BR112019003927B1 - Mistura aditiva, composição, artigo, e, método para estabilizar um material orgânico contra a degradação induzida por luz, calor ou oxidação descrição - Google Patents
Mistura aditiva, composição, artigo, e, método para estabilizar um material orgânico contra a degradação induzida por luz, calor ou oxidação descrição Download PDFInfo
- Publication number
- BR112019003927B1 BR112019003927B1 BR112019003927-9A BR112019003927A BR112019003927B1 BR 112019003927 B1 BR112019003927 B1 BR 112019003927B1 BR 112019003927 A BR112019003927 A BR 112019003927A BR 112019003927 B1 BR112019003927 B1 BR 112019003927B1
- Authority
- BR
- Brazil
- Prior art keywords
- tert
- butyl
- bis
- alkyl
- hydroxy
- Prior art date
Links
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
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- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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Abstract
Uma mistura aditiva contendo (A) pelo menos um composto da fórmula (I) em que R1 e R2, independentemente um do outro, são hidrogênio, alquila-C1-C22, -0-, -OH, -CH2CN, alcóxi-C1-C18, alcóxi-C2-C18 substituído por -OH; cicloalcóxi-C5-C12, alquenila-C3-C6, alquenilóxi-C3-C6, fenilalquila- C7-C9 não substituída ou substituída na fenila por 1, 2 ou 3 alquila-C1-C4; ou acila-C1-C8; e R3 e R4, independentemente um do outro, são alquila-C1-C22 ou um grupo da fórmula (Ia) em que R0 tem um dos significados de R1 e R2, e (B) pelo menos um aditivo antirrisco.
Description
[001] A presente invenção refere-se a uma mistura aditiva contendo um composto específico de amina estericamente impedida e um aditivo antirrisco, uma composição contendo um material orgânico suscetível a degradação induzida por luz, calor ou oxidação e a mistura aditiva, bem como um artigo feito da referida composição e o uso da mistura aditiva para estabilizar um material orgânico contraluz, calor ou oxidação. Os artigos feitos a partir da composição de acordo com a presente invenção têm uma superfície essencialmente livre de aderência em longo prazo com eflorescência nula ou reduzida.
[002] Compostos de amina estericamente impedida adequados são, por exemplo, descritos em WO-A-2015/055.563.
[003] A presente invenção refere-se em particular a uma mistura aditiva contendo
[004] (A) pelo menos um composto da fórmula (I) em que R1 e R2, independentemente um do outro, são hidrogênio, alquila-C1-C22, -O, -OH, -CH2CN, alcóxi-C1-C18, alcóxi-C2-C18 substituído por -OH; cicloalcóxi-C5-C12, alquenila-C3-C6, alquenilóxi-C3-C6, fenilalquila- C7-C9 não substituída ou substituída na fenila por 1, 2 ou 3 alquila-C1-C4; ou acila-C1-C8; e R3 e R4, independentemente um do outro, são alquila-C1-C22 ou um grupo da fórmula (Ia) em que R0 tem um dos significados de R1 e R2, e (B) pelo menos um aditivo antirrisco.
[005] Aditivos antirriscos são agentes que melhoram a resistência a riscos dos plásticos. O grupo de aditivos antirriscos é bem conhecido, em particular para melhorar a resistência a riscos das poliolefinas termoplásticas automotivas (TPOs automotivas). Um aditivo antirriscos também pode ser nomeado como, por exemplo, aditivo resistente a riscos.
[006] A razão em peso dos componentes (A):(B) é por exemplo 1:30 a 30:1, 1:20 a 20:1 ou 1:10 a 10:1, preferivelmente 1:5 a 5:1, em particular 1: 3 a 3:1.
[007] Exemplos de alquila com até 22 átomos de carbono são metila, etila, propila, isopropila, n-butila, sec-butila, isobutila, terc-butila, 2-etilbutila, n-pentila, isopentila, 1-metilpentila, 1,3-dimetil-butila, n-hexila, 1-metil- hexila, n-heptila, iso-heptila, 1,1,3,3-tetra-metil-butila, 1-metil-heptila, 3- metil-heptila, n-octila, 2-etil-hexila, 1,1,3-tri-metil-hexila, 1,1,3,3-tetra- metilpentila, nonila, decila, undecila, 1-metil-undecila, dodecila, 1,1,3,3,5,5- hexa-metil-hexila, tridecila, tetradecila, pentadecila, hexadecila, heptadecila, octadecila e eicosila. Um significado preferido é alquila-C1-C4. R1 e R2 são preferencialmente metila e R3 e R4 são de preferência n-butila.
