CN1777494A - 天然产物复合物 - Google Patents
天然产物复合物 Download PDFInfo
- Publication number
- CN1777494A CN1777494A CNA2004800107111A CN200480010711A CN1777494A CN 1777494 A CN1777494 A CN 1777494A CN A2004800107111 A CNA2004800107111 A CN A2004800107111A CN 200480010711 A CN200480010711 A CN 200480010711A CN 1777494 A CN1777494 A CN 1777494A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- hydroxyl
- mixture
- hydroxy
- triazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 7
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- PXMNMQRDXWABCY-UHFFFAOYSA-N 1-(4-chlorophenyl)-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol Chemical compound C1=NC=NN1CC(O)(C(C)(C)C)CCC1=CC=C(Cl)C=C1 PXMNMQRDXWABCY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002023 wood Substances 0.000 abstract description 10
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Abstract
本发明公开了对微生物生长的有害效果起保护的天然产物复合物,其含有至少一种天然产物、至少一种热塑性树脂和抗真菌剂。复合物通过在其中加入至少一种选自光稳定剂和选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物进一步有利地保护以防止气候和颜色形成。光稳定剂选自紫外光吸收剂和空间位阻胺。金属氧化物是例如CaO。天然产物是例如木屑、亚麻、***、黄麻、洋麻或稻壳。热塑性树脂是例如聚乙烯或聚丙烯。抗真菌剂和有效辅助添加剂经熔融加工,例如挤出、共同捏合、拉挤成形和注塑加入,抗真菌剂是例如噻苯咪唑。
Description
天然产物复合物,例如木材/塑料复合物通过经熔融挤出在其中加入抗真菌剂有效防止微生物。进一步包括光稳定剂和/或某些防污添加剂有效地保护复合物防止光、热、氧、潮湿和化学作用的有害影响。
木材和木材复合物防止微生物是已知的。
US6,323,224教导了使用已知的硝基亚甲基或硝基亚氨基化合物作为用于消灭昆虫的防止技术材料的试剂,还公开了杀真菌剂、杀菌剂和杀藻剂的同时使用。
US6,527,981公开了用作广谱杀真菌木材防腐剂的吡咯和氯化胺的同时使用。
JP-A-2000 017773教导了防虫塑胶木材。
JP-A-06 143205教导了防霉木材塑料复合物的生产。
JP-A-2000 136105公开了防止虫害的木材。
US公开的申请No.2001/0027217公开了用于木材或木材复合物板,其含有酚化合物和其它抗虫、抗担子菌、抗白蚁和抗真菌剂。
Mokuzai Kenkyu Shiryo(1983),17,122-31公开了化学抑制以在橡胶木材上预防木材变色和发霉。
US6,290,885公开了天然产物复合物。
天然产物复合物在暴露于日光和气候时在非常短的时间内(通常几周)改变成银灰外观。此外,经过化学相互作用(与金属的鞣酸相互作用)和/或真菌生长会出现黑色锈渍。需要用特定的涂层和/或用不同化学品清洁的重复表面处理以处理这些问题。
化学相互作用是例如与金属源(铁钉)的鞣酸相互作用,产生不需要的锈蚀,微生物生长、气候(热、光、潮湿和氧)和化学相互作用的结果均导致不需要的颜色变化。
出乎意料的是,我们发现抗真菌剂在经熔融挤出加入天然产物复合物时,抗真菌剂是尤其有效的。噻苯咪唑、至少一种选自光稳定剂和/或至少一种选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物的组合是用于保护天然产物复合物以防微生物、气候和化学相互作用的尤其有效的体系。
本发明的保护体系经熔融挤出加入天然产物复合物提供了长期的改善耐候和颜色稳定性的效果,这以成本有效的途径提供了不需维修的产品。
公开了制备防止由于微生物生长、气候和化学相互作用引起的颜色变化的天然产物复合物的方法,该方法包括将天然产物、至少一种热塑性树脂、抗真菌剂混合成混合物,熔融加工该混合物。
公开了制备防止由于微生物生长、气候和化学相互作用引起的颜色变化的天然产物复合物的方法,该方法包括混合至少一种天然产物、至少一种热塑性树脂、抗真菌剂和至少一种选自光稳定剂和/或选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物成混合物,熔融加工混合物。
抗真菌剂是例如在US公开号2001/0027217和U.S.No.6,323,224和6,527,981中公开的那些。
抗真菌剂是例如苯并咪唑、卤代苯酚、取代的三嗪、异硫代azolinones、异噻唑、氧基联苯氧基胂、噻苯咪唑和/或无机化合物(含有铜、银、锡、锌等的物质)。
抗真菌剂是例如选自噻苯咪唑、噻苯咪唑的盐(例如与连二磷酸)、10,10’氧基联苯氧基胂、tebuconazole、tolnaftate、二-(2-吡啶-1-氧化物)锌、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-辛基-4-异噻唑啉、正丁基-1,2-苯并异噻唑啉-3-酮、多菌灵和它们的混合物。
卤代苯酚是例如2,4,4’-三氯-2’-羟基二苯基醚。
卤代苯酚和无机化合物在例如2001年9月21日申请的US专利申请No.09/957,959中公开。
噻苯咪唑和进一步与至少一种光稳定剂和/或至少一种选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物结合的噻苯咪唑是保护天然产物复合物防止微生物和风化尤其有效的体系。本发明的添加剂体系在保护天然产物复合物防止由于微生物的生长、风化(光、热、氧和潮湿)和化学相互作用引起的锈蚀是尤其有效的。
噻苯咪唑是2-(4-噻唑基)苯并咪唑,CAS#148-79-8。
噻苯咪唑是例如对例如交链孢菌属、曲霉菌属,例如曲霉菌niger、曲霉菌repens和aspeffllus flavus、金杆菌pullulans、葡萄胞属、毛壳菌globosum、枝孢菌herbarum、镰刀菌属、青霉菌属、葡萄穗霉菌属、ventriculum属等。
抗真菌剂以例如基于整个混合物重量计,按重量计0.05%-3%的含量存在于本发明的复合物中。例如抗真菌剂以基于整个混合物重量计,按重量计约0.05%-约1.0%的含量存在,例如抗真菌剂以基于整个混合物重量计,按重量计约0.1%-约0.8%,约0.2%-约0.6%或约0.3%-约0.5%的含量存在。例如,抗真菌剂以按重量计约0.05%-约0.5%,约0.05%-约0.6%或约0.05%-约0.8%存在。例如抗真菌剂以按重量计约0.1%-1.0%,约0.2%-约1.0%,或约0.3%-约1.0%存在。
光稳定剂选自空间位阻胺光稳定剂(HALS)和紫外光吸收剂(UVA),例如2H-苯并***、二苯酮、苯甲酸酯、丙烯酸酯、丙二酸酯、草酰胺、水杨酸酯、苯并噁嗪-4-酮和s-三嗪。
2H-苯并***或2-(2-羧基苯基)-2H-苯并***是例如在US专利3,004,896、3,055,896、3,072,585、3,074,910、3,189,615、3,218,332、3,230,194、4,127,586、4,226,763、4,275,004、4,278,589、4,315,848、4,347,180、4,383,863、4,675,352、4,681,905、4,853,471、5,268,450、5,278,314、5,280,124、5,319,091、5,410,071、5,436,349、5,516,914、5,554,760、5,563,242、5,574,166、5,607,987、5,977,219和6,166,218中公开的物质,例如2-(2-羟基-5-甲基苯基)-2H-苯并***、2-(3,5-二-叔丁基-2-羟基苯基)-2H-苯并***、2-(2-羟基-5-叔丁基苯基)-2H-苯并***、2-(2-羟基-5-叔辛基苯基)-2H-苯并***、5-氯-2-(3,5-二-叔丁基-2-羟基苯基)-2H-苯并***、5-氯-2-(3-叔丁基-2-羟基-5-甲基苯基)-2H-苯并***、2-(3-仲丁基-5-叔丁基-2-羟基苯基)-2H-苯并***、2-(2-羟基-4-辛氧基苯基)-2H-苯并***、2-(3,5-二-叔戊基-2-羟基苯基)-2H-苯并***