TW201520201A - 受阻胺光安定劑 - Google Patents
受阻胺光安定劑 Download PDFInfo
- Publication number
- TW201520201A TW201520201A TW103136062A TW103136062A TW201520201A TW 201520201 A TW201520201 A TW 201520201A TW 103136062 A TW103136062 A TW 103136062A TW 103136062 A TW103136062 A TW 103136062A TW 201520201 A TW201520201 A TW 201520201A
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- TW
- Taiwan
- Prior art keywords
- butyl
- compound
- bis
- composition
- formula
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
- A01G9/14—Greenhouses
- A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4427—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems
- A61K31/4439—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems containing a five-membered ring with nitrogen as a ring hetero atom, e.g. omeprazole
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4427—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems
- A61K31/444—Non condensed pyridines; Hydrogenated derivatives thereof containing further heterocyclic ring systems containing a six-membered ring with nitrogen as a ring heteroatom, e.g. amrinone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/53—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with three nitrogens as the only ring hetero atoms, e.g. chlorazanil, melamine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
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Abstract
本發明提供一種式(I)化合物:
□其中R1及R2彼此獨立地為氫、C1-C22烷基、-O、-OH、-CH2CN、C1-C18烷氧基、由-OH取代之C2-C18烷氧基;C5-C12環烷氧基、C3-C6烯基、C3-C6烯氧基、未經取代或在苯基上由1、2或3個C1-C4烷基取代之C7-C9苯基烷基;或C1-C8醯基;且R3及R4彼此獨立地為C1-C22烷基或式(Ia)之基團
□其中R0具有R1及R2之含義之一。
Description
本發明係關於空間受阻胺化合物、用該空間受阻胺化合物安定以對抗由光、熱或氧化所致之降解的有機材料、該空間受阻胺化合物作為安定劑之用途及用於製備空間受阻胺化合物之方法。
空間受阻胺化合物描述於例如EP-A-107615、EP-A-227640、EP-A-357223、US-A-5244948及US-A-5268401中。
特定言之,本發明係關於一種式(I)化合物
其中R1及R2彼此獨立地為氫、C1-C22烷基、-O、-OH、-CH2CN、C1-C18烷氧基、由-OH取代之C2-C18烷氧基;C5-C12環烷氧基、C3-C6烯基、C3-C6烯氧基、未經取代或在苯基上由1、2或3個C1-C4烷基取代之C7-C9苯基烷基;或C1-C8醯基;且R3及R4彼此獨立地為C1-C22烷基或式(Ia)之基團
其中R0具有R1及R2之含義之一。
具有至多22個碳原子之烷基之實例為甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、2-乙基丁基、正戊基、異戊基、1-甲基戊基、1,3-二甲基丁基、正己基、1-甲基己基、正庚基、異庚基、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、十八烷基及二十基。一種較佳含義為C1-C4烷基。R1及R2較佳為甲基且R3及R4較佳為正丁基。
具有至多18個碳原子之烷氧基之實例為甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、戊氧基、異戊氧基、己氧基、庚氧基、辛氧基、癸氧基、十二烷氧基、十四烷氧基、十六烷氧基及十八烷氧基。R0、R1及R2之較佳含義為甲氧基、乙氧基、丙氧基、辛氧基或十一烷氧基。
C3-C6烯氧基之實例為1-丙烯氧基及2-丙烯氧基。
由-OH取代之C2-C18烷氧基之實例為2-羥基乙基。
C5-C12環烷氧基之實例為環戊氧基、環己氧基、環庚氧基、環辛氧基、環癸氧基及環十二烷氧基。C5-C8環烷氧基(特定言之,環戊氧基及環己氧基)較佳。
C7-C9苯基烷基之實例為苯甲基及2-苯乙基。
在苯基上由1、2或3個C1-C4烷基取代之C7-C9苯基烷基為例如甲基苯甲基、二甲基苯甲基、三甲基苯甲基或第三丁基苯甲基。
C3-C6烯基之實例為烯丙基、2-甲基烯丙基、丁烯基、戊烯基及己烯基。烯丙基較佳。位置1上之碳原子較佳為飽和的。
C1-C8醯基之實例為甲醯基、乙醯基、丙醯基、丁醯基、戊醯基、己醯基、庚醯基、辛醯基、丙烯醯基、甲基丙烯醯基及苯甲醯基。C1-C8烷醯基、C3-C8烯醯基及苯甲醯基較佳。乙醯基及丙烯醯基尤其較佳。
R1及R2彼此獨立地為氫、C1-C8烷基、C1-C18烷氧基或環己氧基且R3及R4彼此獨立地為C1-C6烷基的式(I)化合物較佳。
式(I)化合物較佳為式(A)之化合物。
可類似於已知方法來製備式(I)化合物,例如藉由使式(II)化合物
與吡咯啶在有機溶劑中,視情況在有機或無機鹼存在下反應。
根據一較佳實施例,使式(II)化合物與例如0.8至5當量吡咯啶在有機溶劑(例如,甲苯、二甲苯、氯苯、硝基苯、均三甲苯、乙苯、醇(諸如甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇),N-甲基-2-吡咯啶酮、二甲基甲醯胺、1,4-二噁烷、酯或吡咯啶)中,在有或無
水之情況下,在例如0至10當量鹼金屬氫氧化物(諸如LiOH、NaOH、KOH)、碳酸鹽或碳酸氫鹽(諸如NaHCO3、Na2CO3、K2CO3)、固體鹼、沸石、離子交換樹脂、基於胺之鹼或有機鹼存在下進行反應。式(II)化合物在有機溶劑中之濃度較佳為0.1莫耳至3莫耳。該反應可例如在大氣壓或高達60巴之高壓下進行。所使用之溫度視反應時間(例如2小時至24小時)而在例如30℃與180℃之間變化。
式(II)之起始物質可類似於已知方法,例如,如US-A-5,268,401中所描述來製備。
本發明之另一實施例為一種含有對由光、熱或氧化所致之降解敏感的有機物質及式(I)化合物的組合物。
可安定之有機物質之實例為:
1. 單烯烴及二烯烴之聚合物,例如聚丙烯、聚異丁烯、聚丁-1-烯、聚-4-甲基戊-1-烯、聚乙烯基環己烷、聚異戊二烯或聚丁二烯,以及環烯烴(例如環戊烯或降冰片烯)之聚合物,聚乙烯,其可視情況交聯,例如高密度聚乙烯(HDPE)、高密度高分子量聚乙烯(HDPE-HMW)、高密度超高分子量聚乙烯(HDPE-UHMW)、中密度聚乙烯(MDPE)、低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)、(VLDPE)及(ULDPE)。
聚烯烴(亦即,前一段中所例示之單烯烴聚合物,較佳為聚乙烯及聚丙烯)可藉由不同方法且尤其藉由以下方法製備:
a)自由基聚合(通常在高壓及高溫下)。
b)使用通常含有週期表第IVb、Vb、VIb或VIII族中之一或多種金屬的催化劑的催化聚合。此等金屬通常具有一或多個配體,通常為氧化物、鹵化物、醇化物、酯、醚、胺、烷基、烯基及/或芳基,其可經π配位或σ配位。此等金屬錯合物可呈游離形式或固定於基質上,通常在活化氯化鎂、氯化鈦(III)、氧化鋁或氧化矽上。此等催化劑可
溶或不可溶於聚合介質中。催化劑可單獨用於聚合中或可使用其他活化劑,通常為烷基金屬、金屬氫化物、烷基金屬鹵化物、烷基金屬氧化物或金屬烷基氧烷(metal alkyloxane),該等金屬為週期表第Ia、IIa及/或IIIa族元素。活化劑可以其他酯、醚、胺或矽烷基醚基團便利地進行改質。此等催化劑系統通常稱為Phillips、Standard Oil Indiana、Ziegler(-Natta)、TNZ(DuPont)、茂金屬或單位點催化劑(SSC)。
2. 第1)項下所提及之聚合物之混合物,例如聚丙烯與聚異丁烯、聚丙烯與聚乙烯之混合物(例如PP/HDPE、PP/LDPE)及不同類型聚乙烯之混合物(例如LDPE/HDPE)。