[008] Exemplos de alcóxi tendo até 18 átomos de carbono são metóxi, etóxi, propóxi, isopropóxi, butóxi, isobutóxi, pentóxi, isopentóxi, hexóxi, heptóxi, octóxi, decilóxi, dodecilóxi, tetradecilóxi, hexadecilóxi e octadecilóxi. Os significados preferidos de R0, R1 e R2 são metóxi, etóxi, propóxi, octóxi ou undecilóxi.
[009] Exemplos de alqueniloxi-C3-C6 são 1-propeniloxi e 2- propenilóxi.
[0010] Um exemplo de alcoxi-C2-C18 substituído por -OH é 2-hidroxi- 2-metilpropilóxi.
[0011] Exemplos de cicloalcóxi-C5-C12 são ciclo-pentóxi, ciclo- hexóxi, ciclo-heptóxi, ciclo-octóxi, ciclo-decilóxi e ciclo-dodecilóxi. Cicloalcóxi-C5-C8, em particular ciclo-pentóxi e ciclo-hexóxi, é preferido.
[0012] Exemplos de fenilalquila-C7-C9 são benzila e 2-feniletila.
[0013] A fenilalquila-C7-C9 que é substituída no radical fenila por 1, 2 ou 3 alquila-C1-C4 é por exemplo, metilbenzila, dimetilbenzila, trimetilbenzila ou terc-butilbenzila.
[0014] Exemplos de alquenila-C3-C6 são alila, 2-metalila, butenila, pentenila e hexenila. Alila é o preferido. O átomo de carbono na posição 1 é de preferência saturado.
[0015] Exemplos de acila-C1-C8 são formila, acetila, propionila, butirila, pentanoíla, hexanoíla, heptanoíla, octanoíla, acriloíla, metacriloíla e benzoíla. Alcanoíla-C1-C8, alquenoíla-C3-C8 e benzoíla são preferidos. Acetila e o acriloíla são especialmente preferidos.
[0016] Um composto da fórmula (I) em que R1 e R2 independentemente um do outro são hidrogênio, alquila-C1-C8, alcoxila-C1- C18 ou ciclo-hexiloxila e R3 e R4, independentemente um do outro, são C1-C6- alquila é preferido.
[0018] Os compostos da fórmula (I) podem ser preparados em analogia com métodos conhecidos, por exemplo, como descrito em WO-A- 2015/055563 fazendo reagir um composto da fórmula (II) com pirrolidina em um solvente orgânico, opcionalmente na presença de uma base orgânica ou inorgânica.
[0019] De acordo com uma forma de realização preferida, o composto da fórmula (II) reage com, por exemplo, 0,8 a 5 equivalentes de pirrolidina em um solvente orgânico, por exemplo, tolueno, xileno, clorobenzeno, nitrobenzeno, mesitileno, etilbenzeno, um álcool tal como metanol, etanol, n- propanol, i-propanol, n-butanol, t-butanol; N-metil-2-pirrolidona, dimetilformamida, 1,4-dioxano, um éster ou pirrolidina; com ou sem água, na presença de, por exemplo, 0 a 10 equivalentes de um hidróxido de metal alcalino tal como LiOH, NaOH, KOH; um carbonato ou hidrogenocarbonato tal como NaHCO3, Na2CO3, K2CO3; uma base sólida, um zeólito, uma resina de troca iônica, uma base a base de amina ou uma base orgânica. A concentração do composto da fórmula (II) no solvente orgânico é de preferência 0,1-3 molar. A reação pode ser realizada, por exemplo, sob pressão atmosférica ou pressão elevada até 60 bar. As temperaturas usadas variam entre, por exemplo, 30°C e 180°C na dependência do tempo de reação de, por exemplo, 2h às 24h.
[0020] Os materiais de partida da fórmula (II) podem ser preparados em analogia com métodos conhecidos, por exemplo, como descrito na US-A- 5.268.401.