、2-(3,5-二-α-枯基-2-羟基苯基)-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-(ω-羟基-八(亚乙氧基)羰基-乙基)-苯基)-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基)乙基苯基)-2H-苯并***、十二烷基化2-(2-羟基-5-甲基苯基)-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基乙基)苯基)-5-氯-2H-苯并***、2-(3-叔丁基-5-(2-(2-乙基己氧基)-羰基乙基)-2-羟基苯基)-5-氯-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)-5-氯-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-甲氧基羰基乙基)苯基)-2H-苯并***、2-(3-叔丁基-5-(2-(2-乙基己氧基)羰基乙基)-2-羟基苯基)-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-异辛氧基羰基乙基)苯基)-2H-苯并***、2,2’-亚甲基-双(4-叔辛基-(6-2H-苯并***-2-基)苯酚)、2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***、2-(2-羟基-3-叔辛基-5-α-枯基苯基)-2H-苯并***、5-氟-2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并***、5-氯-2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并***、5-氯-2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***、2-(3-叔丁基-2-羟基-5-(2-异辛氧基羰基乙基)苯基)-5-氯-2H-苯并***、5-三氟甲基-2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***、5-三氟甲基-2-(2-羟基-5-叔辛基苯基)-2H-苯并***、5-三氟甲基-2-(2-羟基-3,5-二叔辛基苯基)-2H-苯并***、3-(5-三氟甲基-2H-苯并***-2-基)-5-叔丁基-4-羟基肉桂酸氢甲酯、5-丁基磺酰基-2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***、5-三氟甲基-2-(2-羟基-3-α-枯基-5-叔丁基苯基)-2H-苯并***、5-三氟甲基-2-(2-羟基-3,5-二叔丁基苯基)-2H-苯并***、5-三氟甲基-2-(2-羟基-3,5-二-α-枯基苯基)-2H-苯并***、5-丁基磺酰基-2-(2-羟基-3,5-二叔丁基苯基)-2H-苯并***和5-苯基磺酰基-2-(2-羟基-3,5-二叔丁基苯基)-2H-苯并***。
二苯酮或2-羟基二苯酮是例如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。
取代和未取代的苯甲酸的酯是例如4-叔丁基苯基水杨酸酯、苯基水杨酸酯、辛基苯基水杨酸酯、二苯甲酰基间苯二酚、双(4-叔丁基苯甲酰基)间苯二酚、苯甲酰基间苯二酚、2,4-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯、十六烷基3,5-二叔丁基-4-羟基苯甲酸酯、十八烷基3,5-二叔丁基-4-羟基苯甲酸酯、2-甲基-4,6-二叔丁基苯基3,5-二叔丁基-4-羟基苯甲酸酯。
丙烯酸酯和丙二酸酯是例如α-氰基-β,β-二苯基丙烯酸乙酯或异辛基酯、α-羰基甲氧基-肉桂酸甲酯、α-氰基-β-甲基-p-甲氧基-肉桂酸甲酯或酰基酯、α-羰基甲氧基-p-甲氧基-肉桂酸甲酯、N-(β-羰基甲氧基-β-氰基乙烯基)-2-甲基-二氢吲哚,SanduvorPR25、二甲基p-甲氧基亚苄基丙二酸酯(CAS#7443-25-6)和SanduvorPR31,二-(1,2,2,6,6-五甲基哌啶-4-基)p-甲氧基亚苄基丙二酸酯(CAS#147783-69-5)。
草酰胺是例如4,4’-二辛氧基草酰替苯胺、2,2’-二乙氧基草酰替苯胺、2,2′-二辛氧基-5,5’-二-叔丁氧基草酰替苯胺、2,2’-双十二氧基-5,5’-二-叔丁氧基草酰替苯胺、2-乙氧基-2’-乙基草酰替苯胺、N,N’-二(3-二甲基氨基丙基)草酰胺、2-乙氧基-5-叔丁基-2’-乙氧基草酰胺和它们与2-乙氧基-2’-乙基-5,4’-二-叔丁氧基草酰胺的混合物、o-和p-甲氧基二取代的草酰替苯胺的混合物和o-和p-乙氧基二取代的草酰替苯胺的混合物。
苯并噁嗪酮UV吸收剂是例如2,2’-p-亚苯基-二(3,1-苯并噁嗪-4-酮),Cyasorb3638(CAS#18600-59-4)。
s-三嗪或三芳基-o-羟基苯基-s-三嗪,例如已知的商业s-三嗪是例如如US3,843,371、4,619,956、4,740,542、5,096,489、5,106,891、5,298,067、5,300,414、5,354,794、5,461,151、5,476,937、5,489,503、5,543,518、5,556,973、5,597,854、5,681,955、5,726,309、5,736,597、5,942,626、5,959,008、5,998,116、6,013,704、6,060,543、6,187,919、6,242,598和6,468,958中所公开的,例如4,6-二-(2,4-二甲基苯基)-2-(2-羟基-4-辛氧基苯基)-s-三嗪,Cyasorb1164,Cytec Corp、4,6-二-(2,4-二甲基苯基)-2-(2,4-二羟基苯基)-s-三嗪、2,4-二(2,4-二羟基苯基)-6-(4-氯苯基)-s-三嗪、2,4-二[2-羟基-4-(2羟基乙氧基)苯基]-6-(4-氯苯基)-s-三嗪、2,4-二[2-羟基-4-(2-羟基-4-(2-羟基乙氧基)苯基)-6-(2,4-二甲基苯基)-s-三嗪、2,4-二[2-羟基-4-(2-羟基乙氧基)苯基]-6-(4-溴苯基)-s-三嗪、2,4-二[2-羟基-4-(2-乙酰氧基乙氧基)苯基]-6-(4-氯苯基)-s-三嗪、2,4-二(2,4-二羟基苯基)-6-(2,4-二甲基苯基)-s-三嗪、2,4-二(4-联苯基)-6-(2-羟基-4-辛氧基羰基亚己基氧苯基)-s-三嗪、2-苯基-4-[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-6-[2-羟基-4-(3-仲戊氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-苄氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4-二(2-羟基-4-正丁氧基苯基)-6-(2,4-二-正丁氧基苯基)-s-三嗪、2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-壬氧基*-2-羟基丙氧基)-5-α-枯基苯基]-s-三嗪(*表示辛氧基、壬氧基和癸氧基的混合物)、亚甲基二-{2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-s-三嗪}、以5∶4∶1比率在3∶5’、5∶5’和3∶3’位置桥接的亚甲基桥接二聚体混合物、2,4,6-三(2-羟基-4-异辛氧基羰基亚异丙基氧基苯基)-s-三嗪、2,4-二(2,4-二甲基苯基)-6-(2-羟基-4-己氧基-5-α-枯基苯基)-s-三嗪、2-(2,4,6-三甲基苯基)-4,6-二[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-s-三嗪、2,4,6-三[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-s-三嗪、4,6-二-(2,4-二甲基苯基)-2-(2-羟基-4-(3-十二烷氧基-2-羟基丙氧基)-苯基)-s-三嗪和4,6-二-(2,4-二甲基苯基)-2-(2-羟基-4-(3-十三烷氧基-2-羟基丙氧基)-苯基)-s-三嗪的混合物,Tinuvin400,Ciba Specialty Chemicals Corp.、4,6-二-(2,4-二甲基苯基)-2-(2-羟基-4-(3-(2-乙基己氧基)-2-羟基丙氧基)-苯基)-s-三嗪和4,6-二苯基-2-(4-己氧基-2-羟基苯基)-s-三嗪。
紫外光吸收剂(UVA)尤其选自2H-苯并***、二苯酮和s-三嗪。
例如,本发明的紫外光吸收剂选自
2-(2-羟基-5-甲基苯基)-2H-苯并***;
2-(2-羟基-5-叔辛基苯基)-2H-苯并***;
2-(2-羟基-3,5-二-叔戊基苯基)-2H-苯并***;
3-(苯并***-2-基)-5-叔丁基4-羟基肉桂酸氢辛基酯;
2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并***;