3. 單烯烴及二烯烴彼此或與其他乙烯基單體之共聚物,例如乙烯/丙烯共聚物,線型低密度聚乙烯(LLDPE)及其與低密度聚乙烯(LDPE)之混合物,丙烯/丁-1-烯共聚物、丙烯/異丁烯共聚物、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/乙烯基環己烷共聚物、乙烯/環烯烴共聚物(例如乙烯/降冰片烯,如COC)、乙烯/1-烯烴共聚物(其中1-烯烴係原位產生);丙烯/丁二烯共聚物、異丁烯/異戊二烯共聚物、乙烯/乙烯基環己烯共聚物、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/丙烯酸共聚物及其鹽(離聚物)以及乙烯與丙烯及諸如己二烯、二環戊二烯或亞乙基-降冰片烯之二烯的三元共聚物;及該等共聚物彼此及與以上第1)項中所提及之聚合物的混合物,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及交替或無規聚伸烷基/一氧化碳共聚物及其與其他聚合物(例如聚醯胺)之混合物。
4. 烴類樹脂(例如C5-C9),包括其氫化改質形式(例如增黏劑)及聚烯烴與澱粉之混合物。
第1.)項至第4.)項之均聚物及共聚物可具有任何立體結構,包括對排、同排、半同排(hemi-isotactic)或雜排;其中雜排聚合物較佳。亦包括立體嵌段聚合物。
5. 聚苯乙烯、聚(對甲基苯乙烯)、聚(α-甲基苯乙烯)。
6. 由乙烯基芳族單體衍生之芳族均聚物及共聚物,包括苯乙烯,α-甲基苯乙烯,乙烯基甲苯(尤其是對乙烯基甲苯)之所有異構體,乙基苯乙烯、丙基苯乙烯、乙烯基聯苯、乙烯基萘及乙烯基蒽之所有異構體,及其混合物。均聚物及共聚物可具有任何立體結構,包括對排、同排、半同排或雜排;其中雜排聚合物較佳。亦包括立體嵌段聚合物。
6a. 包括前述乙烯基芳族單體及選自乙烯、丙烯、二烯、腈、酸、順丁烯二酸酐、順丁烯二醯亞胺、乙酸乙烯酯及氯乙烯或丙烯酸衍生物及其混合物之共聚單體的共聚物,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/順丁烯二酸酐、苯乙烯/丙烯腈/丙烯酸甲酯;高衝擊強度苯乙烯共聚物與另一聚合物之混合物,例如聚丙烯酸酯、二烯聚合物或乙烯/丙烯/二烯三元共聚物;及苯乙烯嵌段共聚物,諸如苯乙烯/丁二烯/苯乙烯、苯乙烯/異戊二烯/苯乙烯、苯乙烯/乙烯/丁烯/苯乙烯或苯乙烯/乙烯/丙烯/苯乙烯。
6b. 由第6.)項下所提及之聚合物氫化而衍生之氫化芳族聚合物,尤其包括藉由使雜排聚苯乙烯氫化而製備之聚環己基乙烯(PCHE),通常稱為聚乙烯基環己烷(PVCH)。
6c. 由第6a.)項下所提及之聚合物氫化而衍生之氫化芳族聚合物。
均聚物及共聚物可具有任何立體結構,包括對排、同排、半同
排或雜排;其中雜排聚合物較佳。亦包括立體嵌段聚合物。
7. 乙烯基芳族單體(諸如苯乙烯或α-甲基苯乙烯)之接枝共聚物,例如苯乙烯於聚丁二烯上、苯乙烯於聚丁二烯-苯乙烯或聚丁二烯-丙烯腈共聚物上;苯乙烯及丙烯腈(或甲基丙烯腈)於聚丁二烯上;苯乙烯、丙烯腈及甲基丙烯酸甲酯於聚丁二烯上;苯乙烯及順丁烯二酸酐於聚丁二烯上;苯乙烯、丙烯腈及順丁烯二酸酐或順丁烯二醯亞胺於聚丁二烯上;苯乙烯及順丁烯二醯亞胺於聚丁二烯上;苯乙烯及丙烯酸烷基酯或甲基丙烯酸烷基酯於聚丁二烯上;苯乙烯及丙烯腈於乙烯/丙烯/二烯三元共聚物上;苯乙烯及丙烯腈於聚丙烯酸烷基酯或聚甲基丙烯酸烷基酯上、苯乙烯及丙烯腈於丙烯酸酯/丁二烯共聚物上,以及其與第6)項下所列之共聚物之混合物,例如稱為ABS、MBS、ASA或AES聚合物之共聚物混合物。
8. 含鹵素聚合物,諸如聚氯丁二烯、氯化橡膠、異丁烯-異戊二烯之氯化及溴化共聚物(鹵丁基橡膠)、氯化或磺氯化聚乙烯、乙烯及氯化乙烯之共聚物、表氯醇均聚物及共聚物,尤其是含鹵素之乙烯基化合物之聚合物,例如聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯以及其共聚物,諸如氯乙烯/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. 由α,β-不飽和酸及其衍生物衍生之聚合物,諸如聚丙烯酸酯及聚甲基丙烯酸酯;聚甲基丙烯酸甲酯、聚丙烯醯胺及聚丙烯腈,其經丙烯酸丁酯衝擊改質。
10. 第9)項下所提及之單體與彼此或與其他不飽和單體之共聚物,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/鹵化乙烯共聚物或丙烯腈/甲基丙烯酸烷基酯/丁二烯三元共聚物。
11. 由不飽和醇及胺或其醯基衍生物或縮醛衍生之聚合物,例如
聚乙烯醇、聚乙酸乙烯酯、聚硬脂酸乙烯酯、聚苯甲酸乙烯酯、聚順丁烯二酸乙烯酯、聚乙烯醇縮丁醛、聚鄰苯二甲酸烯丙酯或聚烯丙基三聚氰胺;以及其與以上第1)項中所提及之烯烴之共聚物。
12. 環醚之均聚物及共聚物,諸如聚烷二醇、聚氧化乙烯、聚氧化丙烯或其與雙縮水甘油醚之共聚物。
13. 聚縮醛,諸如聚甲醛及含有氧化乙烯作為共聚單體之彼等聚甲醛;經熱塑性聚胺基甲酸酯、丙烯酸酯或MBS改質之聚縮醛。
14. 聚苯醚及聚苯硫醚,及聚苯醚與苯乙烯聚合物或聚醯胺之混合物。
15. 一方面由羥基封端之聚醚、聚酯或聚丁二烯衍生且另一方面由脂族或芳族聚異氰酸酯衍生之聚胺基甲酸酯以及其前驅物。
16. 由二胺及二羧酸及/或由胺基羧酸或相應內醯胺衍生之聚醯胺及共聚醯胺,例如聚醯胺4、聚醯胺6、聚醯胺6/6、6/10、6/9、6/12、4/6、12/12、聚醯胺11、聚醯胺12、以間二甲苯二胺及己二酸為起始物之芳族聚醯胺;由己二胺及間苯二甲酸或/及對苯二甲酸製備且有或無彈性體作為改質劑之聚醯胺,例如聚2,4,4-三甲基六亞甲基對苯二甲醯胺或聚間伸苯基間苯二甲醯胺;以及上述聚醯胺與聚烯烴、烯烴共聚物、離聚物或化學鍵結或接枝之彈性體的嵌段共聚物;或與聚醚之嵌段共聚物,例如與聚乙二醇、聚丙二醇或聚丁二醇之嵌段共聚物;以及經EPDM或ABS改質之聚醯胺或共聚醯胺;及在處理期間縮合之聚醯胺(RIM聚醯胺系統)。
17. 聚脲、聚醯亞胺、聚醯胺-醯亞胺、聚醚醯亞胺、聚酯醯亞胺、聚乙內醯脲及聚苯并咪唑。
18. 由二羧酸及二醇及/或由羥基羧酸或相應內酯或交酯衍生之聚酯,例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚對苯二甲酸1,4-二羥基甲基環己烷酯、聚萘二甲酸伸烷基酯及聚羥基苯甲酸
酯,以及由羥基封端之聚醚衍生之共聚醚酯,以及經聚碳酸酯或MBS改質之聚酯。共聚酯可包含,例如(但不限於)聚丁二酸/對苯二甲酸伸丁酯、聚己二酸/對苯二甲酸伸丁酯、聚己二酸/對苯二甲酸四亞甲酯、聚丁二酸/己二酸伸丁酯、聚丁二酸/碳酸伸丁酯、聚3-羥基丁酸酯/辛酸酯共聚物、聚3-羥基丁酸酯/己酸酯/癸酸酯三元共聚物。此外,脂族聚酯可包含例如(但不限於)聚(羥基烷酸酯)類,特定言之,聚(丙內酯)、聚(丁內酯)、聚(新戊內酯)、聚(戊內酯)及聚(己內酯),聚丁二酸伸乙酯、聚丁二酸伸丙酯、聚丁二酸伸丁酯、聚丁二酸伸己酯、聚己二酸伸乙酯、聚己二酸伸丙酯、聚己二酸伸丁酯、聚己二酸伸己酯、聚乙二酸伸乙酯、聚乙二酸伸丙酯、聚乙二酸伸丁酯、聚乙二酸伸己酯、聚癸二酸伸乙酯、聚癸二酸伸丙酯、聚癸二酸伸丁酯及聚乳酸(PLA)以及經聚碳酸酯或MBS改質之相應聚酯。術語「聚乳酸(PLA)」表示較佳聚L-交酯之均聚物及其與其他聚合物之任何摻合物或混合物(alloy);乳酸或交酯與其他單體之共聚物,該等其他單體為諸如羥基-羧酸,如(例如)乙醇酸、3-羥基-丁酸、4-羥基-丁酸、4-羥基-戊酸、5-羥基-戊酸、6-羥基-己酸及其環狀形式;術語「乳酸」或「交酯」包括L-乳酸、D-乳酸、其混合物及二聚物,亦即L-交酯、D-交酯、內消旋交酯及其任何混合物。
19. 聚碳酸酯及聚酯碳酸酯。
20. 聚酮。
21. 聚碸、聚醚碸及聚醚酮。
22. 一方面由醛衍生且另一方面由酚、脲及三聚氰胺衍生之交聯聚合物,諸如苯酚/甲醛樹脂、脲/甲醛樹脂及三聚氰胺/甲醛樹脂。
23. 乾性及非乾性醇酸樹脂。
24. 由飽和及不飽和二羧酸與多元醇之共聚酯且以乙烯基化合物作為交聯劑衍生之不飽和聚酯樹脂,以及其低可燃性含鹵素改質形
式。
25. 由經取代之丙烯酸酯衍生之可交聯丙烯酸系樹脂,例如環氧丙烯酸酯、胺基甲酸酯丙烯酸酯或聚酯丙烯酸酯。
26. 與三聚氰胺樹脂、脲樹脂、異氰酸酯、異氰脲酸酯、聚異氰酸酯或環氧樹脂交聯之醇酸樹脂、聚酯樹脂及丙烯酸酯樹脂。
27. 由脂族、環脂族、雜環或芳族縮水甘油基化合物衍生之交聯環氧樹脂,例如雙酚A及雙酚F之二縮水甘油醚產物,其在有或無促進劑之情況下與慣用硬化劑(諸如酸酐或胺)交聯。
28. 天然聚合物,諸如纖維素、橡膠、明膠及其經化學改質之同源衍生物,例如乙酸纖維素、丙酸纖維素及丁酸纖維素,或纖維素醚,諸如甲基纖維素;以及松香及其衍生物。
29. 前述聚合物之摻合物(聚摻合物),例如PP/EPDM、聚醯胺/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/熱塑性PUR、PC/熱塑性PUR、POM/丙烯酸酯、POM/MBS、PPO/HIPS、PPO/PA 6.6及共聚物、PA/HDPE、PA/PP、PA/PPO、PBT/PC/ABS或PBT/PET/PC。
30. 天然存在及合成之有機物質,其為純單體化合物或此等化合物之混合物,例如礦物油、動物及植物脂肪、油及蠟或基於合成酯(例如,鄰苯二甲酸酯、己二酸酯、磷酸酯或偏苯三酸酯)之油、脂肪及蠟以及合成酯與礦物油之任何重量比之混合物,通常為用作紡絲組合物之混合物,以及此等物質之水乳液。
31. 天然或合成橡膠之水乳液,例如羧基苯乙烯/丁二烯共聚物之天然乳膠。
聚烯烴、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲脂、聚醯胺或聚甲醛特別受關注。
根據較佳實施例,有機物質為熱塑性彈性體。