[0021] Exemplos de aditivos antirriscos são amidas de ácidos graxos saturados ou insaturados, por exemplo, erucamida, oleamida e estearamida, bem como um poli(organo)siloxano e misturas dos mesmos.
[0022] Os aditivos antirriscos da presente invenção são conhecidos dos versados na técnica. Eles podem ser preparados em analogia com métodos conhecidos. A maioria deles está comercialmente disponível.
[0023] Os aditivos antirriscos de poli(organo)siloxano comercialmente disponíveis preferidos são: TEGOMER® AntiScratch100, TEGOMER® M-Si 2650, TEGOPREN® 6846, TEGOMER® H-Si 6440 P, TEGOMER® AntiScratch 200, GENIOPLAST® S, GENIOPLAST® Pellet P e GENIOPLAST® Pellet P plus.
[0024] Um aditivo antirriscos de poli(organo)siloxano preferido refere-se a uma mistura de sílica e polímero de silicone (por exemplo 0-50% em peso, preferencialmente 30% em peso, de sílica fumada e 50 a 0% em peso, preferivelmente 70% em peso de polímero de silicone).
[0025] Outros aditivos antirriscos de poli(organo)siloxano são compostos da fórmula em que R é alquila, um resíduo de poliéster, um resíduo de acrilato, epóxi, hidroxialquila, aminoalquila, etc.
[0026] Outro aditivo antirriscos preferido é o IRGASURF® SR 100.
[0027] Uma mistura aditiva particularmente preferida da presente invenção contém um composto da fórmula (A) e a erucamida ou oleamida aditiva antirriscos.
[0028] O aditivo antirriscos também pode estar presente na mistura aditiva da presente invenção na forma de um masterbatch. Um masterbatch antirriscos contém, por exemplo, um polímero orgânico e até 50% em peso, relativo ao peso do polímero orgânico, do aditivo antirrisco.
[0029] Uma outra forma de realização da presente invenção é uma composição contendo um material orgânico susceptível a degradação induzida pela luz, calor e oxidação e a mistura aditiva de acordo com a presente invenção.
[0030] Exemplos de materiais orgânicos que podem ser estabilizados: 1. Polímeros de mono-olefinas e diolefinas, por exemplo, polipropileno, poli-isobutileno, polibut-1-eno, poli-4-metilpent-l-eno, polivinilciclo-hexano, poli-isopreno ou polibutadieno, bem como polímeros de ciclo-olefinas, por exemplo, de ciclopenteno ou norborneno, polietileno (que opcionalmente pode ser reticulado), por exemplo, polietileno de alta densidade (HDPE), polietileno de alta densidade e alto peso molecular (HDPE-HMW), polietileno de alta densidade e peso molecular ultra-alto (HDPE-UHMW), polietileno de média densidade (MDPE), polietileno de baixa densidade (LDPE), polietileno de baixa densidade linear (LLDPE), (VLDPE) e (ULDPE).
[0031] As poliolefinas, isto é, os polímeros de mono-olefinas exemplificados no parágrafo anterior, preferencialmente polietileno e polipropileno, podem ser preparados por métodos diferentes, e especialmente pelos seguintes: a) polimerização radical (normalmente sob alta pressão e a temperatura elevada).
[0032] b) polimerização catalítica usando um catalisador que normalmente contém um ou mais do que um metal dos grupos IVb, Vb, VIb ou VIII da Tabela Periódica. Estes metais têm usualmente um ou mais do que um ligante, tipicamente óxidos, halogenetos, alcoolatos, ésteres, éteres, aminas, alquilas, alquenilas e/ou arilas que podem ser π- ou o-coordenados. Estes complexos de metal podem estar na forma livre ou fixados em substratos, tipicamente em cloreto de magnésio ativado, cloreto de titânio (III), alumina ou óxido de silício. Estes catalisadores podem ser solúveis ou insolúveis no meio de polimerização. Os catalisadores podem ser usados por si próprios na polimerização ou podem ser usados outros ativadores, tipicamente alquilas metálicas, hidretos metálicos, halogenetos alquílicos metálicos, óxidos alquílicos metálicos ou alquiloxanos metálicos, sendo os referidos metais elementos dos grupos Ia, IIa e/ou IIIa da Tabela Periódica. Os ativadores podem ser modificados convenientemente com mais grupos éster, éter, amina ou éter silílico. Estes sistemas catalisadores são normalmente denominados Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metaloceno ou catalisadores de local único (SSC).