2-(2-羟基-5-叔丁基苯基)-2H-苯并***;
2-(2-羟基-3,5-二-叔丁基苯基)-2H-苯并***;
2-(2-羟基-3-叔丁基-5-甲基苯基)-2H-苯并***;
2-(2-羟基-3-仲丁基-5-叔丁基苯基)-2H-苯并***;
2-(2-羟基-4-辛氧基苯基)-2H-苯并***;
2-(2-羟基-3-十二烷基-5-甲基苯基)-2H-苯并***;
2-[2-羟基-3,5-二(α,α-二甲基苄基)苯基]-2H-苯并***;
2-[2-羟基-3-(α,α-二甲基苄基)-5-叔辛基苯基]-2H-苯并***;
2-[2-羟基-3-叔丁基-5-[2-(ω-羟基-八(亚乙氧基)羰基)乙基]-苯基]-2H-苯并***;
2-{2-羟基-3-叔丁基-5-[2-(辛氧基)羰基]乙基}苯基}-2H-苯并***;
5-三氟甲基-2-(2-羟基-3-α-枯基-5-叔辛基苯基)-2H-苯并***;
5-氯-2-(3,5-二-叔丁基-2-羟基苯基)-2H-苯并***;
2-(3-叔丁基-2-羟基-5-(2-辛氧基羰基乙基)苯基)-5-氯-2H-苯并***;
4-辛氧基-2-羟基二苯酮;
4-甲氧基-2-羟基二苯酮;
4-甲氧基-2,2’-二羟基二苯酮;
4,4’-二乙氧基-2,2’-二羟基二苯酮;
2,4-二[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-6-三甲基苯基-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-(2-羟基-4-辛氧基苯基)-s-三嗪,CYASORB1164,Cytec;
2,4-二苯基-6-(2-羟基-4-己氧基苯基)-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-十二-/十三烷氧基-2-羟基丙氧基)-苯基]-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-十二-/十三烷氧基-2-羟基丙氧基)-5-a-枯基苯基]-s-三嗪;
2,4,6-三(2,4-二羟基苯基)-s-三嗪与异辛基α-卤代丙酸酯的反应产物;
2-(2,4-二丁氧基苯基)-4,6-二(2-羟基-4-丁氧基苯基)-s-三嗪;
2,4-二(4-联苯基)-6-(2-羟基-4-辛氧基羰基亚乙氧基苯基)-s-三嗪;
2-苯基-4-[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-6-[2-羟基-4-(3-仲-戊氧基-2-羟基丙氧基)苯基]-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-苄氧基-2-羟基丙氧基)苯基]-s-三嗪;
2,4-二(2-羟基-4-丁氧基苯基)-6-(2,4-二-丁氧基苯基)-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-壬氧基*-2-羟基丙氧基)-5-α-枯基苯基]-s-三嗪(*表示辛氧基、壬氧基和癸氧基的混合物);
亚甲基二-{2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-丁氧基-2-羟基-丙氧基)苯基]-s-三嗪},以5∶4∶1比率在3∶5’、5∶5’和3∶3’位置桥接的亚甲基桥接二聚体混合物;
2,4,6-三(2-羟基-4-异辛氧基羰基亚异丙基氧基苯基)-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-(2-羟基-4-己氧基-5-α-枯基苯基)-s-三嗪;和
2,4,6-三[2-羟基-4-(3-仲丁氧基-2-羟基丙氧基)苯基]-s-三嗪。
在本发明的另一实施方案中,紫外光吸收剂选自
2-(2-羟基-5-叔辛基苯基)-2H-苯并***;
2-[2-羟基-3-(α,α-二甲基苄基)-5-叔辛基苯基]-2H-苯并***;
2-{2-羟基-3-叔丁基-5-[2-(ω-羟基-八(亚乙氧基)羰基)乙基]-苯基}-2H-苯并***;
2-{2-羟基-3-叔丁基-5-[2-(辛氧基)羰基]乙基}苯基}-2H-苯并***;
4-辛氧基-2-羟基二苯酮;
4-甲氧基-2-羟基二苯酮;
2,4-二[2-羟基-4-(3-丁氧基-2-羟基丙氧基)苯基]-6-三甲基苯基-s-三嗪;
2,4,6-三(2,4-二羟基苯基)-s-三嗪与异辛基α-卤代-丙酸酯的反应产物;
2,4-二(4-联苯基)-6-(2-羟基-4-辛氧基羰基亚乙氧基苯基)-s-三嗪;
2,4-二(2,4-二甲基苯基)-6-[2-羟基-4-(3-壬氧基*-2-羟基丙氧基)-5-α-枯基苯基]-s-三嗪(*表示辛氧基、壬氧基和癸氧基的混合物);和
2,4,6-三(2-羟基-4-异辛氧基羰基亚异丙基氧基苯基)-s-三嗪。
本发明的位阻胺是例如单体化合物或低聚或聚合化合物。
本发明的空间位阻胺是例如N-H、N-OH、N-烷基、N-烷氧基、N-环烷氧基、N-酰基、N-酰氧基、N-芳烷氧基、N-羟基烷氧基或N-羟基环烷氧基位阻胺。
本发明的位阻胺是例如四甲基哌啶基的。
烷基是直链或支链的,是例如甲基、乙基、正丙基、正丁基、仲丁基、叔丁基、正己基、正辛基、2-乙基己基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十六烷基或正十八烷基。
环烷基包括环戊基和环己基;典型芳烷基包括苄基、α-甲基-苄基、α,α-二甲基苄基和苯乙基。
位阻胺稳定剂是现有技术中已知的,它们在例如US5,004,770、5,204,473、5,096,950、5,300,544、5,112,890、5,124,378、5,145,893、5,216,156、5,844,026、6,117,995、6,271,377、6,392,041、6,376,584、6,472,456和2001年8月15日申请的US专利申请Nos.60/312,517和2000年11月16日申请的09/714,717。
US6,271,377、6,392,041和6,376,584公开了位阻羟基烷氧基胺和羟基环烷氧基胺稳定剂。位阻羟基烷氧基胺稳定剂还称为N-羟基烷氧基位阻胺或NORo1 HALS。
本发明的空间位阻胺稳定剂是例如4-羟基-2,2,6,6-四甲基哌啶、1-烯丙基-4-羟基-2,2,6,6-四甲基哌啶、1-苄基-4-羟基-2,2,6,6-四甲基哌啶、二(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、二(2,2,6,6-四甲基-4-哌啶基)琥珀酸酯、二(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、二(1-辛基氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、二(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二叔丁基-4-羟基苄基丙二酸酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的缩合物、N,N′-二(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-1,3,5-三嗪的线性或环状缩合物、三(2,2,6,6-四甲基-4-哌啶基)次氮基三乙酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷-四羧酸酯、1,1’-(1,2-乙烷二基)-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-硬脂基氧基-2,2,6,6-四甲基哌啶、二(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]癸烷-2,4-二酮、二(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、二(1-辛氧基-2,2,6,6-四甲基哌啶基)琥珀酸酯、N,N′-二(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-1,3,5-三嗪的线性或环状缩合物、2-氯-4,6-双(4-正丁基氨基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪和1,2-二(3-氨基丙基氨基)乙烷的缩合物、2-氯-4,6-双(4-正丁基氨基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪和1,2-二(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]癸烷-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、4-十六烷基氧基-和4-十八烷基氧基-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)六亚甲基二胺和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)己烷和2,4,6-三氯-1,3,5-三嗪的缩合产物以及4-丁基氨基-2,2,6,6-四甲基哌啶(CAS Reg.No.[136504-96-6])、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-氧代螺[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-氧代螺[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-哌啶基氧基羰基)-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-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]硅氧烷、马来酸酐-α-烯烃共聚物与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。