熱塑性彈性體之實例包括聚烯烴熱塑性彈性體及嵌段共聚物型聚苯乙烯熱塑性彈性體。聚烯烴熱塑性彈性體包含聚烯烴樹脂(諸如充當硬鏈段之聚丙烯及聚乙烯)及橡膠組合物(諸如充當軟鏈段之乙烯-丙烯-二烯彈性體(EPDM))。嵌段共聚物型聚苯乙烯熱塑性彈性體包含充當硬鏈段之聚苯乙烯及充當軟鏈段之聚二烯(諸如聚丁二烯或聚異戊二烯)。
或者,聚烯烴彈性體及聚苯乙烯彈性體之摻合物亦可用作本發明之熱塑性彈性體。用於將軟鏈段及硬鏈段組合於熱塑性彈性體中的方法可大致分為簡單摻合、藉由共聚進行植入及動態交聯。聚苯乙烯熱塑性彈性體鏈段之組合包括苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-乙烯丙烯-苯乙烯嵌段共聚物(SEPS)、四種共聚物中任一種之氫化聚合物、無規SBR之氫化聚合物(HSBR)及聚丙烯與選自此等聚合物之一或多個任意成員之摻合物。(SBR=苯乙烯丁二烯橡膠)。
所關注的是熱塑性聚烯烴,特定言之,含有基於乙烯及/或丙烯之橡膠相的聚乙烯或聚丙烯。
視待安定之有機物質之性質、最終用途及其他添加劑之存在而定,式(I)化合物可以各種比例使用。
大體而言,相對於有機物質之重量,使用0.01重量%至5重量%式(I)化合物為適當的,較佳為0.05%至2%,特定言之為0.05%至1%。
可在此等物質聚合或交聯之前、期間或之後將式(I)化合物添加(例如)至聚合物質。此外,其可以純物質形式併入聚合物質中或封裝在蠟、油或聚合物中。
大體而言,式(I)化合物可藉由各種製程併入有機物質中,該等
製程為諸如以粉末形式進行乾混或以溶液或懸浮液形式或亦以母體混合物形式進行濕混,該母體混合物含有2.5重量%至25重量%濃度之式(I)化合物;在此等操作中,聚合物可呈粉末、顆粒、溶液、懸浮液形式或以乳膠形式使用。
根據本發明之組合物之處理實例為:
射出吹塑、擠出、吹塑、滾塑(rotomolding)、模內裝飾(反向注入)、瀝鑄模製(slush molding)、射出模製、共射模製、成形、壓縮模製、壓製、膜擠出(鑄造膜;吹製膜)、纖維紡絲(編織、非編織)、拉製(單軸、雙軸)、退火、深拉伸、壓延、機械轉化、燒結、共擠出、塗佈、層壓、交聯(輻射、過氧化物、矽烷)、氣相沈積、焊接、膠合、硫化、熱成形、管擠出、型面擠出、全張擠出;全張澆濤、旋塗、捆紮、發泡、再循環/再加工、擠出塗佈、減黏(過氧化物、熱)、纖維熔噴(fiber melt blown)、紡黏、表面處理(電暈放電、火焰、電漿)、滅菌(藉由γ射線、電子束)、凝膠塗佈、膠帶擠出、SMC製程或塑性溶膠。
根據本發明之組合物宜用於製備各種成型製品。實例為:
I-1)浮動裝置、船舶應用、駁船、浮標、用於甲板之木塑複合板、橋墩、舟船、小輕艇、船槳及海灘加強件。
I-2)汽車應用,特定言之,保險桿、儀錶板、電池組、後內襯板及前內襯板、引擎蓋下之模製部件、帽架、行李箱內襯、內部襯板、氣囊蓋、用於配件之電子模製品(燈)、用於儀錶板之嵌板、前燈玻璃、儀錶面板、外部襯板、車內裝飾、汽車燈、前燈、停車燈、後燈、刹車燈、內部及外部裝飾;門板;油箱;玻璃前側;後窗;座椅靠背、外部面板、線路絕緣、用於密封的型面擠出、覆蓋層、支柱蓋、底盤部件、排氣系統、燃料過濾器/填充器、燃料泵、燃料箱、車旁飾板、可摺疊車頂、外後視鏡、外部裝飾、緊固件/固定件、前
端模組、玻璃、鉸鏈、鎖定系統、行李箱/行李架、壓製/衝壓部件、密封件、側邊衝撞保護、消聲器/隔音器及天窗。
I-3)道路交通裝置,特定言之,樹立標誌、用於道路標記的樁、汽車輔助設施、三角警告牌、醫用箱、頭盔、輪胎。
I-4)用於飛機、火車、機動車(汽車、摩托車)之裝置,包括陳設品。
I-5)用於太空應用(特定言之,火箭及衛星)之裝置,例如返回防護罩。
I-6)用於建築及設計、採礦應用、聲學靜音系統、街道安全帶及掩蔽所之裝置。
II-1)通用及電氣/電子裝置(個人電腦、電話、攜帶型電話、印表機、電視機、音訊及視訊裝置)、花盆、衛星電視碗(TV bowl)及面板裝置中之設備、外殼及覆蓋物。
II-2)用於其他材料之護套(諸如鋼或織物)。
II-3)用於電子工業之裝置,特定言之,用於插頭(尤其是電腦插頭)之絕緣材料、用於電氣及電子部件之外殼、印刷板及用於電子資料儲存之材料,諸如晶片、核對卡或信用卡。
II-4)電器,特定言之,洗衣機、滾筒、烤箱(微波爐)、洗碗機、攪拌機及熨斗。
II-5)用於燈(例如,路燈、燈罩)的罩蓋。
II-6)在電線及電纜方面之應用(半導體、絕緣體及電纜護套)。
II-7)用於冷凝器、冰箱、加熱裝置、空調、電子器件封裝、半導體、咖啡機及真空清潔器之箔。
III-1)技術製品,諸如嵌齒輪(齒輪)、滑動配件、間隔物、螺釘、螺栓、手柄及旋鈕。
III-2)轉子葉片、通風機及風車葉片、太陽能裝置、游泳池、游
泳池罩蓋、游泳池內襯、池塘內襯、壁櫥、衣櫥、隔牆、板條牆(slat wall)、摺疊牆、屋頂、百葉窗(例如,捲簾百葉窗)、配件、管道之間的接頭、套筒及傳送帶。
III-3)衛生製品,特定言之,淋浴隔間、馬桶坐圈、罩蓋及水槽。
III-4)保鍵製品,特定言之,尿布(嬰兒、成人尿失禁)、女性衛生用品、沐浴簾、毛刷、墊子、浴盆、移動廁所、牙刷及便盆。
III-5)用於水、廢水及化學品之管道(交聯或未交聯)、用於電線及電纜保護之管道、用於氣體、油及污物之管道、排水溝、下降管及排水系統。
III-6)任何幾何形狀之型面(窗格)及壁板。
III-7)玻璃替代品,特定言之擠出板、用於建築物(單層、雙層或多層)之玻璃、飛行器、學校、擠出片、用於建築玻璃之窗貼膜、火車、運輸及衛生製品。
III-8)板(牆、切割板)、擠出塗層(感光紙、四角紙盒(tetrapack)及管道塗層)、筒倉、木材替代物、木塑複合板、木質複合材料、牆壁、表面、傢俱、裝飾箔、地板覆蓋物(內部及外部應用)、地板材料、遮泥板及地磚。
III-9)進氣歧管及排氣歧管。
III-10)水泥應用、混凝土應用、複合應用及罩蓋、側線及覆蓋層、扶手、欄桿、廚房工作台、屋面、屋面板、地磚及防水布。
IV-1)板(牆壁及切割板)、托盤、人工草皮、人造草皮(astroturf)、用於環形運動場(體育競技)之人工覆蓋物、用於環形運動場(體育競技)之人工地板及跑道終點線。
IV-2)連續編織物及切段、纖維(地毯/衛生製品/地工織物/絲狀纖維;過濾器;抹布/窗簾(百葉窗)/醫學應用)、散裝纖維(諸如袍服/防
護服之應用)、網、繩索、電纜、繫帶、細繩、線、安全帶、衣服、貼身衣、手套;靴子;橡膠靴、內衣、服裝、泳衣、便服、傘(太陽傘、陽傘)、降落傘、滑翔傘、帆、「氣球綢」、露營製品、帳篷、氣床、日光浴床位、散裝袋及袋子。
IV-3)隔膜、隔離物、用於屋頂之罩蓋及密封件、隧道、渣坑、池塘、牆頂隔膜、土工膜、游泳池、窗簾(百葉窗)/遮陽板、遮陽篷、天篷、牆紙、食品封裝及包裝(可撓的及堅硬的)、醫學封裝(可撓的及堅硬的)、氣囊/安全帶、靠手及頭枕、地毯、中央控制台、儀錶板、座艙、門、頂部控制台模組、門飾板、車頂內襯(headliner)、內部照明、內部後視鏡、包裹架、後行李箱蓋、座椅、轉向柱、方向盤、紡織品及行李箱飾板。
V-1)膜(封裝、渣坑、層壓、捆包、游泳池、廢料袋、壁紙、延伸膜、酒椰、脫鹽膜、電池及連接器)。
V-2)農業用薄膜(溫室罩蓋、隧道、護根物、青貯料、捆包),尤其是在農業化學製品之集中應用之存在下。
VI-1)食品封裝及包裝(可撓的及堅硬的)、BOPP、BOPET、瓶子。
VI-2)儲存系統,諸如盒子(板條箱)、行李箱、衣櫥、家用收納盒、集裝架、架子、軌道、螺絲盒、小盒及罐子。
VI-3)濾筒、注射器、醫學應用、用於任何運輸之容器、廢料籃及廢料箱、廢料袋、箱子、垃圾箱、垃圾袋、帶輪垃圾箱、一般容器、用於水/用後水/化學品/氣體/油/汽油/柴油之儲罐;儲罐內襯、盒子、板條箱、電池外殼、溝槽、諸如活塞之醫療裝置、眼科應用、診斷裝置及用於藥品泡殼之封裝。
VII-1)擠壓塗層(相紙、四角紙盒、管道塗層)、任何類型家用製品(例如,電器、熱水瓶/衣架)、緊固系統(諸如插座夾、電線夾及電
纜夾)、拉鏈、罩殼、鎖及搭扣罩殼。
VII-2)支撐裝置、用於休閒時間之製品,諸如運動及健身裝置、體操墊、滑雪靴、單線溜冰鞋、滑雪板、整板溜冰鞋、運動表面(例如,網球場);螺旋蓋、用於瓶子及罐子之蓋子及塞子。
VII-3)普通傢俱、發泡製品(靠墊、緩衝器)、泡沫、海綿、洗碗布、墊子、庭院用椅、運動場座椅、桌子、長椅、玩具、建築套件(板/圖形/球)、小劇場、滑梯及玩具車輛。
VII-4)用於光學及磁性資料儲存之物質。
VII-5)廚房用具(吃、喝、烹飪、儲存)。
VII-6)用於CD、匣式磁帶及視訊帶之盒子;DVD電子製品、任何種類之辦公用品(原子筆、印章及印台、滑鼠、架子、音軌)、具有任何體積及內含物(飲料、清潔劑、化妝品,包括香水)之瓶子及膠帶。
VII-7)鞋類(鞋子/鞋底)、鞋墊、鞋罩、黏合劑、結構黏合劑、食品盒(水果、蔬菜、肉、魚)、合成紙、瓶子標籤、長椅、人工關節(人類)、印刷板(柔版)、印刷電路板及顯示技術。
VII-8)填充聚合物裝置(滑石、白堊、瓷土(高嶺土)、矽灰石、顏料、碳黑、TiO2、雲母、奈米複合物質、白雲石、矽酸鹽、玻璃、石棉)。
由根據本發明之組合物製造之汽車內部或外部裝飾材料較佳。特定言之,較佳成型製品為以上第I-2項下所列舉之彼等製品。亦關注用於車頂、座椅或儀錶板之覆面材料。
需要時可將用於合成聚合物之一或多種習知添加劑(諸如抗氧化劑、UV吸收劑、鎳安定劑、顏料、填充劑、塑化劑、腐蝕抑制劑及金屬鈍化劑)添加至含有式(I)化合物之有機物質中。
習知添加劑之實例為:
1. 抗氧化劑
1.1. 烷基化一元酚,例如2,6-二第三丁基-4-甲基苯酚、2-第三丁基-4,6-二甲基苯酚、2,6-二第三丁基-4-乙基苯酚、2,6-二第三丁基-4-正丁基苯酚、2,6-二第三丁基-4-異丁基苯酚、2,6-二環戊基-4-甲基苯酚、2-(α-甲基環己基)-4,6-二甲基苯酚、2,6-二(十八烷基)-4-甲基苯酚、2,4,6-三環己基苯酚、2,6-二第三丁基-4-甲氧基甲基苯酚、側鏈呈線性或分枝狀之壬基苯酚,例如,2,6-二-壬基-4-甲基苯酚、2,4-二甲基-6-(1'-甲基十一-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十七-1'-基)苯酚、2,4-二甲基-6-(1'-甲基十三-1'-基)苯酚及其混合物。