[0033] 2. Misturas dos polímeros mencionados em 1), por exemplo misturas de polipropileno com poli-isobutileno, polipropileno com polietileno (por exemplo PP/HDPE, PP/LDPE) e misturas de diferentes tipos de polietileno (por exemplo LDPE/HDPE).
[0034] 3. Copolímeros de mono-olefinas e diolefinas entre si ou com outros monômeros de vinila, por exemplo copolímeros de etileno/propileno, polietileno linear de baixa densidade (LLDPE) e misturas dos mesmos com polietileno de baixa densidade (LDPE), copolímeros de propileno/but-1-eno, copolímeros de propileno/isobutileno, copolímeros de etileno/but-1-eno, copolímeros de etileno/hexeno, copolímeros de etileno/metilpenteno, copolímeros de etileno/hepteno, copolímeros de etileno/octeno, copolímeros de etileno/vinilciclo-hexano, copolímeros de etileno/ciclo-olefina (por exemplo, etileno/norborneno como COC), copolímeros de etileno/1-olefinas, onde a 1-olefina é gerada in situ; copolímeros de propileno/butadieno, copolímeros de isobutileno/isopreno, copolímeros de etileno/vinilciclo- hexeno, copolímeros de etileno/acrilato de alquila, copolímeros de etileno/ metacrilato de alquila, copolímeros de etileno/acetato de vinila ou copolímeros de etileno/ácido acrílico e seus sais (ionômeros) bem como terpolímeros de etileno com propileno e um dieno tal como hexadieno, diciclopentadieno ou etilideno-norborneno; e misturas de tais copolímeros uns com os outros e com polímeros mencionados em 1) acima, por exemplo copolímeros de polipropileno/etileno-propileno, copolímeros de LDPE/ etileno-acetato de vinilo (EVA), copolímeros de LDPE/etileno-ácido acrílico (EAA), LLDPE/EVA, LLDPE/EAA e copolímeros de polialquileno/ monóxido de carbono alternados ou aleatórios e misturas dos mesmos com outros polímeros, por exemplo poliamidas.
[0035] 4. Resinas de hidrocarbonetos (por exemplo, C5-C9) incluindo modificações hidrogenadas das mesmas (por exemplo, agentes de adesividade) e misturas de polialquilenos e amido.
[0036] Homopolímeros e copolímeros de 1.) - 4.) podem ter qualquer estereoestrutura incluindo sindiotática, isotática, hemi-isotática ou atática; onde polímeros atáticos são preferidos. Polímeros de estereobloco também estão incluídos.
[0037] 5. Poliestireno, poli(p-metilestireno), poli (α-metilestireno).
[0038] 6. Homopolímeros e copolímeros aromáticos derivados de monômeros vinílicos aromáticos, incluindo estireno, α-metilestireno, todos os isômeros de vinil tolueno, especialmente p-viniltolueno, todos os isômeros de etil estireno, propil estireno, vinil bifenila, vinil naftaleno e vinil antraceno e misturas dos mesmos. Homopolímeros e copolímeros podem ter qualquer estereoestrutura incluindo sindiotática, isotática, hemi-isotática ou atática; onde polímeros atáticos são preferidos. Polímeros de estereobloco também estão incluídos.
[0039] 6a. Copolímeros incluindo os monômeros e comonômeros vinílicos aromáticos acima mencionados selecionados de etileno, propileno, dienos, nitrilas, ácidos, anidridos maleicos, maleimidas, acetato de vinila e cloreto de vinila ou derivados acrílicos e misturas dos mesmos, por exemplo estireno/butadieno, estireno/acrilonitrila, estireno/etileno (interpolímeros), estireno/metacrilato de alquila, estireno/butadieno/acrilato de alquila, estireno/ butadieno/metacrilato de alquila, estireno/anidrido maleico, estireno/ acrilonitrila/acrilato de metila; misturas de alta resistência ao impacto de copolímeros de estireno e outro polímero, por exemplo, um poliacrilato, um polímero de dieno ou um terpolímero de etileno/propileno/dieno; e copolímeros em bloco de estireno tais como estireno/butadieno/estireno, estireno/isopreno/estireno, estireno/etileno/butileno/estireno ou estireno/ etileno/propileno/estireno.