空间位阻胺还可以是在US5,980,783中描述的化合物,即组分I-a)、I-b)、I-c)、I-d)、I-e)、I-f)、I-g)、I-h)、I-i)、I-j)、I-k)或I-1)的化合物,尤其是在所述US5,980,783的64-72栏中列出的光稳定剂1-a-1、1-a-2、1-b-1、1-c-1、1-c-2、1-d-1、1-d-2、1-d-3、1-e-1、1-f-1、1-g-1、1-g-2或1-k-1。
空间位阻胺还可以是在US6,046,304和6,297,299中描述的化合物之一,例如在权利要求10或38或实施例1-12或D-1至D-5中描述的化合物。
本发明的空间位阻胺还可以是在N-原子被羟基-取代烷氧基取代的物质,例如化合物,如1-(2-羟基-2-甲基丙氧基)-4-十八碳酰氧基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-十六碳酰氧基-2,2,6,6-四甲基哌啶、1-氧基-4-羟基-2,2,6,6-四甲基哌啶与叔戊醇的碳游离基的反应产物、1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶、1-(2-羟基-2-甲基丙氧基)-4-氧代-2,2,6,6-四甲基哌啶、二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)癸二酸酯、二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6四甲基哌啶-4-基)己二酸酯、二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)琥珀酸酯、二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)戊二酸酯或2,4-二{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]-N-丁基氨基}-6-(2-羟基乙基氨基)-s-三嗪。
本发明的合适位阻胺包括例如:
二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
二(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯;
二(1,2,2,6,6-五甲基哌啶-4-基)(3,5-二-叔丁基-4-羟基苄基)丁基丙二酸酯;
4-苯甲酰基氧基-2,2,6,6-四甲基哌啶;
4-硬脂基氧基-2,2,6,6-四甲基哌啶;
三(2,2,6,6-四甲基哌啶-4-基)次氮基三乙酸酯;
2,4-二氯-6-叔辛基氨基-s-三嗪和4,4’-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)的聚缩合产物;
1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的聚缩合产物;
4,4′-六亚甲基二-(氨基-2,2,6,6-四甲基-哌啶)和1,2-二溴乙烷的聚缩合产物;
四(2,2,6,6-四甲基哌啶-4-基)1,2,3,4-丁烷四羧酸酯;
四(1,2,2,6,6-五甲基哌啶-4-基)1,2,3,4-丁烷四羧酸酯;
2,4-二氯-6-吗啉代-s-三嗪和4,4′-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)的聚缩合产物;
N,N’,N”,N-四[(4,6-二(丁基-1,2,2,6,6-五甲基哌啶-4-基)-氨基-s-三嗪-2-基1)-1,10-二氨基-4,7-二氮杂癸烷;
八亚甲基二(2,2,6,6-四甲基哌啶-4-羧酸酯);
N-2,2,6,6-四甲基哌啶-4-基-正十二烷基琥珀酰亚胺;
N-1,2,2,6,6-五甲基哌啶-4-基-正十二烷基琥珀酰亚胺;
N-1-乙酰基-2,2,6,6-四甲基哌啶-4-基-正十二烷基琥珀酰亚胺;
4-C15-C17链烷酰氧基-2,2,6,6-四甲基哌啶;
2,4-二氯-6-环己基氨基-s-三嗪和4,4′-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)的聚缩合产物;
1,5-二(2,2,6,6-四甲基哌啶-4-基)-1,5-二氮杂-4-氧代丙烷;
甲基丙烯酸甲酯、丙烯酸乙酯和2,2,6,6-四甲基哌啶-4-基丙烯酸酯的共聚物;
N-十八烷基马来酰亚胺、苯乙烯和N-(2,2,6,6-四甲基哌啶-4-基)马来酰亚胺;
1,3,5-三[3-(2,2,6,6-哌啶-4-基氨基)-2-羟基-丙基]异氰脲酸酯;
含有由N-[2-(2,2,6,6-四甲基哌啶-4-基)草酰亚氨-1-基]马来酰亚胺产生的单元的烯烃共聚物;
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;
3-(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-20-基)丙酸C12-C14烷基酯;
表氯醇与2,2,4,4-四甲基-7-氧杂-3,20-二氮杂-21-氧代-二螺[5,1,11,2]二十一烷的反应产物;
1,3-二(2,2,6,6-四甲基哌啶-4-基)2,4-双十三烷基丁烷四羧酸酯;
1,3-二(1,2,2,6,6-五甲基哌啶-4-基)2,4-双十三烷基丁烷四羧酸酯;
3,9-二(1,1-二甲基-2-羟基乙基)-2,4,8,10-四氧杂螺[5.5]十一烷、1,2,3,4-丁烷四羧酸四甲酯和2,2,6,6-四甲基-4-羟基哌啶的聚缩合产物;
3,9-二(1,1-二甲基-2-羟基乙基)-2,4,8,10-四氧杂螺[5.5]十一烷、1,2,3,4-丁烷四羧酸四甲酯和1,2,2,6,6-五甲基-4-羟基哌啶的聚缩合产物;
1,4-二(2,2,6,6-四甲基哌啶-4-基)-2,2-二甲基-1,4-二氮杂4-氧代丙烷;
4-氨基-2,2,6,6-四甲基哌啶和四甲醇基亚乙酰基二脲的反应产物;
1,6-六亚甲基二[N-甲酰基-N-(2,2,6,6-四甲基哌啶-4-基)胺];
N-(2,2,6,6-四甲基哌啶-4-基)马来酰亚胺和C20-C24-α-烯烃的共聚物;
聚[3-(2,2,6,6-四甲基哌啶-4-基氧基)丙基-甲基-硅氧烷];
2,4-二氯-6-[N-丁基-N-(2,2,6,6-四甲基哌啶-4-基)氨基]-s-三嗪和1,10-二氨基-4,7-二氮杂癸烷的聚缩合产物;
3-(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-20-基)丙酸十二烷基酯;
1-环己基氧基-2,2,6,6-四甲基-4-十八烷基氨基哌啶;
二(1-辛氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
(2,4-二[(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)丁基氨基]-6-(2-羟基-乙基氨基-s-三嗪;
二(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)己二酸酯;
2,4-二[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪;
1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶;
1-(2-羟基-2-甲基丙氧基)-4-氧代-2,2,6,6-四甲基哌啶;
1-(2-羟基-2-甲基丙氧基)-4-十八碳酰氧基-2,2,6,6-四甲基哌啶;
二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)己二酸酯;
2,4-二{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]-N-丁基-氨基}-6-(2-羟基乙基氨基)-s-三嗪;