1.2. 烷基硫代甲基苯酚,例如,2,4-二辛基硫代甲基-6-第三丁基苯酚、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、2,6-二-十二基硫代甲基-4-壬基苯酚。
1.3. 氫醌及烷基化氫醌,例如2,6-二第三丁基-4-甲氧基苯酚、2,5-二第三丁基氫醌、2,5-二-第三戊基氫醌、2,6-二苯基-4-十八烷氧基苯酚、2,6-二第三丁基氫醌、2,5-二第三丁基-4-羥基苯甲醚、3,5-二第三丁基-4-羥基苯甲醚、硬脂酸3,5-二第三丁基-4-羥基苯酯、己二酸雙(3,5-二第三丁基-4-羥基苯基)酯。
1.4. 生育酚,例如α-生育酚、β-生育酚、γ-生育酚、δ-生育酚及其混合物(維生素E)。
1.5. 羥基化硫代二苯基醚,例如2,2'-硫代雙(6-第三丁基-4-甲基苯酚)、2,2'-硫代雙(4-辛基苯酚)、4,4'-硫代雙(6-第三丁基-3-甲基苯酚)、4,4'-硫代雙(6-第三丁基-2-甲基苯酚)、4,4'-硫代雙(3,6-二-第二戊基苯酚)、4,4'-雙(2,6-二甲基-4-羥基苯基)二硫醚。
1.6. 亞烷基雙酚,例如2,2'-亞甲基雙(6-第三丁基-4-甲基苯酚)、2,2'-亞甲基雙(6-第三丁基-4-乙基苯酚)、2,2'-亞甲基雙[4-甲基-6-(α甲基環己基)苯酚]、2,2'-亞甲基雙(4-甲基-6-環己基苯酚)、2,2'-亞甲基
雙(6-壬基-4-甲基苯酚)、2,2'-亞甲基雙(4,6-二第三丁基苯酚)、2,2'-亞乙基雙(4,6-二第三丁基苯酚)、2,2'-亞乙基雙(6-第三丁基-4-異丁基苯酚)、2,2'-亞甲基雙[6-(α甲基苯甲基)-4-壬基苯酚]、2,2'-亞甲基雙[6-(α,α二甲基苯甲基)-4-壬基苯酚]、4,4'-亞甲基雙(2,6-二第三丁基苯酚)、4,4'-亞甲基雙(6-第三丁基-2-甲基苯酚)、1,1-雙(5-第三丁基-4-羥基-2-甲基苯基)丁烷、2,6-雙(3-第三丁基-5-甲基-2-羥基苯甲基)-4-甲基苯酚、1,1,3-參(5-第三丁基-4-羥基-2-甲基苯基)丁烷、1,1-雙(5-第三丁基-4-羥基-2-甲基-苯基)-3-正十二烷基巰基丁烷、乙二醇雙[3,3-雙(3'-第三丁基-4'-羥基苯基)丁酸酯]、雙(3-第三丁基-4-羥基-5-甲基-苯基)二環戊二烯、對苯二甲酸雙[2-(3'-第三丁基-2'-羥基-5'-甲基苯甲基)-6-第三丁基-4-甲基苯基]酯、1,1-雙(3,5-二甲基-2-羥基苯基)丁烷、2,2-雙(3,5-二第三丁基-4-羥基苯基)丙烷、2,2-雙(5-第三丁基-4-羥基-2-甲基苯基)-4-正十二烷基巰基丁烷、1,1,5,5-四(5-第三丁基-4-羥基-2-甲基苯基)戊烷。
1.7. O-苯甲基、N-苯甲基及S-苯甲基化合物,例如3,5,3'5'-四-第三丁基-4,4'-二羥基二苯甲基醚、4-羥基-3,5-二甲基苯甲基巰基乙酸十八烷基酯、4-羥基-3,5-二第三丁基苯甲基巰基乙酸十三烷基酯、參(3,5-二第三丁基-4-羥基苯甲基)胺、二硫代對苯二甲酸雙(4-第三丁基-3-羥基-2,6-二甲苯甲基)酯、雙(3,5-二第三丁基-4-羥基苯甲基)硫醚、3,5-二第三丁基-4-羥基苯甲基巰基乙酸異辛酯。
1.8. 羥基苯甲基化丙二酸酯,例如2,2-雙(3,5-二第三丁基-2-羥基苯甲基)丙二酸二-十八烷基酯、2-(3-第三丁基-4-羥基-5-甲基苯甲基)丙二酸二-十八烷基酯、2,2-雙(3,5-二第三丁基-4-羥基苯甲基)丙二酸二(十二烷基)巰基乙酯、2,2-雙(3,5-二第三丁基-4-羥基苯甲基)丙二酸雙[4-(1,1,3,3-四甲基丁基)苯基]酯。
1.9. 芳族羥基苯甲基化合物,例如1,3,5-參(3,5-二第三丁基-4-羥
基-苯甲基)-2,4,6-三甲基苯、1,4-雙(3,5-二第三丁基-4-羥苯甲基)-2,3,5,6-四甲基苯、2,4,6-參(3,5-二第三丁基-4-羥苯甲基)苯酚。
1.10. 三嗪化合物,諸如2,4-雙(辛基巰基)-6-(3,5-二第三丁基-4-羥基苯胺基)-1,3,5-三嗪、2-辛基巰基-4,6-雙(3,5-二第三丁基-4-羥基苯胺基)-1,3,5-三嗪、2-辛基巰基-4,6-雙(3,5-二第三丁基-4-羥基苯氧基)-1,3,5-三嗪、2,4,6-參(3,5-二第三丁基-4-羥基苯氧基)-1,3,5-三嗪、1,3,5-參(3,5-二第三丁基-4-羥基苯甲基)異三聚氰酸酯、1,3,5-參(4-第三丁基-3-羥基-2,6-二甲基苯甲基)異三聚氰酸酯、2,4,6-參(3,5-二第三丁基-4-羥基苯乙基)-1,3,5-三嗪、1,3,5-參(3,5-二第三丁基-4-羥基苯基丙醯基)六氫-1,3,5-三嗪及1,3,5-參(3,5-二環己基-4-羥基苯甲基)異三聚氰酸酯。
1.11. 苯甲基磷酸酯,例如2,5-二第三丁基-4-羥苯甲基磷酸二甲酯、3,5-二第三丁基-4-羥苯甲基磷酸二乙酯、3,5-二第三丁基-4-羥苯甲基磷酸二十八烷基酯、5-第三丁基-4-羥基-3-甲基苯甲基磷酸二十八烷基酯、3,5-二第三丁基-4-羥苯甲基磷酸之單乙醚之鈣鹽。
1.12. 醯胺基苯酚,例如4-羥基月桂醯苯胺、4-羥基硬脂醯苯胺、N-(3,5-二第三丁基-4-羥基苯基)胺基甲酸辛酯。
1.13. β-(3,5-二第三丁基-4-羥基苯基)丙酸與一元醇或多元醇之酯,例如與甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、異氰脲酸參(羥基乙基)酯、N,N'-雙(羥基乙基)乙二醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷之酯。
1.14. β-(5-第三丁基-4-羥基-3-甲基苯基)丙酸與一元醇或多元醇之酯,例如與甲醇、乙醇、正辛醇、異辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙
二醇、三乙二醇、異戊四醇、異氰脲酸參(羥基乙基)酯、N,N'-雙(羥基乙基)乙二醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷;3,9-雙[2-{3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基}-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5.5]十一烷之酯。
1.15. β-(3,5-二環己基-4-羥基苯基)丙酸與一元醇或多元醇之酯,例如與甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、異氰脲酸參(羥基乙基)酯、N,N'-雙(羥基乙基)乙二醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷之酯。
1.16. 3,5-二第三丁基-4-羥基苯基乙酸與一元醇或多元醇之酯,例如與甲醇、乙醇、辛醇、十八醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、異戊四醇、異氰脲酸參(羥基乙基)酯、N,N'-雙(羥基乙基)乙二醯胺、3-硫雜十一醇、3-硫雜十五醇、三甲基己二醇、三羥甲基丙烷、4-羥基甲基-1-磷雜-2,6,7-三氧雜雙環[2.2.2]辛烷之酯。
1.17. β-(3,5-二第三丁基-4-羥基苯基)丙酸之醯胺,例如,N,N'-雙(3,5-二第三丁基-4-羥基苯基丙醯基)己二醯胺、N,N'-雙(3,5-二第三丁基-4-羥基-苯基丙醯基)三亞甲基二胺、N,N'-雙(3,5-二第三丁基-4-羥基苯基丙醯基)醯肼、N,N'-雙[2-(3-[3,5-二第三丁基-4-羥基苯基]丙醯氧基)乙基]乙二醯胺(Naugard®XL-1,由Uniroyal提供)。
1.18. 抗壞血酸(維生素C)
1.19. 胺類抗氧化劑,例如N,N'-二異丙基對苯二胺、N,N'-二第二丁基對苯二胺、N,N'-雙(1,4-二甲基戊基)對苯二胺、N,N'-雙(1-乙基-3-甲基戊基)對苯二胺、N,N'-雙(1-甲基庚基)對苯二胺、N,N'-二環己
基對苯二胺、N,N'-二苯基對苯二胺、N,N'-雙(2-萘基)對苯二胺、N-異丙基-N'-苯基對苯二胺、N-(1,3-二甲基丁基)-N'-苯基對苯二胺、N-(1-甲基庚基)-N'-苯基對苯二胺、N-環己基-N'-苯基對苯二胺、4-(對甲苯胺磺醯)二苯胺、N,N'-二甲基-N,N'-二第二丁基對苯二胺、二苯胺、N-烯丙基二苯胺、4-異丙氧基二苯胺、N-苯基-1-萘胺、N-(4-第三辛基苯基)-1-奈胺、N-苯基-2-萘胺、辛基化二苯胺(例如p,p'-二第三辛基二苯胺)、4-正丁基-胺基苯酚、4-丁醯基胺基苯酚、4-壬醯基胺基苯酚、4-十二醯基胺基苯酚、4-十八醯基胺基苯酚、雙(4-甲氧基苯基)胺、2,6-二第三丁基-4-二甲胺基-甲酚、2,4'-二胺基二苯甲烷、4,4'-二胺基二苯甲烷、N,N,N',N'-四-甲基-4,4'-二胺基二苯甲烷、1,2-雙[(2-甲基苯基)胺基]乙烷、1,2-雙(苯基-胺基)丙烷、(鄰甲苯基)二胍、雙[4-(1',3'-二甲基丁基)苯基]胺、第三-辛基化N-苯基-1-萘胺、單烷基化與二烷基化第三丁基/第三辛基二苯胺之混合物、單烷基化與二烷基化壬基二苯胺之混合物、單烷基化與二烷基化十二烷基二苯胺之混合物、單烷基化與二烷基化異丙基/異己基二苯胺之混合物、單烷基化與二烷基化第三丁基二苯胺之混合物、2,3-二氫-3,3-二甲基-4H-1,4-苯并噻嗪、啡噻嗪、單烷基化與二烷基化第三丁基/第三辛基啡噻嗪之混合物、單烷基化與二烷基化第三辛基啡噻嗪之混合物、N-烯丙基啡噻嗪、N,N,N',N'-四苯基-1,4-二胺基丁-2-烯。
