5-三嗪。
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US4331586A (en) | 1981-07-20 | 1982-05-25 | American Cyanamid Company | Novel light stabilizers for polymers |
US4619956A (en) | 1985-05-03 | 1986-10-28 | American Cyanamid Co. | Stabilization of high solids coatings with synergistic combinations |
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US6051164A (en) * | 1998-04-30 | 2000-04-18 | Cytec Technology Corp. | Methods and compositions for protecting polymers from UV light |
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