2,4-二[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N′-二(3-氨基丙基)乙二胺)的反应产物[CAS Reg.No.191680-81-6];和
下式的化合物:
其中n是1-15,它在US6,117,995的实施例2中公开。
例如,本发明的位阻胺是选自如下的化合物:
二(2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
二(1,2,2,6,6-五甲基哌啶-4-基)癸二酸酯;
二(1,2,2,6,6-五甲基哌啶-4-基)(3,5-二-叔丁基-4-羟基苄基)丁基丙二酸酯;
2,4-二氯-6-叔辛基氨基-s-三嗪和4,4’-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)聚缩合产物;
1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的聚缩合产物;
N,N’,N”,N-四[(4,6-二(丁基-1,2,2,6,6-五甲基哌啶-4-基)-氨基-s-三嗪-2-基)-1,10-二氨基-4,7-二氮杂癸烷;
二(1-辛氧基-2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
2,4-二[(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)丁基氨基]-6-(2-羟基-乙基氨基-s-三嗪;
二(1-环己基氧基-2,2,6,6-四甲基哌啶-4-基)己二酸酯;
2,4-二[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪;
1-(2-羟基-2-甲基丙氧基)-4-羟基-2,2,6,6-四甲基哌啶;
1-(2-羟基-2-甲基丙氧基)-4-氧代-2,2,6,6-四甲基哌啶;
1-(2-羟基-2-甲基丙氧基)-4-十八碳酰氧基-2,2,6,6-四甲基哌啶;
二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)癸二酸酯;
二(1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基)己二酸酯;
2,4-二{N-[1-(2-羟基-2-甲基丙氧基)-2,2,6,6-四甲基哌啶-4-基]-N-丁基-氨基}-6-(2-羟基乙基氨基)-s-三嗪;
2,4-二[(1-环己基氧基-2,2,6,6-哌啶-4-基)丁基氨基]-6-氯-s-三嗪与N,N′-二(3-氨基丙基)乙二胺)的反应产物[CAS Reg.No.191680-81-6];和或
下式的化合物:
其中n是1-15。
可以预计,可采用不同种类的紫外光吸收剂的组合,同样,可采用不同种类的位阻胺(例如未取代的位阻胺和N-烷氧基位阻胺)。同样,可有利地采用紫外光吸收剂和位阻胺的组合。
因此,感兴趣的是包含至少两种不同空间位阻胺光稳定剂或至少一种空间位阻胺光稳定剂和至少一种紫外光吸收剂的方法。
光稳定剂可以基于整个混合物的重量,按重量计0.1%-5%,例如按重量计约0.2%-约3%或按重量计约0.5%-约2%的含量应用于本发明的复合物中。例如,基于整个混合物重量,光稳定剂以按重量计约0.1%-约3%,约0.1%-约2%,约0.2%-约5%或约0.5%-约5%存在。
基于整个混合物的重量,Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐以按重量计0.5%-10%存在于本发明的复合物中。例如,基于整个混合物的重量,这些添加剂以按重量计约1%-约8%,约2%-约6%或约3%-约5%存在。例如,这些添加剂以按重量计约0.5%-约5%,约0.5%-约6%,或约0.5%-约8%存在。例如,这些添加剂以按重量计约1%-约10%,约2%-约10%或约3%-约10%存在。
感兴趣的是方法,其中选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物是水滑石、Al2O3、CaO、MgO或ZnO。
氧化钙(CaO)、氧化镁(MgO)和氧化锌(ZnO)是在本发明中尤其有效的添加剂的特定实例。
天然产物复合物通过组合木材(纤维)、木屑、椰子壳、甘蔗begasse、亚麻、***、黄麻、洋麻、稻壳等与热塑性树脂提供。它们可以是例如在US6,290,885和6,511,757中公开的天然纤维/塑料复合物,热塑性树脂组分和天然产物组分均可来自再生的材料。
复合物是挤出产物形式,例如压制木材、粒子板、木屑板、胶合板、夹板、叠层材料等。
复合物可用作建筑和房屋材料,例如装饰、栅栏、框架和成型、窗和门轮廓、招牌、屋顶、壁板等。它们可以用于例如汽车应用,例如内部仪表板、架子和备用轮胎盖。天然产物复合物适用于基础结构,例如木板路、码头和相关结构。它们还可用于消费者/工业应用,例如作为野餐桌、公园长椅、托盘等。复合物可用于替代目前由木材、热塑性塑料或金属或其组合生产的部件。
热塑性树脂是合成树脂,其选自:
1.单烯烃和二烯烃的聚合物,例如聚丙烯、聚异丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基环己烷、聚异戊烯或聚丁二烯,以及环烯烃,例如环戊烯或降冰片烯的聚合物、聚乙烯(它任选可交联),例如高密度聚乙烯(HDPE)、高密度和高分子量聚乙烯(HDPE-HMW)、高密度和超高分子量聚乙烯(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)、(VLDPE)和(ULDPE);
2.在1)中提到的聚合物的混合物,例如聚丙烯与聚异丁烯、聚丙烯和聚乙烯的混合物(例如PP/HDPE、PP/LDPE)和不同类型的聚乙烯的混合物(例如LDPE/HDPE);
3.单烯烃和二烯烃互相或与其它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(LLDPE)和其与低低密度聚乙烯(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-烯烃是就地产生的、丙烯/丁二烯共聚物、异丁烯/异戊烯共聚物、乙烯/乙烯基环己烯共聚物、乙烯/烷基丙烯酸酯共聚物、乙烯/烷基甲基丙烯酸酯共聚物、乙烯/乙烯基乙酸酯共聚物或乙烯/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;和该共聚物互相和与在如上1)中提到的聚合物的混合物,例如聚丙烯/乙烯-丙烯共聚物、LDPE/乙烯-乙烯基乙酸酯共聚物(EVA)、LDPE/乙烯-丙烯酸共聚物(EAA)、LLDPE/EVA、LLDPE/EAA和交互或无规聚烯烃/一氧化碳共聚物和它们与其它聚合物,例如聚酰胺的混合物;
4.烃树脂(例如C5-C9),包括其氢化改性(例如增粘剂)和聚烯烃和淀粉的混合物;1.)-4.)的均聚物和共聚物可带有任何立体结构,包括间规、全规、半全规或无规的,其中优选无规聚合物。还包括立体嵌段聚合物;
5.聚苯乙烯、聚(p-甲基苯乙烯)、聚(α-甲基苯乙烯);
6.由乙烯基芳香单体,包括苯乙烯、α-甲基苯乙烯衍生的芳香均聚物和共聚物,乙烯基甲苯的所有异构体,尤其是p-乙烯基甲苯、乙基苯乙烯、丙基苯乙烯、乙烯基联苯、乙烯基萘和乙烯基蒽的所有异构体和它们的混合物。均聚物和共聚物可带有任何立体结构,包括间规、全规、半全规或无规的,其中优选无规聚合物。还包括立体嵌段聚合物;
6a.共聚物,包括上述乙烯基芳香单体和选自乙烯、丙烯、二烯烃、腈、酸、马来酸酐、马来酰亚胺、乙烯基乙酸酯和乙烯基氯化物或丙烯酸衍生物和它们的混合物的共聚单体,例如苯乙烯/丁二烯、苯乙烯/丙烯腈、苯乙烯/乙烯(互聚物)、苯乙烯/甲基丙烯酸酯烷基酯、苯乙烯/丁二烯/丙烯酸烷基酯、苯乙烯/丁二烯/甲基丙烯酸酯烷基酯、苯乙烯/马来酸酐、苯乙烯/丙烯腈/丙烯酸甲酯、苯乙烯共聚物和其它聚合物的高冲击强度混合物,例如聚丙烯酸酯、二烯烃聚合物或乙烯/丙烯/二烯烃三元共聚物;和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;
6b.由上述6.)提到的聚合物的氢化得到的氢化芳香聚合物,尤其包括通过氢化通常称为聚乙烯基环己烷(PVCH)的无规聚苯乙烯衍生的聚环己基乙烯(PCHE);
6c.由上述6a.)提到的聚合物的氢化得到的氢化芳香聚合物,均聚物和共聚物可带有任何立体结构,包括间规、全规、半全规或无规的,其中优选无规聚合物。还包括立体嵌段聚合物;
7.乙烯基芳香单体,例如苯乙烯或α-甲基苯乙烯的接枝共聚物,例如接枝在聚丁二烯上的苯乙烯、接枝在聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上的苯乙烯;接枝在聚丁二烯上的苯乙烯和丙烯腈(或甲基丙烯腈);接枝在聚丁二烯上的苯乙烯、丙烯腈和甲基丙烯酸酯甲酯;接枝在聚丁二烯上的苯乙烯和马来酸酐;接枝在聚丁二烯上的苯乙烯、丙烯腈和马来酸酐或马来酰亚胺;接枝在聚丁二烯上的苯乙烯和马来酰亚胺;接枝在聚丁二烯上的苯乙烯和丙烯酸烷基酯;接枝在乙烯/丙烯/二烯烃三元共聚物上的苯乙烯和丙烯腈;接枝在聚丙烯酸烷基酯或聚甲基丙烯酸酯烷基酯上的苯乙烯和丙烯腈;接枝在丙烯酸酯/丁二烯共聚物上的苯乙烯和丙烯腈以及它们与在6)中提到的共聚物的混合物,例如称为ABS、MBS、ASA或AES聚合物的共聚物混合物。