2. UV吸收劑及光安定劑
2.1. 2-(2'-羥基苯基)苯并三唑,例如2-(2'-羥基-5'-甲基苯基)-苯并三唑、2-(3',5'-二第三丁基-2'-羥基苯基)苯并三唑、2-(5'-第三丁基-2'-羥基苯基)苯并三唑、2-(2'-羥基-5'-(1,1,3,3-四甲基丁基)苯基)苯并三唑、2-(3',5'-二第三丁基-2'-羥基苯基)-5-氯-苯并三唑、2-(3'-第三丁基-2'-羥基-5'-甲基苯基)-5-氯-苯并三唑、2-(3'-第二丁基-5'-第三丁基-2'-羥基苯基)苯并三唑、2-(2'-羥基-4'-辛氧基苯基)苯并三唑、2-(3',5'-二-
第三戊基-2'-羥基苯基)苯并三唑、2-(3',5'-雙-(α,α-二甲苯甲基)-2'-羥基苯基)苯并三唑、2-(3'-第三丁基-2'-羥基-5'-(2-辛氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3'-第三丁基-5'-[2-(2-乙基己氧基)-羰基乙基]-2'-羥基苯基)-5-氯-苯并三唑、2-(3'-第三丁基-2'-羥基-5'-(2-甲氧基羰基乙基)苯基)-5-氯-苯并三唑、2-(3'-第三丁基-2'-羥基-5'-(2-甲氧基羰基乙基)苯基)苯并三唑、2-(3'-第三丁基-2'-羥基-5'-(2-辛氧基羰基-乙基)苯基)苯并三唑、2-(3'-第三丁基-5'-[2-(2-乙基己氧基)羰基乙基]-2'-羥基-苯基)苯并三唑、2-(3'-十二烷基-2'-羥基-5'-甲基苯基)苯并三唑、2-(3'-第三丁基-2'-羥基-5'-(2-異辛氧基羰基乙基)苯基苯并三唑、2,2'-亞甲基-雙[4-(1,1,3,3-四甲基丁基)-6-苯并三唑-2-基苯酚];2-[3'-第三丁基-5'-(2-甲氧基羰基乙基)-2'-羥基苯基]-2H-苯并三唑與聚乙二醇300之酯基轉移產物,其中R=3'-第三丁基-4'-羥基-5'-2H-苯并三唑-2-基苯基、2-[2'-羥基-3'-(α,α-二甲苯甲基)-5'-(1,1,3,3-四甲基丁基)-苯基]-苯并三唑;2-[2'-羥基-3'-(1,1,3,3-四甲基丁基)-5'-(α,α-二甲苯甲基)-苯基]苯并三唑。
2.2. 2-羥基二苯甲酮,例如4-羥基、4-甲氧基、4-辛氧基、4-癸氧基、4-十二烷氧基、4-苯甲氧基、4,2',4'-三羥基及2'-羥基-4,4'-二甲氧基衍生物。
2.3. 經取代及未經取代之苯甲酸之酯,例如水楊酸4-第三丁基-苯酯、水楊酸苯酯、水楊酸辛基苯酯、二苯甲醯間苯二酚、雙(4-第三丁基苯甲醯基)間苯二酚、苯甲醯間苯二酚、3,5-二第三丁基-4-羥基苯甲酸2,4-二第三丁基苯酯、3,5-二第三丁基-4-羥基苯甲酸十六烷基酯、3,5-二第三丁基-4-羥基苯甲酸十八烷基酯、3,5-二第三丁基-4-羥基苯甲酸2-甲基-4,6-二第三丁基苯酯。
2.4. 丙烯酸酯,例如α-氰基-β,β二苯基丙烯酸乙酯、α-氰基-β,β二苯基丙烯酸異辛酯、α-甲氧羰基肉桂酸甲酯、α-氰基-β-甲基-對甲
氧基肉桂酸甲酯、α-氰基-β-甲基-對甲氧基-肉桂酸丁酯、α-甲氧羰基-對甲氧基肉桂酸甲酯、N-(β-甲氧羰基-β-氰基乙烯基)-2-甲基吲哚啉、四(α-氰基-β,β二苯基丙烯酸)新戊酯。
2.5. 鎳化合物,例如2,2'-硫代-雙[4-(1,1,3,3-四甲基丁基)苯酚]之鎳錯合物,諸如1:1或1:2錯合物,具有或不具有其他配體,諸如正丁胺、三乙醇胺或N-環己基二乙醇胺;二丁基二硫代胺基甲酸鎳;單烷基酯(例如4-羥基-3,5-二第三丁基苯甲基膦酸甲酯或乙酯)之鎳鹽;酮肟(例如2-羥基-4-甲基苯基十一烷基酮肟)之鎳錯合物;1-苯基-4-月桂醯基-5-羥基吡唑之鎳錯合物,具有或不具有其他配體。
2.6. 空間受阻胺,例如碳酸雙(1-十一烷氧基-2,2,6,6-四甲基-4-哌啶基)酯、雙(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(2,2,6,6-四甲基-4-哌啶基)丁二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、雙(1,2,2,6,6-五甲基-4-哌啶基)正丁基-3,5-二第三丁基-4-羥基苯甲基丙二酸酯、1-(2-羥基乙基)-2,2,6,6-四甲基-4-羥基哌啶與丁二酸之縮合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)己二胺與4-第三辛基胺基-2,6-二氯-1,3,5-三嗪之線性或環狀縮合物、參(2,2,6,6-四甲基-4-哌啶基)氮基三乙酸酯、肆(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯、1,1'-(1,2-乙烷二基)-雙(3,3,5,5-四甲基哌嗪酮)、4-苯甲醯-2,2,6,6-四甲基哌啶、4-硬脂醯氧基-2,2,6,6-四甲基哌啶、雙(1,2,2,6,6-五甲基哌啶基)-2-正丁基-2-(2-羥基-3,5-二第三丁基苯甲基)-丙二酸酯、3-正辛基-7,7,9,9-四甲基-1,3,8-三氮雜螺[4.5]癸烷-2,4-二酮、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)癸二酸酯、雙(1-辛氧基-2,2,6,6-四甲基哌啶基)丁二酸酯、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)己二胺與4-嗎啉基-2,6-二氯-1,3,5-三嗪之線性或環狀縮合物、2-氯-4,6-雙(4-正丁基胺基-2,2,6,6-四甲基哌啶基)-1,3,5-三嗪與1,2-雙(3-胺基丙基胺基)-乙烷之縮合物、2-氯-4,6-二-(4-
正丁基胺基-1,2,2,6,6-五甲基哌啶基)-1,3,5-三嗪與1,2-雙(3-胺基丙基胺基)乙烷之縮合物、8-乙醯基-3-十二烷基-7,7,9,9-四甲基-1,3,8-三氮雜螺[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)吡咯啶-2,5-二酮、3-十二烷基-1-(1,2,2,6,6-五甲基-4-哌啶基)吡咯啶-2,5-二酮、4-十六氧基-2,2,6,6-四甲基哌啶與4-硬脂醯氧基-2,2,6,6-四甲基哌啶之混合物、N,N'-雙(2,2,6,6-四甲基-4-哌啶基)己二胺與4-環己基胺基-2,6-二氯-1,3,5-三嗪之縮合物、1,2-雙(3-胺基丙基胺基)乙烷與2,4,6-三氯-1,3,5-三嗪以及4-丁基胺基-2,2,6,6-四甲基哌啶(CAS登記號[136504-96-6])之縮合物;1,6-己二胺與2,4,6-三氯-1,3,5-三嗪以及N,N-二丁基胺及4-丁基胺基-2,2,6,6-四甲基哌啶(CAS登記號[192268-64-7])之縮合物;N-(2,2,6,6-四甲基-4-哌啶基)-正十二烷基丁二醯亞胺、N-(1,2,2,6,6-五甲基-4-哌啶基)-正十二烷基丁二醯亞胺、2-十一烷基-7,7,9,9-四甲基-1-氧雜-3,8-二氮雜-4-側氧基-螺-[4,5]癸烷、7,7,9,9-四甲基-2-環十一烷基-1-氧雜-3,8-二氮雜-4-側氧基-螺-[4,5]癸烷與表氯醇之反應產物、1,1-雙(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'-雙-甲醯基-N,N'-雙(2,2,6,6-四甲基-4-哌啶基)己二胺、4-甲氧基亞甲基丙二酸與1,2,2,6,6-五甲基-4-羥基哌啶之二酯、聚[甲基丙基-3-氧基-4-(2,2,6,6-四甲基-4-哌啶基)]矽氧烷、順丁烯二酸酐-α-烯烴共聚物與2,2,6,6-四甲基-4-胺基哌啶或1,2,2,6,6-五甲基-4-胺基哌啶之反應產物、2,4-雙[N-(1-環己氧基-2,2,6,6-四甲基哌啶-4-基)-正丁基胺基]-6-(2-羥基乙基)胺基-1,3,5-三嗪、1-(2-羥基-2-甲基丙氧基)-4-十八烯醯氧基-2,2,6,6-四甲基哌啶、5-(2-乙基己醯基)-氧基甲基-3,3,5-三甲基-2-嗎啉酮、Sanduvor(Clariant;CAS登記號106917-31-1]、5-(2-乙基己醯基)氧基甲基-3,3,5-三甲基-2-嗎啉酮、2,4-雙[(1-環己氧基-2,2,6,6-哌啶-4-基)丁基胺基]-6-氯-均三嗪與N,N'-雙(3-胺丙基)乙二胺)之反應產物、1,3,5-參(N-環己基-N-(2,2,6,6-四甲基哌嗪-3-酮-
4-基)胺基)-均三嗪、1,3,5-參(N-環己基-N-(1,2,2,6,6-五甲基哌嗪-3-酮-4-基)-胺基)-均三嗪、
2.7. 乙二醯胺,例如4,4'-二辛氧基乙二醯苯胺、2,2'-二乙氧基乙二醯苯胺、2,2'-二辛氧基-5,5'-二第三丁基乙二醯苯胺、2,2'-二十二烷氧基-5,5'-二第三丁基乙二醯苯胺、2-乙氧基-2'-乙基乙二醯苯胺、N,N'-雙(3-二甲基胺丙基)乙二醯胺、2-乙氧基-5-第三丁基-2'-乙基乙二醯苯胺及其與2-乙氧基-2'-乙基-5,4'-二第三丁基乙二醯苯胺之混合物、鄰甲氧基與對甲氧基分佈之乙二醯苯胺之混合物及鄰乙氧基與對乙氧基分佈之乙二醯苯胺之混合物。
2.8. 2-(2-羥基苯基)-1,3,5-三嗪,例如2,4,6-參(2-羥基-4-辛氧基苯基)-1,3,5-三嗪、2-(2-羥基-4-辛氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2,4-二羥基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4-雙(2-羥基-4-丙氧基苯基)-6-(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-辛氧基苯基)-4,6-雙(4-甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-十二烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-十三烷氧基苯基)-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羥基-4-(2-羥基-3-丁氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三嗪、2-[2-羥基-4-