[0040] 6b. Polímeros aromáticos hidrogenados derivados da hidrogenação de polímeros mencionados em 6.), especialmente incluindo o policiclo-hexiletileno (PCHE) preparado por hidrogenação de poliestireno atático, frequentemente referido como polivinilciclo-hexano (PVCH).
[0041] 6c. Polímeros aromáticos hidrogenados derivados da hidrogenação de polímeros mencionados em 6a.).
[0042] Homopolímeros e copolímeros podem ter qualquer estéreoestrutura incluindo sindiotática, isotática, hemi-isotática ou atática; onde polímeros atáticos são preferidos. Polímeros de estéreobloco também estão incluídos.
[0043] 7. Copolímeros de enxerto de monômeros aromáticos de vinila tais como estireno ou α-metilestireno, por exemplo, estireno em polibutadieno, estireno em copolímeros de polibutadieno-estireno ou polibutadieno-acrilonitrila; estireno e acrilonitrila (ou metacrilonitrila) em polibutadieno; estireno, acrilonitrila e metacrilato de metila em polibutadieno; estireno e anidrido maleico em polibutadieno; estireno, acrilonitrila e anidrido maleico ou maleimida em polibutadieno; estireno e maleimida em polibutadieno; estireno e acrilatos ou metacrilatos de alquila em polibutadieno; estireno e acrilonitrila em terpolímeros de etileno/propileno/dieno; estireno e acrilonitrila em acrilatos de polialquila ou metacrilatos de polialquila, estireno e acrilonitrila em copolímeros de acrilato/butadieno, bem como misturas dos mesmos com os copolímeros listados em 6), por exemplo, as misturas de copolímero conhecidas como polímeros ABS, MBS, ASA ou AES.
[0044] 8. Polímeros contendo halogênio, tais como policloropreno, borrachas cloradas, copolímero clorado e bromado de isobutileno-isopreno (borracha de halobutila), polietileno clorado ou sulfofluorado, copolímeros de etileno e etileno clorado, homopolímeros e copolímeros de epicloridrina, especialmente polímeros de compostos vinílicos contendo halogênio, por exemplo, cloreto de polivinila, cloreto de polivinilideno, fluoreto de polivinila, fluoreto de polivinilideno, assim como os copolímeros dos mesmos tais como cloreto de vinila/cloreto de vinilideno, cloreto de vinila/acetato de vinila ou copolímeros cloreto de vinilideno/acetato de vinila.
[0045] 9. Polímeros derivados de ácidos α,β-insaturados e derivados dos mesmos, tais como poliacrilatos e polimetacrilatos; polimetilmetacrilatos, poliacrilamidas e poliacrilonitrilas, modificados por impacto com acrilato de butila.
[0046] 10. Copolímeros dos monômeros mencionados em 9) entre si ou com outros monômeros insaturados, por exemplo copolímeros de acrilonitrila/butadieno, copolímeros de acrilonitrila/acrilato de alquila, copolímeros de acrilonitrila/acrilato de alcoxialquila ou de acrilonitrila/ halogeneto de vinila ou terpolímeros de acrilonitrila/ metacrilato de alquila/ butadieno.
[0047] 11. Polímeros derivados de álcoois e aminas insaturados ou os derivados acila ou acetais dos mesmos, por exemplo, álcool polivinílico, acetato de polivinila, estearato de polivinila, benzoato de polivinila, maleato de polivinila, butiral de polivinila, ftalato de polialila ou polialil melamina; bem como os seus copolímeros com olefinas mencionados em 1) acima.
[0048] 12. Homopolímeros e copolímeros de éteres cíclicos tais como polialquileno glicóis, óxido de polibutileno, óxido de polipropileno ou copolímeros dos mesmos com éteres bisglicidílicos.
[0049] 13. Poliacetais tais como polioximetileno e os polioximetilenos que contêm óxido de etileno como comonômero; poliacetais modificados com poliuretanos termoplásticos, acrilatos ou MBS.