8.含卤素聚合物,例如聚氯丁烯、氯化橡胶、异丁烯-异戊烯的氯化和溴化共聚物(卤代丁基橡胶)、氯化或磺氯化聚乙烯、乙烯和氯化乙烯的共聚物、表氯醇均和共聚物,尤其是含卤素乙烯基化合物的聚合物,例如聚氯乙烯氯(PVC)、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯以及它们的共聚物,例如乙烯基氯/偏二氯乙烯、乙烯基氯/乙烯基乙酸酯或偏二氯乙烯/乙烯基乙酸酯共聚物;
9.由α,β未取代的酸和其衍生物衍生的聚合物,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,用丙烯酸丁酯改性冲击;
10.在9)中提到的单体相互间或与其它不饱和单体的共聚物,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/乙烯基卤化物共聚物或丙烯腈/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其乙缩醛衍生的聚合物,例如聚乙烯基醇、聚乙烯基乙酸酯、聚乙烯基硬脂酸酯、聚乙烯基苯甲酸酯、聚乙烯基马来酸酯、聚乙烯基丁缩醛、聚烯丙基邻苯二甲酸酯或聚烯丙基三聚氰胺以及它们与在1)提到的烯烃的共聚物;
12.环醚的均聚物和共聚物,例如聚亚烷基二醇、聚环氧乙烷、聚环氧丙烷或它们与二缩水甘油基醚的共聚物;
13.聚缩醛,例如聚甲醛和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.聚亚苯甲基氧化物或硫化物,和聚亚苯甲基氧化物与苯乙烯聚合物或聚酰胺的混合物;
15.由一方面由羟基封端的聚醚、聚酯或聚丁二烯和另一方面脂族或芳香聚异氰酸酯衍生的聚氨酯及其前体;
16.由二胺和二羧酸和/或由氨基羧酸或相应的内酰胺衍生的聚酰胺或共聚酰胺,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、由m-二甲苯二胺和己二酸得到的芳香聚酰胺、由六亚甲基二胺和间苯二甲酸或/和对苯二甲酸与或不与弹性体作为改性剂制备的聚酰胺,例如聚-2,4,4,-三甲基六亚甲基对苯二甲酰胺或聚-m-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、离聚体或化学粘合或接枝弹性体的嵌段共聚物;或与聚醚,例如聚乙二醇、聚丙二醇或聚丁二醇的嵌段共聚物;以及用EPDM或ABS改性的聚酰胺或共聚酰胺;和在加工中缩合的聚酰胺(RIM聚酰胺体系);
17.聚脲、聚亚酰胺、聚酰胺-亚酰胺、聚醚亚酰胺、聚酯亚酰胺、聚海因和聚苯并咪唑;
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,例如聚对苯二甲酸乙二醇酯(PET)、二醇改性的聚对苯二甲酸乙二醇酯(PETG)、聚对苯二甲酸丁二醇酯、聚-1,4-二甲醇基环己烷对苯二甲酸酯、聚萘二甲酸亚烷基酯(PAN)和聚羧基苯甲酸酯,以及由羟基封端的聚醚衍生的嵌段共聚醚酯和用聚碳酸酯或MBS改性的聚酯;
19.聚碳酸酯和聚酯碳酸酯;
20.聚酮;
21.聚砜和聚醚砜和聚醚酮;
22.一方面由醛,另一方面由酚、脲和三聚氰胺衍生的交联聚合物,例如酚醛树脂、脲醛树脂和三聚氰胺树脂;
23.干燥和非干燥醇酸树脂;
24.由饱和和不饱和二羧酸与多羧基醇和作为交联剂的乙烯基化合物的共聚酯衍生的不饱和聚酯树脂,以及其低可燃性的含卤素改性。
25.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、聚氨酯丙烯酸酯或聚酯丙烯酸酯;
26.与三聚氰胺树脂、脲树脂、异氰酸酯、异氰脲酸酯、聚异氰酸酯或环氧树脂交联的醇酸树脂、聚酯树脂和丙烯酸树脂;
27.由脂族、环脂族、杂环或芳香缩水甘油基化合物衍生的交联环氧树脂,例如双酚A和双酚F的二缩水甘油基醚产物,它用常规硬化剂,例如酐或胺,用或不用加速剂交联;和
28.上述聚合物的共混物(高分子共混物),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。
聚烯烃,即在上述段落中举例的单烯烃的聚合物,优选聚乙烯和聚丙烯可通过不同的,尤其是通过如下方法制备:
a)自由基聚合(通常在高压和高温下)。
b)使用通常含有一种或多于一种周期表IVb、Vb、V1b或VIII族金属的催化剂的催化聚合。这些金属通常含有一种或超过一种的配位体,通常是氧化物、卤化物、醇盐、酯、醚、胺、烷基、烯基和/或芳基,它们可以是π-或σ-配位。这些金属配合物可以是游离形式或固定在基质上,通过在活化氯化镁、氯化钛(III)、氧化铝或氧化硅上。这些偶合剂可溶解或不溶解于聚合介质中,催化剂可本身用于聚合反应中或进一步使用活化剂,通常是金属烷基化物、金属氢化物、金属烷基卤、金属烷基氧化物或金属烷氧基化物,所述化合物是周期表Ia、IIa和/或IIIa族的元素。活化剂可方便地用酯、醚、胺或甲硅烷基醚基团改性。这些催化剂体系通常称为Philips、Standard Oil、Indiana、Ziegler(-Natta)、TNZ(DuPont)、茂金属或单一部位催化剂(SSC)。
本发明的热塑性树脂尤其选自聚乙烯(PE)、聚丙烯(PP)、工程热塑性聚烯烃(TPO)、聚苯乙烯(PS)、聚氯乙烯(PVC)和它们的混合物。
本发明的复合物尤其是PE、PP、PS或PVC与木屑。
任何可模压的聚烯烃或聚烯烃混合物可用于本发明,包括高和低密度聚乙烯、聚丙烯、离聚体、其它共聚物,包括工程热塑性聚烯烃(TPO),它可由与橡胶结合的聚丙烯组成。聚烯烃组分选自例如HDPE和聚丙烯,例如选自消费者或工业使用后的废塑料,尤其是废HDPE,例如由用过的牛奶壶或食品袋回收的那些。对本领域技术人员显然的是,纯塑料可以同样有效地使用,虽然失去了有成果地利用废塑料的效益。
本发明的复合物含有例如基于整个混合物按重量计约20%-约80%的热塑性树脂,例如,基于整个混合物,热塑性树脂以按重量计约30%-约50%,或约35%-约45%存在。因此,基于整个混合物的重量,天然产物以按重量计约80%-约20%,约70%-约50%,或约65%-约55%。
此外,添加剂可用于本发明的复合物中,例如选自位阻酚抗氧化剂、有机磷化合物、羟胺、硝酮、氧化胺和苯并呋喃酮的加工稳定剂。
本发明的混合物还可包括水滑石,水滑石还称为hycite或DHT4A。
水滑石是天然或合成的,天然水滑石被认为具有结构Mg6Al2(OH)6CO3.4 H2O、
合成水滑石的典型经验式是Al2Mg4.35OH11.36CO3(1.67).xH2O。
合成产物的实例包括Mg0.7Al0.3(OH)2(CO3)0.15.054 H2O、Mg4.5Al2(OH)13CO3.3.5H2O和Mg4.2Al(OH)12.4CO3。
本发明的混合物还可含有粘土或纳米级填料。
纳米级填料具有低于约200nm的粒度,优选低于约100nm,更优选低于约50nm。
纳米级填料是例如通过气相或溶胶-凝胶法生产的纳米级氧化物,例如SiO2,SiO2[例如来自Degussa的Aerosil2;来自DuPont的Ludox;来自Nissan Chemical的Snowtex;来自Bayer的Levasil或来自Fuji Silysia Chemical的Sylysia]、TiO2[例如来自Nanophase的NanoTek]、ZrO2、SnO2、MgO、ZnO[例如来自Elementis的ActivoxB或DurhanTZO]、CeO2、In2O3、In2O3或混合氧化物,包括胶体氧化硅[例如Klebosol]或有机溶胶[例如来自Clariant的HilinkOG],或多面体低聚silsesquioxanes[例如来自HybridPlastics的POSS],带有相容或反应有机改性,如烃、硅烷或硅氧烷链,含或不含官能团,如羟基、氨基、巯基、环氧或乙烯基团,或天然或改性半合成或合成的[例如来自CO-OP Chemicals的Somasif]页硅酸盐、亲有机物质沉淀的碳酸钙[例如来自Solvay的Socal]或离子交换水滑石[例如来自Ciba Specialty Chemicals的Hycite713]。
填料是例如亲有机物质改性的天然或合成页硅酸盐或该页硅酸盐的混合物。尤其优选的填料是亲有机物质改性的蒙脱石[例如来自Nanocor的Nanomer或来自Suedchemie的Nanofil]、膨润土[例如来自Southern Clay Products的Cloisite]、贝得石、锂蒙脱石、皂石、绿脱石、锌蒙脱石、蛭石、ledikites、magadiites、kenyaites或stevensites。
本发明的混合物还可包括附加的生物杀灭剂,例如抗菌和/或抗藻类化合物。例如抗藻类化合物,例如2-甲硫基-4-环丙基氨基-6-(a,β-二甲基丙基氨基)-s-三嗪、4,5-二氯-N-正辛基-异噻唑啉-3-酮、2-甲硫基-4-环丙基氨基-6-叔丁基氨基-s-三嗪和2-甲硫基-4-乙基氨基-6-(a,β-二甲基丙基氨基)-s-三嗪和抗菌化合物,例如银、胶体银、纳米银、涂银微粒、银化合物,例如Ag2O、AgCl、AgNO3、Ag2SO4、银-沸石、银-玻璃化合物和银锆酸盐。