(2-羥基-3-辛氧基丙氧基)苯基]-4,6-雙(2,4-二甲基)-1,3,5-三嗪、2-[4-(十二烷氧基/十三烷氧基-2-羥基丙氧基)-2-羥基苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-[2-羥基-4-(2-羥基-3-十二烷氧基丙氧基)苯基]-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2-(2-羥基-4-己氧基)苯基-4,6-二苯基-1,3,5-三嗪、2-(2-羥基-4-甲氧基苯基)-4,6-二苯基-1,3,5-三嗪、2,4,6-參[2-羥基-4-(3-丁氧基-2-羥基丙氧基)苯基]-1,3,5-三嗪、2-(2-羥基苯基)-4-(4-甲氧基苯基)-6-苯基-1,3,5-三嗪、2-{2-羥基-4-[3-(2-乙基己基-1-氧)-2-羥基丙氧基]苯基}-4,6-雙(2,4-二甲基苯基)-1,3,5-三嗪、2,4-雙(4-[2-乙基己氧基]-2-羥基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2-(4,6-雙-二苯基-4-基-1,3,5-三嗪-2-基)-5-(2-乙基-正己氧基)苯酚。
3. 金屬鈍化劑,例如N,N'-二苯基乙二醯胺、N-水楊醛-N'-水楊醯肼、N,N'-雙(水楊醯基)肼、N,N'-雙(3,5-二第三丁基-4-羥基苯丙醯基)肼、3-水楊醯胺基-1,2,4-三唑、雙(苯亞甲基)乙二醯基二醯肼、乙二醯苯胺、間苯二醯基二醯肼、癸二醯基雙苯基醯肼、N,N'-二乙醯基己二醯基二醯肼、N,N'-雙(水楊醯基)乙二醯基二醯肼、N,N'-雙(水楊醯基)硫代丙醯基二醯肼。
4. 亞磷酸酯及亞膦酸二酯,例如亞磷酸三苯酯、亞磷酸二苯基烷基酯、亞磷酸苯基二烷基酯、亞磷酸參(壬基苯基)酯、亞磷酸三月桂酯、亞磷酸三(十八烷基)酯、二硬脂醯異戊四醇二亞磷酸酯、亞磷酸參(2,4-二第三丁基苯基)酯、二異癸基異戊四醇二亞磷酸酯、雙(2,4-二第三丁基苯基)異戊四醇二亞磷酸酯、雙(2,4-二異丙苯基苯基)異戊四醇二亞磷酸酯、雙(2,6-二第三丁基-4-甲基苯基)異戊四醇二亞磷酸酯、二異癸氧基異戊四醇二亞磷酸酯、雙(2,4-二第三丁基-6-甲基苯基)異戊四醇二亞磷酸酯、雙(2,4,6-參(第三丁基苯基)異戊四醇二亞磷酸酯、三硬脂醯山梨糖醇三亞磷酸酯、二亞磷酸肆(2,4-二第三丁基苯基)4,4'-伸聯苯酯、6-異辛氧基-2,4,8,10-四第三丁基-12H-二苯并
[d,g]-1,3,2-二氧雜磷黴素、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)甲酯、亞磷酸雙(2,4-二第三丁基-6-甲基苯基)乙酯、6-氟-2,4,8,10-四第三丁基-12-甲基-二苯并[d,g]-1,3,2-二氧雜磷黴素、2,2',2"-氮基[三乙基參(3,3',5,5'-四第三丁基-1,1'-聯苯-2,2'-二基)亞磷酸酯]、2-乙基己基(3,3',5,5'-四第三丁基-1,1'-聯苯-2,2'-二基)亞磷酸酯、5-丁基-5-乙基-2-(2,4,6-三第三丁基苯氧基)-1,3,2-二氧雜磷雜環丙烷。
以下亞磷酸酯尤其較佳:
亞磷酸參(2,4-二第三丁基苯基)酯(Irgafos®168,Ciba Specialty Chemicals Inc.)、亞磷酸參(壬基苯基)酯、
5. 羥胺,例如N,N-二苯甲基羥胺、N,N-二乙基羥胺、N,N-二辛基羥胺、N,N-二月桂基羥胺、N,N-二(十四烷基)羥胺、N,N-二(十六烷基)羥胺、N,N-二(十八烷基)羥胺、N-十六烷基-N-十八烷基羥胺、N-十七烷基-N-十八烷基羥胺、由氫化動物脂胺衍生之N,N-二烷基羥胺。
6. 硝酮,例如N-苯甲基-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、由氫化動物脂胺衍生之N,N-二烷基羥胺衍生之硝酮。
7. 含硫增效劑,例如硫代二丙酸二月桂酯、硫代二丙酸二(十四烷基)酯(dimistryl thiodipropionate)、硫代二丙酸二硬脂醯酯、異戊四醇肆[3-(十二烷基硫)丙酸酯]或二硬脂醯二硫化物。
8. 過氧化物清除劑,例如β-硫二丙酸之酯,例如月桂基、硬脂醯、十四烷基或十三烷基酯、巰基苯并咪唑或2-巰基苯并咪唑之鋅鹽、二丁基二硫胺基甲酸鋅、二(十八烷基)二硫化物、異戊四醇肆(β-十二烷基巰基)丙酸酯。
9. 聚醯胺安定劑,例如與碘化物及/或磷化合物組合之銅鹽及二價錳鹽。
10. 鹼性共安定劑,例如三聚氰胺、聚乙烯吡咯啶酮、雙氰胺、
三聚氰酸三烯丙酯、脲衍生物、肼衍生物、胺、聚醯胺、聚胺基甲酸酯、高級脂肪酸之鹼金屬鹽及鹼土金屬鹽,例如硬脂酸鈣、硬脂酸鋅、山崳酸(behenate)鎂、硬脂酸鎂、蓖麻油酸鈉及棕櫚酸鉀、鄰苯二酚酸銻或鄰苯二酚酸鋅。
11. 成核劑,例如無機物,諸如滑石、金屬氧化物(諸如二氧化鈦或氧化鎂),較佳為鹼土金屬之磷酸鹽、碳酸鹽或硫酸鹽;有機化合物,諸如單羧酸或聚羧酸及其鹽,例如4-第三丁基苯甲酸、己二酸、二苯基乙酸、丁二酸鈉或苯甲酸鈉;聚合化合物,諸如離子共聚物(離聚物)。尤其較佳為1,3:2,4-雙(3',4'-二甲基苯亞甲基)山梨糖醇、1,3:2,4-二(對甲基二苯亞甲基)山梨糖醇及1,3:2,4-二(苯亞甲基)山梨糖醇。
12. 填充劑及增強劑,例如碳酸鈣、矽酸鹽、玻璃纖維、玻璃珠、石棉、滑石、高嶺土、雲母、硫酸鋇、金屬氧化物及氫氧化物、碳黑、石墨、木粉及麵粉或其他天然產物纖維、合成纖維。
13. 其他添加劑,例如塑化劑、潤滑劑、乳化劑、顏料、流變添加劑、催化劑、流動控制劑、光學增亮劑、耐火劑、抗靜電劑及發泡劑。
14. 苯并呋喃酮及吲哚啉酮,例如U.S.4,325,863、U.S.4,338,244、U.S.5,175,312、U.S.5,216,052、U.S.5,252,643、DE-A-4316611、DE-A-4316622、DE-A-4316876、EP-A-0589839、EP-A-0591102、EP-A-1291384中所描述之彼等苯并呋喃酮及吲哚啉酮或3-[4-(2-乙醯氧基乙氧基)苯基]-5,7-二第三丁基苯并呋喃-2-酮、5,7-二第三丁基-3-[4-(2-硬脂醯氧基乙氧基)苯基]苯并呋喃-2-酮、3,3'-雙[5,7-二第三丁基-3-(4-[2-羥基乙氧基]苯基)苯并呋喃-2-酮]、5,7-二第三丁基-3-(4-乙氧基苯基)苯并呋喃-2-酮、3-(4-乙醯氧基-3,5-二甲基苯基)-5,7-二第三丁基苯并呋喃-2-酮、3-(3,5-二甲基-4-特戊醯氧苯基)-5,7-
二第三丁基苯并呋喃-2-酮、3-(3,4-二甲基苯基)-5,7-二第三丁基苯并呋喃-2-酮、3-(2,3-二甲基苯基)-5,7-二第三丁基苯并呋喃-2-酮、3-(2-乙醯基-5-異辛基苯基)-5-異辛基苯并呋喃-2-酮。
酚系抗氧化劑較佳。所關注的是上文第1項下所列出之彼等酚系抗氧化劑。特別關注的是酚系抗氧化劑及製程安定劑,諸如異戊四醇肆[3,5-二第三丁基-4-羥基苯基丙酸酯]、十八烷基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、1,3,5-參(3,5-二第三丁基-4-羥基-苯甲基)-2,4,6-三甲基苯、N,N'-雙(3,5-二第三丁基-4-羥基苯基丙醯基)己二醯胺、1,3,5-參[3,5-二第三丁基-4-羥苯甲基]異氰脲酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯、雙(1,2,2,6,6-五甲基哌啶-4-基)-丁基(3,5-二第三丁基-4-羥苯甲基)丙二酸酯)及參[2,4-二第三丁基苯基]亞磷酸酯。
更佳添加劑為異戊四醇肆[3-(十二烷基硫)丙酸酯]及硬脂酸鈣。
諸如TiO2及碳黑之顏料更佳。亦關注諸如滑石之填充劑。
較佳添加劑亦為空間受阻胺光安定劑及/或UV吸收劑,特定言之,上文第2項下所列出之彼等添加劑。
式(I)化合物與習知添加劑之重量比為例如1:100至100:1,較佳為1:100至10:1,特定言之為1:10至10:1。
本發明之另一目標為一種用於安定有機物質以對抗由光、熱或氧化所致之降解的方法,其包含將至少一種式(I)化合物併入該有機物質中。
以下實例更詳細地說明本發明。除非另有說明,否則本申請案中所提及的所有百分比及份數均以重量計。
實例1:製備2N,4N'-二丁基-2N,4N'-雙(1,2,2,6,6-五甲基-4-哌啶基)-6-吡咯啶-1-基-1,3,5-三嗪-2,4-二胺(=化合物A)
起始物質2N,4N'-二丁基-6-氯-2N,4N'-雙(1,2,2,6,6-四甲基吡咯啶-
4-基)-1,3,5-三嗪-2,4-二胺為已知的並且可類似於已知方法,例如,如US-A-5,268,401之實例2A中所描述來製備。
方法A:
在鋼質高壓釜中添加43.19g 2N,4N'-二丁基-6-氯-2N,4N'-雙(1,2,2,6,6-四甲基哌啶-4-基)-1,3,5-三嗪-2,4-二胺、5.6g吡咯啶、15g氫氧化鈉水溶液(30%)及30g二甲苯。使用氬氣對反應器進行三次閃蒸。隨後,將反應器加熱至160℃後維持20小時。完全轉化之後,用水及甲苯稀釋反應混合物,進行相分離且用水將有機層洗滌若干次。經硫酸鈉乾燥之後,獲得51.1g白色固化固體。將該產物溶解於150ml熱己烷中且過濾並乾燥晶體。作為產出,分離41.6g白色產物(為理論值之89%)。