其它可使用的添加剂是加工助剂/润滑剂,例如用于改善挤出能力、化学发泡剂,例如用于降低重量、冲击改性剂、粘合剂、着色剂、填料、交联剂和阻燃剂。
已知的阻燃剂是例如有机卤素化合物、三聚氰胺基化合物、含磷化合物和金属氢氧化物。
本发明的抗真菌剂、光稳定剂和Ca、Mg、Al或Zn的氧化物、氢氧化物或硅酸盐和附加的其它添加剂经挤出混合加入本发明的复合物中。
本发明的添加剂和任选其它组分可单独地或混合在一起加入复合物材料中,如果需要,单独的组分可在加入复合物前互相混合,例如通过干混、压紧,作为母料或在熔融物中。
在复合物中加入本发明的添加剂和任选其它组分通过已知方法进行,例如以粉末形式的干混或以在例如惰性溶剂、水或油中的溶液、分散液或悬浮液形式湿混。本发明的添加剂和任选其它添加剂可例如在模塑之前或之后加入,还可通过向复合物材料加入溶解的或分散的添加剂或添加剂混合物加入,带有或没有随后的溶剂或悬浮/分散剂的蒸发。它们可直接加入加工装置(例如挤出机、密炼机等),例如作为干混合物或粉末或作为溶液或分散液或悬浮液或熔融物。
加入过程可在任何配备搅拌器的食品容器中,例如在封闭的装置,例如捏合机、混合机或搅拌容器。加入过程优选在挤出机或捏合机中进行,加工是否在惰性气氛或在氧存在下进行是非实质的。
添加剂或添加剂混合物向复合物中的加入可在常规混合机中进行,其中热塑性树脂熔融,与添加剂混合。合适的机器是本领域技术人员已知的,它们主要是混合机、捏合机和挤出机。
加工优选在挤出机中通过在加工中加入添加剂或添加剂混合物进行。
尤其优选的加工机器是单螺杆挤出机、逆时针旋转或同步旋转的双螺杆挤出机、行星齿轮挤出机、环挤出机或共同捏合机。还可以使用带有至少一个气体除去腔室的加工机器,它可施加真空。
熔融加入包括例如挤出、共同捏合、拉挤成形和注塑。
合适的挤出机或捏合机在例如Handbuchder Kunststoffex-trusion,Vol.1 Gmndlagen,Editors F.Hensen,W.Knappe,H.Potente,1989,pp.3-7,ISBN:3-446-14339-4(Vol.2Extrusionsanlagen1986,ISBN 3446-14329-7)中描述。
例如,螺杆长度是1-60螺杆直径,优选35-48螺杆直径,螺杆的旋转速度优选是每分钟10-600转(rpm),非常尤其优选25-30rpm。
最大生产量取决于螺杆直径、旋转速度和驱动力。本发明的方法还可通过改变上述参数或采用输送定量的稳重机在低于最大生产量的水平进行。
如果加入许多组分,它们可预混合或单独加入。
本发明的添加剂和任选其它添加剂还可以母料(“浓缩物”)形式加入复合物中,基于载体树脂的重量,母料以按重量计约1%-约90%,约1%-约75%或约2%-约65%的浓度含有添加剂。树脂载体不需要是与最终加入添加剂的热塑性树脂有相同结构,载体优选不同于热塑性树脂。
在该操作中,载体树脂可以粉末、颗粒、溶液、悬浮液形式或以乳胶形式使用。
有利的是采用聚酯作为载体树脂,例如聚对苯二甲酸乙二醇酯(PET)、PET共聚物或乙二醇改性的聚对苯二甲酸乙二醇酯(PETG)。
例如,有利的是在聚烯烃复合物中经PET载体树脂加入本发明的添加剂。与使用纯添加剂的混合物相比,经浓缩物加入本发明添加剂的真实效果是:
-较好操作,
-改善的工业卫生和环境事宜和
-改善的计量精确性控制。
本发明的添加剂可本身或以包胶囊形式(例如在蜡、油或聚合物中)加入。
适合用作本发明的树脂的聚酯是已知的,在例如US5,807,932中描述。
聚酯,即新鲜聚酯和循环聚酯,可以是由脂族、环脂族或芳香二羧酸和二醇或羟基羧酸构成的均聚酯或共聚酯。
脂族二羧酸可含有2-40个碳原子,环脂族二羧酸含有6-10个碳原子,芳香二羧酸含有8-14个碳原子,脂族羟基羧酸可含有2-12个碳原子,芳香和环脂族羟基羧酸可含有7-14个碳原子。
脂族二醇还可含有2-12个碳原子,环脂族二醇可含有5-18个碳原子,芳香二醇可含有6-16个碳原子。
术语芳香二醇是指二醇,其两个羟基键合至一个或不同的芳香烃基。
对于聚酯还可以是少量支化的,例如基于存在的二羧酸,0.1-3mol%的单体含有超过两个官能团(例如季戊四醇、三苯六甲酸、1,3,5-三-(羟基苯基)苯、2,4-二羟基苯甲酸或2-(4-羧基苯基)-2-(2,4-二羟基苯基)丙烷)。
在含有至少两种单体的聚酯中,后者可以随机分布或以嵌段形式排列。
合适的二羧酸是直链和支链的,饱和的,脂族二羧酸、芳香二羧酸和环脂族二羧酸。
合适的脂族二羧酸是含有2-40个碳原子的羧酸,例如草酸、丙二酸、二甲基丙二酸、琥珀酸、庚二酸、己二酸、三甲基己二酸、癸二酸、壬二酸和二聚酸(不饱和,脂族羧酸,例如油酸的二聚产物)和烷基化丙二酸和琥珀酸,例如十八烷基琥珀酸。
合适的环脂族二羧酸是1,3-环丁烷二羧酸、1,3-环戊烷二羧酸、1,3-和1,4-环己烷二羧酸、1,3-和1,4-(二羧基甲基)环己烷和4,4’-二环己基二羧酸。
合适的芳香二羧酸尤其是对苯二甲酸、间苯二甲酸、邻苯二甲酸、1,3-、1,4-、2,6-和2,7-萘二羧酸、4,4’-联苯二羧酸、二(4-羧基苯基)砜、4,4’-二苯酮二羧酸、1,1,3-三甲基-5-羧基-3-(p-羧基苯基)二氢化茚、二(4-羧基苯基)醚、二(p-羧基苯基)甲烷和二(p-羧基苯基)乙烷。
优选是芳香二羧酸,尤其是对苯二甲酸、间苯二甲酸和2,6-萘二羧酸。
其它合适的二羧酸是含有-CO-NH-基团的物质,它们在DE-A-2414349中描述,同样合适的含有N-杂环的二羧酸,例如由羧基烷基化的、羧基苯基化或羧基苄基化的单氨基-s-三嗪二羧酸衍生的物质(参见DE-A 2 121 184和2 533 675)、单-或二海因、卤代或未卤代苯并咪唑或仲班酸。在这些化合物中,羧基烷基可含有3-20个碳原子。
合适的脂族二醇是直链和支链脂族二醇,尤其是分子中含有2-12,尤其是2-6个碳原子的物质,例如乙二醇、二乙二醇、1,2-和1,3-丙二醇、1,2-、1,3-、2,3-和1,4-丁二醇、戊二醇、新戊二醇、1,6-己二醇和1,12-十二烷二醇。合适环脂族二醇的实例是1,4-二羧基环己烷,其它合适的脂族二醇是例如1,4-二(羟基甲基)环己烷、芳香脂族二醇,例如对二甲苯二醇和2,5-二氯-对二甲苯二醇、2,2-(对羰基乙氧基苯基)丙烷和聚氧化烯基二醇,例如二乙二醇、三乙二醇、聚乙二醇和聚丙二醇。亚烷基二醇优选是直链,尤其含有2-4个碳原子。
优选的二醇是亚烷基二醇、1,4-二羟基环己烷和1,4-二(羟基甲基)环己烷。尤其优选乙二醇、二乙二醇、1己-二(羟基甲基)环己烷、1,4-丁二醇和1,2-和1,3-丙二醇。
其它合适的脂族二醇是β-羟基烷基化的,尤其是β-羟基乙基化双酚,例如2,2-双(4’-(β-羟基乙氧基)苯基)丙烷。其它双酚如下给出。
其它组的合适脂族二醇含有在DE-A-1 812 003,2 342 432,2 342372 and 2 453 326中描述的杂环二醇。实例是N,N′-二(β-羟基-乙基)-5,5-二甲基海因、N,N′-二(β-羟基丙基)-5,5-二甲基海因、亚甲基-二(N-(β-羟基乙基)-5-甲基-5-乙基海因)、亚甲基双(N-(β-羟基乙基)-5,5-二甲基海因)、N,N’-二(β-羟基乙基)苯并咪唑酮、N,N’-二(β-羟基乙基)四氯苯并咪唑酮和N,N’-二(β-羟基乙基)四溴苯并咪唑酮。
合适的芳香二醇是单环双酚,尤其是每个芳环上带有羟基的双环双酚。术语芳香优选是指烃-芳香基,例如亚苯基或亚萘基。紫外,例如对苯二酚、间苯二酚和1,5-、2,6-和2,7-二羟基萘,尤其提及应是双酚,它可以由如下结构式描述:
羟基可以在间位,但尤其在对位上,在这些分子中,R’和R”可以是含有1-6个碳原子的烷基、卤素,例如氯或溴,或尤其是氢,A可以是直接的键或-O-、-S-、-(O)S(O)-、-C(O)-、-P(O)(C1-C20烷基)-、取代或未取代的次烷基、次环烷基或亚烷基。
取代或未取代的次烷基的实例是次乙基、1,1-和2,2-次丙基、2,2-次丁基、1,1-次异丁基、次戊基、次己基、次庚基、次辛基、二氯次乙基和三氯次乙基。
取代或未取代的亚烷基的实例是亚甲基、亚乙基、苯基亚甲基、二苯基亚甲基和甲基苯基亚甲基。次环烷基的实例是次环戊基、次环己基、次环庚基和次环辛基。
双酚的实例是二(p-羟基苯基)醚和硫醚、二(p-羟基苯基)-砜、二(p-羟基苯基)甲烷、二(4-羟基苯基)-2,2’-联苯、苯基对苯二酚、1,2-二(p-羟基苯基)乙烷、1-苯基二(p-羟基苯基)甲烷、二苯基二(p-羟基苯基)甲烷、二苯基二(p-羟基苯基)乙烷、二(3,5-二甲基-4-羟基苯基)砜、二(3,5-二甲基-4-羟基苯基)-p-二异丙基苯、二(3,5-二甲基-4-羟基苯基)-m-二异丙基苯、2-二(3’,5’-二甲基-4’-羟基苯基)丙烷、1,1-和2,2-二(p-羟基苯基)丁烷,2,2-二(p-羟基苯基)六氟丙烷、1,1-二氯-和1,1,1-三氯-2,2-二(p-羟基苯基)乙烷、1,1-二(p-羟基苯基)环戊烷,尤其是2,2-二(p-羟基苯基)丙烷(二双酚A)和1,1-二(p-羟基苯基)环己烷(双酚C)。
羟基羧酸的合适聚酯是例如聚己内酯、聚新戊内酯和4-羟基环己烷羧酸和4-羧基苯甲酸的聚酯。