TLC(正己烷/乙酸乙酯2:1加5滴氫氧化銨溶液):Rf=0.82。
1 H NMR:(400MHz,三氯甲烷-d):ppm 5.17(2H,m),3.49(4H,dd),3.33(4H,dd),2.25(6H,s),1.87(4H,dd),1.67-1.50(12H,m),1.37-1.22(4H,m),1.16(12H,s),1.10(12H,s),0.96-0.86(6H,m)。
方法B:
將93.4g之2N,4N'-二丁基-6-氯-2N,4N'-雙(1,2,2,6,6-四甲基哌啶-4-基)-1,3,5-三嗪-2,4-二胺溶解於86.5ml二甲苯中。添加12.0g吡咯啶、23.2g氫氧化鈉水溶液(30%)及29.9g水並且將溶液加熱至70℃後維持3小時。完全反應之後,進行相分離且用水將有機相洗滌若干次。在200℃、50毫巴下移除溶劑。將熱熔體填充在板上並且冷卻降溫。產物(90.0g(為理論值之90%))為棕黃色熔體,其凝固溫度為75℃-80℃。
形式指定:
在用結晶物質進行種晶之後,可在擠出機上將所獲得之凝固產物轉化成高度結晶產物形式。
熔點:165℃-172℃
實例2:安定熱塑性聚丙烯
基礎調配物:
79.275重量%熱塑性聚丙烯(Daplen® EE013 AE,Borealis;熔體流動速率:11g/10min(ISO 1133);密度:905kg/m3(ISO 1183)20重量%滑石,0.225重量%碳,及0.5重量%TiO2。
製備測試樣本:
在Pappermaier® ESK-150混合機中預先混合基礎調配物。在Mixaco Lab CM12高速混合機上將此混合物與0.2重量%化合物(A)合併,且隨後在220℃下在Berstorff® ZE 25×32D擠出機上進行混配。隨後在240℃下在Engel HL65射出模製機上對全部調配物進行射出模製。
根據國際規範SAE J2412,將射出模製之塊狀物40mm×60mm×2mm或25mm×60mm×2mm曝露於人工風化。所量測之參數為色彩偏差(δE)及60°光澤度。
結果列出於表1及表2中。
實例3:安定熱塑性聚丙烯
類似於實例2中所描述之方法來製備測試樣本且在人工風化之後根據VW PV1306標準評估其黏性。
評估參數:
一個循環對應於96小時。
上文所示之結果清楚地揭示化合物A未進一步增加熱塑性聚丙烯樣品之黏性。
實例4:安定熱塑性丙烯腈/丁二烯/苯乙烯(ABS)
以下兩種調配物係基於ABS(Styrolution Terluran®GP-22,其為具有較高衝擊及熱變形抗性之易流動、一般用途射出模製級,意在用於多種應用,具有19cm3/10min熔體容積率,220℃/10kg)製備:
「標準聚合物」:96.00% Terluran®GP-22 3.00%二氧化鈦Kronos®2220 1.00% Acrawax®C粉末
第1號調配物:100.00%「標準聚合物」
第2號調配物:99.65%「標準聚合物」
0.25%化合物A 0.10%石蠟油
製備測試樣本:
在Röhnrad Elite 650混合機中預先混合調配物且隨後在220℃下在Berstorff® ZE 25×32D擠出機上進行混配。混配之後,在80℃下將調配物乾燥2小時且隨後在240℃下在Arburg 320 S射出模製機上射出模製。
根據國際規範ASTM G 155-C1,將大小為68mm×44mm×2mm之射出模製塊曝露於人工風化。所量測之參數為色彩偏差(δE,孔徑20mm、D65、10°)。結果列出於表4中。
實例5:安定熱塑性可撓性聚氯乙烯(PVC)
「標準聚合物」:64.73% Norvinyl®S7060(氯乙烯均聚物)32.36% Palatinol®N(塑化劑)1.61% Drapex®39(環氧化大豆油)1.30% Baerostab®CT 9051 XRF(CaZn安定劑)
第1號調配物:100.00%「標準聚合物」
第2號調配物:99.50%「標準聚合物」0.25% Chimassorb®81(2-羥基-4-辛氧基-二苯甲酮)0.25%化合物A
製備測試樣本:
經滾桶混合機預先混合調配物且隨後在160℃下以0.4mm間隙在Collin®雙輥研磨機上混配7分鐘。隨後根據國際規範ASTM G 154-C1,將所獲得之膜曝露於人工風化。所量測之參數為色彩偏差(δE,孔徑20mm、D65、10°)。結果列出於表5中。
實例6:安定聚甲基丙烯酸甲脂(PMMA)溶液鑄造膜(1)
將10g Plexiglas 7 N(Evonik)與50mg化合物A一起溶解於40g二氯甲烷中。在自動刮刀(Erichsen®)之幫助下以12mm/s之刮刀速度及120μm之間隙高度拉伸膜。隨後根據上述ASTM G 26 C將膜曝露於疝氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃、50-60%相對濕度,連續光,無水噴霧)。根據DIN 6167(1980-01)量測色彩。結果示於表6中。
實例7:安定聚甲基丙烯酸甲脂(PMMA)溶液鑄造膜(2)
將10g Plexiglas 7 N(Evonik)與50mg化合物A及100mg 2,2'-亞甲基雙(6-(2H-苯并三唑-2-基)-4-1,1,3,3-四甲基丁基)苯酚(Tinuvin®360)一起溶解於40g二氯甲烷中。在自動刮刀(Erichsen®)之幫助下以12mm/s之刮刀速度及120μm之間隙高度拉伸膜。將新拉伸之膜乾燥10分鐘。具有25μm厚度之所得膜具有16.3之黃度係數。(DIN
6167(1980-01))。隨後根據上述ASTM G 26 C將此膜曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,無水噴霧)。根據DIN 6167(1980-01)量測色彩。結果示於表7中。
實例8:安定聚甲基丙烯酸甲脂(PMMA)鑄造厚片(1)
將70g新蒸餾之甲基丙烯酸甲酯與70mg月桂醯過氧化物及105mg化合物A混合。在60℃水浴中在扭開式玻璃中對混合物進行除氣並且加熱3小時。將預聚合糖漿傾倒在距離1.8mm且三側密封之兩個玻璃板之間。將此玻璃夾層在烘箱中在60℃下保持16小時,隨後在120℃下保持3小時。所得聚甲基丙烯酸甲脂(PMMA)片具有32.2之黃度係數(DIN 6167(1980-01))。隨後根據上述ASTM G 26 C將此片材曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,無水噴霧)。根據DIN 6167(1980-01)量測色彩。結果示於表8中。
實例9:安定聚甲基丙烯酸甲脂(PMMA)厚片(2)
將70g新蒸餾之甲基丙烯酸甲酯與70mg月桂醯過氧化物、105mg化合物A及105mg 2-(2H-苯并三唑-2-基)-對甲酚(Tinuvin®P)混合。
在60℃水浴中在扭開式玻璃中對混合物進行除氣並且加熱3小時。將預聚合糖漿傾倒在距離1.8mm且在三側密封之兩個玻璃板之間。將此玻璃夾層在烘箱中在60℃下保持16小時,隨後在120℃下保持3小時。所得PMMA片具有32.2之黃度係數(DIN 6167(1980-01))。隨後根據上述ASTM G 26 C將此片材曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,無水噴霧)。根據DIN 6167(1980-01)量測色彩。結果示於表9中。
實例10:安定聚醯胺PA6(1)
對4000g PA6(Ultramid®B40,BASF)低溫進行研磨並且在真空烘箱中於80℃下乾燥4小時。在MTI M20 FU高速混合機中,將經研磨之聚合物與12g Irganox®B 1171(50%參(2,4-二第三丁基苯基)亞磷酸酯及50% N,N'-己烷-1,6-二基-雙[3-(3,5-二第三丁基-4-羥基苯基)丙醯胺)]之摻合物)及10g化合物A混合。隨後在Berstorff®ZE 25×32D上在250℃下混配粉末混合物,且在Heliomat 2000 6K乾燥機中乾燥之後,在Collin®CR-136/350膜擠出線上擠出為50μm厚之膜。
根據ASTM G 155 Cycle 1將此等膜曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,102分鐘乾燥,隨後進行18分鐘水噴霧)。根據DIN 6167(1980-01)量測色彩。結果列出於表10中。
實例11:安定聚醯胺PA6(2)
對4000g PA6(Ultramid®B40,BASF)進行低溫研磨並且在真空烘箱中於80℃下乾燥達4小時。在MTI M20 FU高速混合機中,將經研磨之聚合物與12g Irganox®B 1171(50%參(2,4-二第三丁基苯基)亞磷酸酯及50% N,N'-己烷-1,6-二基-雙[3-(3,5-二第三丁基-4-羥基苯基)丙醯胺)]之摻合物)及20g化合物A混合。隨後在Berstorff®ZE 25×32D上在250℃下混配粉末混合物,且在Heliomat 2000 6K乾燥機中乾燥之後,在Collin®CR-136/350膜擠出線上擠出為50μm厚之膜。
根據ASTM G 155 Cycle 1將此等膜曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,102分鐘乾燥,隨後進行18分鐘水噴霧)。根據DIN 6167(1980-01)量測色彩。結果列出於表11中。
實例12:安定聚甲醛(POM)(1)
對2,500g POM(Ultraform®N2320 003,BASF)進行低溫研磨並且在真空烘箱中於80℃下乾燥4小時。在Mixaco®Lab CM 12高速混合機中,將經研磨之聚合物與7.5g化合物A及3.75g乙烯雙(氧乙烯)雙-(3-(5-第三丁基-4-羥基-間甲苯基)-丙酸酯)(Irganox®245)混合。隨後在Berstorff®ZE 25×32D上在190℃下混配粉末混合物,且在Heliomat
2000 6K乾燥機中乾燥之後,在Engel HL 65上在190℃下射出模製為2mm厚之塊狀物。
根據ASTM G 155 Cycle 1將此等塊狀物曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,102分鐘乾燥,隨後進行18分鐘水噴霧)。根據DIN 6167(1980-01)量測色彩。結果列出於表12中。
實例13:安定聚甲醛(POM)(2)
對2,500g POM(Ultraform®N2320 003,BASF)進行低溫研磨並且在真空烘箱中於80℃下乾燥4小時。在Mixaco®Lab CM 12高速混合機中,將經研磨之聚合物與7.5g化合物A、3.75g乙烯雙(氧乙烯)雙-(3-(5-第三丁基-4-羥基-間甲苯基)-丙酸酯)(Irganox®245)及7.5g 2-(2H-苯并三唑-2-基)-4,6-雙(1-甲基-1-苯乙基)苯酚(Tinuvin®234)混合。隨後在Berstorff®ZE 25×32D上在190℃下混配粉末混合物,且在Heliomat 2000 6K乾燥機中乾燥之後,在Engel HL 65上在190℃下射出模製為2mm厚之塊狀物。。
根據ASTM G 155 Cycle 1將此等塊狀物曝露於氙氣燈(Xe燈,2個硼矽酸鹽過濾器「S」,0.35W/m2,340nm,63℃±3℃,50-60%相對濕度,連續光,102分鐘乾燥,隨後進行18分鐘水噴霧)。根據DIN 6167(1980-01)量測色彩。結果列出於表13中。
實例14:安定農業用低密度聚乙烯(LDPE)膜
如下製備用於農業應用之LDPE膜:將表14-1及表14-2中所列出之100g光安定劑、作為製程安定劑之5g Irganox®B900(80%參(2,4-二第三丁基苯基)亞磷酸酯及20%十八烷基-3-(3,5-二第三丁基-4-羥基苯基)-丙酸酯)及895g聚乙烯粉末(Versalis Riblene®FF 29,特徵在於0.921g/cm3之密度及0.6g/10'之熔體流動指數(190℃/2.16Kg))在渦輪攪拌機中混合。在實驗室規模OMC雙螺桿擠出機( 19mm,L/D=25)中於200℃之最高溫度下擠出母體混合物調配物。將如此獲得之顆粒之所定義等分試樣與50g含有5% Irganox®B900作為製程安定劑之聚乙烯母體混合物及一定量之上述初始聚乙烯(呈球粒形式)混合以獲得10000g調配物,在Rhonrad慢混合機中維持10分鐘,得到含有總計0.6%光安定劑之最終調配物。最後,在半工業性Dolci®吹製擠出機( 40mm,L/D=26)中在210℃之最高溫度下吹製此調配物,以得到150μm厚之膜。
人工風化:
對得自於如上文所描述而製備之調配物之膜樣本進行切割並且曝露在風化儀(Weather-o-Meter;WOM,按照ASTM G155,乾燥循環)中,以便進行加速光風化。曝露之後,在所定義之時間間隔取出樣本且進行拉伸測試:藉助於恆定速度張力計(按照ISO 527)量測殘餘斷裂伸長率,以便評估由於聚合物降解導致之塑膠膜機械性質衰減。評估結果列出於表14-1中:
上表顯示化合物A之優良光安定作用。
人工風化與化學處理(亞硫酸)組合:
對如上文所描述而製備之膜樣本進行切割且浸入0.1 N亞硫酸溶液中24小時。由此模擬由許多農業化學製品所致之酸性環境之效應。
在通風櫃下使薄膜樣本乾燥之後,將經處理之膜曝露於風化儀(WOM,按照ASTM G155,乾燥循環)中,以便進行加速光風化。如上所述,曝露之後在所定義之時間間隔取出調配物樣本且進行拉伸測試。評估結果列出於表14-2中。
上表顯示化合物A在農業化學製品存在下之優良光安定作用。
Claims (19)
- 一種式(I)化合物,
其中R1及R2彼此獨立地為氫、C1-C22烷基、-O、-OH、-CH2CN、C1-C18烷氧基、由-OH取代之C2-C18烷氧基;C5-C12環烷氧基、C3-C6烯基、C3-C6烯氧基、未經取代或在苯基上由1、2或3個C1-C4烷基取代之C7-C9苯基烷基;或C1-C8醯基;且R3及R4彼此獨立地為C1-C22烷基或式(Ia)之基團 其中R0具有R1及R2之含義之一。 - 如請求項1之化合物,其中R1及R2彼此獨立地為氫、C1-C8烷基、C1-C18烷氧基或環己氧基;且R3及R4彼此獨立地為C1-C6烷基。
- 如請求項1之化合物,其中該式(I)化合物為化合物(A)
- 一種組合物,其含有對由光、熱或氧化所致之降解敏感的有機物質及如請求項1之式(I)化合物。
- 如請求項4之組合物,其中該有機物質為熱塑性聚合物。
- 如請求項4之組合物,其中該有機物質為聚烯烴、丙烯腈/丁二烯/苯乙烯、聚氯乙烯、聚甲基丙烯酸甲脂、聚醯胺或聚甲醛。
- 如請求項4之組合物,其中該有機物質為熱塑性聚烯烴。
- 如請求項4之組合物,其中該有機物質為熱塑性聚乙烯或聚丙烯。
- 如請求項4至8中任一項之組合物,其進一步含有酚系抗氧化劑及/或酚系亞磷酸酯。
- 如請求項9之組合物,其中該酚系抗氧化劑為異戊四醇肆[3,5-二第三丁基-4-羥基苯基丙酸酯]、十八烷基-3-(3,5-二第三丁基-4-羥基苯基)丙酸酯、1,3,5-參(3,5-二第三丁基-4-羥基苯甲基)-2,4,6-三甲基苯、N,N'-雙(3,5-二第三丁基-4-羥基苯基丙醯基)己二醯胺或1,3,5-參[3,5-二第三丁基-4-羥苯甲基]異氰脲酸酯、2,4-二第三丁基苯基-3,5-二第三丁基-4-羥基苯甲酸酯或雙(1,2,2,6,6-五甲基哌啶-4-基)-丁基(3,5-二第三丁基-4-羥基苯甲基)丙二酸酯),且該酚系亞磷酸酯為參[2,4-二第三丁基苯基]亞磷酸酯。
- 如請求項4至8中任一項之組合物,其進一步含有與如請求項1中界定之式(I)化合物不同之空間受阻胺光安定劑及/或UV吸收劑。
- 如請求項11之組合物,其中該UV吸收劑係選自由2-(2'-羥基苯基)苯并三唑、2-羥基二苯甲酮、乙二醯胺及2-(2-羥基苯基)-1,3,5-三嗪組成之群。
- 如請求項4至8中任一項之組合物,其進一步含有填充劑及/或顏料。
- 一種汽車內部或外部裝飾材料,其係由如請求項4至13中任一項之組合物製造。
- 如請求項14之汽車內部或外部裝飾材料,其為用於車頂、座椅或儀錶板之材料。
- 一種農業製品,其係由如請求項4至13中任一項之組合物製造。
- 如請求項16之農業製品,其為溫室罩蓋。
- 一種用於安定有機物質以對抗由光、熱或氧化所致之降解的方法,其包含將至少一種如請求項1之式(I)化合物併入該有機物質中。
- 一種用於製備如請求項1之式(I)化合物之方法,其包含使式(II)化合物
與吡咯啶在有機溶劑中,視情況在有機或無機鹼存在下進行反應。
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| TWI752081B (zh) * | 2016-09-12 | 2022-01-11 | 德商巴地斯顏料化工廠 | 添加劑混合物 |
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| AU2018297119B2 (en) | 2017-07-06 | 2022-06-16 | Basf Se | Stabilized polyolefin compositions comprising benzofuranones and hindered amine light stabilizers |
| IT201700078234A1 (it) | 2017-07-11 | 2019-01-11 | 3V Sigma Spa | Ammine impedite |
| US11306191B2 (en) * | 2018-09-17 | 2022-04-19 | Cpg International Llc | Polymer-based construction materials |
| CN109134928B (zh) * | 2018-10-31 | 2020-05-19 | 天集化工助剂(沧州)有限公司 | N-取代的三嗪受阻胺光稳定剂及其制备方法和应用 |
| CN112126060B (zh) | 2019-06-25 | 2022-05-31 | 北京天罡助剂有限责任公司 | 一种聚合型高分子空间位阻胺及其制备方法 |
| KR20230112136A (ko) * | 2020-11-27 | 2023-07-26 | 사이텍 인더스트리스 인코포레이티드 | Uv-c 광에 대한 노출의 유해한 영향으로부터 유기 중합체성 물질을 보호하기 위한 조성물 및 방법 |
| CN115594924A (zh) * | 2021-07-07 | 2023-01-13 | 常熟卓辉光电科技股份有限公司(Cn) | 一种灯罩抑菌材料及其制备方法 |
| JP2023088414A (ja) * | 2021-12-15 | 2023-06-27 | ポリプラスチックス株式会社 | 放射線滅菌を行う用途に用いるポリアセタール樹脂組成物およびポリアセタール樹脂の放射線耐性向上方法 |
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| AU2014336388A1 (en) | 2016-04-07 |
| AR099646A1 (es) | 2016-08-10 |
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| BR112016006262A2 (pt) | 2017-08-01 |
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