同样合适的是主要含有酯键,但还可含有其它键的聚合物,例如聚酯酰胺和聚酯亚酰胺。
芳香二羧酸的聚酯是最重要的,尤其是聚对苯二甲酸亚烷基二醇酯。例如基于聚酯,聚酯由至少30mol%,优选40mol%至少芳香二羧酸和至少30mol%,优选40mol%至少优选含有2-12个碳原子的亚烷基二醇构成。
在此情况下,亚烷基二醇尤其是直链的,含有2-6个碳原子,例如乙二醇、三亚甲基二醇、四亚甲基二醇和六亚甲基二醇,芳香二羧酸尤其是对苯二甲酸和/或间苯二甲酸。
尤其合适的聚酯是PET、PBT和相应的共聚物,尤其优选PET和其共聚物。该方法在PET回收物情况下同样是尤其重要的,所述回收物例如由瓶回收,例如由饮料工业回收得到。这些材料优选含有与乙二醇和/或1,4-二(羟基甲基)环己烷结合的对苯二甲酸、2,6-萘二羧酸和/或间苯二甲酸。
含有本文所述的本发明添加剂的材料可用于生产模制品、注塑制品、外形等。
同样,本发明的主题是根据本发明方法生产的模塑制品。
本发明还涉及至少一种天然产物、至少一种热塑性树脂和抗真菌剂的混合物生产耐由于微生物生长、气候和化学相互作用引起的颜色变化的天然产物复合物的用途。
本发明用如下实施例进一步说明,除非另有说明,百分数和份数按重量计。
实施例1:
向按重量计100份木屑/PE的1∶1混合物中加入如下添加剂混合物:
2.00份CaO;
0.50份ZnO;
0.05份季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯];
0.10份三(2,4-二-叔丁基苯基)亚磷酸酯;
0.25份1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的聚缩合产物和2,4-二氯-6-叔辛基氨基-s-三嗪和4,4’-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)的聚缩合产物的1∶1混合物(HALS混合物);
0.10份硬脂酸钙;
0.50份2-(2-H-苯并***-2-基)-4,6-二叔戊基苯酚(UVA);和
0.25份噻苯咪唑。
基于复合物重量,添加剂混合物以按重量计3.75份总量加入。
不加入添加剂,生产对照配方。
混合物在Haake混合机中在160℃下加工,加工的材料在193℃压塑成40mil薄片。组合物通过将10g材料与10ml蒸馏水放置在petri盘(3.5”直径)中测试颜色稳定性,将铁锈放置在混合物的顶部,样品在室温下放置3天。对照配方在铁锈附近显示强的变色(黑),而含有添加剂的配方保持原外观未变。
组合物还根据ASTM G26,方法A(带喷洒周期)在Xenon-ArcWeatherOmeter中测试耐气候性。根据ASTM D1925,测量黄色系数评价颜色发展,结果概述于表1中。
表1:
实施例 | 曝光 | 最初 | 3周 | 7周 |
1a | 对照(无添加剂) | 54.8 | 26.7 | 12.8 |
1b | 含添加剂配方 | 50.4 | 42.1 | 35.1 |
与对照相比,本发明的复合物获得预防颜色变化的杰出结果。
实施例2:
通过在Leistritz twin-screw(18mm)中,在240℃以150rpm螺杆速度挤出2∶1结合的添加剂混合物/PE树脂制备添加剂浓缩物。
添加剂混合物如下:
67%CaO;
1.3%季戊四醇四[3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯];
2.6%三(2,4-二-叔丁基苯基)亚磷酸酯;
6.5%1-(2-羟基乙基)-2,2,6,6-四甲基-4-羟基哌啶和琥珀酸的聚缩合产物和2,4-二氯-6-叔辛基氨基-s-三嗪和4,4’-六亚甲基二(氨基-2,2,6,6-四甲基哌啶)的聚缩合产物的1∶1混合物(HALS混合物);
2.6%硬脂酸钙;
7%噻苯咪唑。
添加剂浓缩物经在Haake混合机中在160℃下加工加入木屑/PE的1∶1混合物中,加工的材料在193℃压塑成40mil薄片。基于整个组合物最终稀释的浓度按添加剂混合物重量计为2%、4%、6%和8%。制备对照样品,不加入添加剂混合物。组合物根据ASTM G21测试抗真菌活性,压塑样品片在分别用金杆菌pollulans(ATCC 15233)和青霉菌pinophilum(ATCC 11797)接种的琼脂基质上在28℃培养21天。在含有添加剂浓缩所有样品上没有观察到真菌生长,测量在样品周围的真菌生长抑制的如下区域:
0% | 2% | 4% | 6% | 8% | |
金杆菌pollulans | 0mm | 11mm | 17mm | 18mm | 20mm |
青霉菌pinophilum | 0mm | 12mm | 16mm | 20mm | >25mm |
组合物还根据ASTM G26,方法A(带喷洒周期)在Xenon-ArcWeatherOmeter中测试耐气候性。根据ASTM D1925,测量黄色系数评价颜色发展:
0% | 2% | 4% | 6% | 8% | |
原始 | 56.7 | 58.6 | 57.7 | 57.9 | 57.3 |
10周 | 11.8 | 12.5 | 16.5 | 17.1 | 21.1 |
与对照相比,本发明的复合物获得抗真菌活性和预防颜色变化的杰出结果。
对曲霉菌niger的抗真菌功效同样被发现是杰出的。
Claims (15)
1、制备抵抗由于微生物生长、气候和化学相互作用引起的颜色变化的天然产物复合物的方法,该方法包括将天然产物、至少一种热塑性树脂、抗真菌剂混合成混合物,熔融加工该混合物。
2、权利要求1的方法,其还含有至少一种选自光稳定剂的化合物和/或选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物。
3、权利要求1的方法,其中选自抗真菌剂选自噻苯咪唑、10,10’氧基联苯氧基胂、tebuconazole、tolnaftate、二-(2-吡啶-1-氧化物)锌、2-正辛基-4-异噻唑啉-3-酮、4,5-二氯-辛基-4-异噻唑啉、正丁基-1,2-苯并异噻唑啉-3-酮、多菌灵和它们的混合物。
4、权利要求1的方法,其中基于整个混合物重量计,抗真菌剂以按重量计0.05%-3.0%的含量存在。
5、权利要求2的方法,其中光稳定剂选自空间位阻胺光稳定剂、2H-苯并***、二苯酮、苯甲酸酯、丙烯酸酯、丙二酸酯、草酰胺、水杨酸酯、苯并噁嗪-4-酮和s-三嗪。
6、权利要求2的方法,其中基于整个混合物的重量,光稳定剂以按重量计0.1%-5%的含量存在。
7、权利要求2的方法,其中选自Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐的化合物是水滑石、Al2O3、CaO、MgO或ZnO。
8、权利要求2的方法,其中基于整个混合物的重量,Ca、Mg、Al和Zn的氧化物、氢氧化物或硅酸盐以按重量计0.5%-10%存在。
9、权利要求2的方法,其含有至少两种不同空间位阻胺光稳定剂或至少一种空间位阻胺光稳定剂和至少一种紫外光吸收剂。
10、权利要求1的方法,其中天然产物选自木材、锯末、椰子壳、甘蔗begasse、亚麻、***、黄麻、洋麻和稻壳。
11、权利要求1的方法,其中热塑性树脂选自聚乙烯、聚丙烯、工程热塑性聚烯烃(TPO)、聚苯乙烯、聚氯乙烯和它们的混合物。
12、权利要求1的方法,其中抗真菌剂和附加添加剂以载体树脂浓缩物的形式加入混合物中。
13、权利要求12的方法,其中载体树脂不同于热塑性树脂。
14、权利要求13的方法,其中载体树脂是聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸乙二醇酯共聚物或乙二醇改性的聚对苯二甲酸乙二醇酯(PETG)。
15、至少一种天然产物、至少一种热塑性树脂和抗真菌剂的混合物在制备抵抗由于微生物生长、气候和化学相互作用引起的颜色变化的天然产物复合物中的用途。
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102307940A (zh) * | 2009-02-04 | 2012-01-04 | 巴斯夫欧洲公司 | 稳定剂 |
CN102307940B (zh) * | 2009-02-04 | 2014-06-25 | 巴斯夫欧洲公司 | 稳定剂 |
CN103552140A (zh) * | 2013-10-22 | 2014-02-05 | 浙江省林产品质量检测站 | 一种耐候性竹、木质人造板及其制造方法 |
CN109773938A (zh) * | 2019-01-22 | 2019-05-21 | 武秀英 | 中药渣生物基复合材料及其制备方法 |
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AU2004232492A1 (en) | 2004-11-04 |
US20040235983A1 (en) | 2004-11-25 |
CA2522969A1 (en) | 2004-11-04 |
AU2004232492B2 (en) | 2010-02-25 |
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