[0050] 14. Óxidos e sulfetos de polifenileno e misturas de óxidos de polifenileno com polímeros de estireno ou poliamidas.
[0051] 15. Poliuretanos derivados de poliéteres, poliésteres ou polibutadienos terminados por hidroxila, por um lado, e poli-isocianatos alifáticos ou aromáticos, por outro lado, bem como precursores dos mesmos.
[0052] 16. Poliamidas e copoliamidas derivadas de diaminas e ácidos dicarboxílicos e/ou de ácidos aminocarboxílicos ou das lactamas correspondentes, por exemplo, poliamida 4, poliamida 6, poliamida 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, poliamida 11, poliamida 12, poliamidas aromáticas a partir de m-xileno diamina e ácido adípico; poliamidas preparadas a partir de hexametilenodiamina e ácido isoftálico ou/e ácido tereftálico com ou sem um elastômero como modificador, por exemplo, poli-2,4,4-trimetil-hexametileno tereftalamida ou poil-m-fenileno isoftalamida; e também copolímeros em bloco das poliamidas acima mencionadas com poliolefinas, copolímeros de olefina, ionômeros ou elastômeros quimicamente ligados ou enxertados; ou com poliéteres, por exemplo, com polietileno glicol, polipropileno glicol ou politetrametileno glicol; assim como poliamidas ou copolímeros modificados com EPDM ou ABS; e poliamidas condensadas durante o processamento (sistemas de poliamida RIM).
[0053] 17. Poliureias, poli-imidas, poliamidas-imidas, polieterimidas, poliesterimidas, poli-hidotinas e polibenzimidazóis.
[0054] 18. Poliésteres derivados de ácidos dicarboxílicos e dióis e/ou de ácidos hidroxicarboxílicos ou as correspondentes lactonas ou lactidas, por exemplo, tereftalato de polietileno, tereftalato de polibutileno, tereftalato de poli-1,4-dimetilolciclo-hexano, naftalato de polialquileno e poli- hidroxibenzoatos assim como ésteres de copoliéter derivados de poliéteres terminados por hidroxila, e também poliésteres modificados com policarbonatos ou MBS. Os copoliésteres podem compreender, por exemplo - mas não estão limitados a - succinato/tereftalato de polibutileno, adipato/tereftalato de polibutileno, adipato/tereftalato de politetrametileno, succinato/adipato de polibutileno, succinato/carbonato de polibutileno, copolímero de poli-3-hidroxibutirat/octanoato, terpolímero de poli-3- hidroxibutirato/hexanoato/decanoato. Além disso, os poliésteres alifáticos podem compreender, por exemplo - mas não estão limitados a - a classe de poli(hidroxialcanoatos), em particular, poli(propiolactona), poli(butirolactona), poli(pivalolactona), poli(valerolactona) e poli(caprolactona), succinato de polietileno, furanoato de polietileno, succinato de polipropileno, succinato de polibutileno, succinato de poli- hexametileno, adipato de polietileno, adipato de polipropileno, adipato de polibutileno, adipato de poli-hexametileno, oxalato de polietileno, oxalato de polipropileno, oxalato de polibutileno, oxalato de poli-hexametileno, sebacato de polietileno, sebacato de polipropileno, sebacato de polibutileno e ácido poliláctico (PLA) bem como poliésteres correspondentes modificados com policarbonatos ou MBS. O termo “ácido poliláctico (PLA)” designa um homopolímero de preferência poli-L-láctido e qualquer das suas misturas ou ligas com outros polímeros; um copolímero de ácido láctico ou lactido com outros monômeros, tais como ácidos hidroxi-carboxílicos, como por exemplo, ácido glicólico, ácido 3-hidroxi-butírico, ácido 4-hidroxi-butírico, ácido 4- hidroxi-valérico, ácido 5-hidroxi-valérico, ácido 6-hidroxi-capróico e formas cíclicas dos mesmos; os termos “ácido láctico” ou “lactido” incluem ácido L- láctico, ácido D-láctico, misturas e dímeros dos mesmos, isto é, L-lactido, D- lactido, meso-lacida e quaisquer misturas dos mesmos.
[0055] 19. Policarbonatos e carbonatos de poliéster.
[0056] 20. Policetonas.
[0057] 21. Polissulfonas, poliéter sulfonas e poliéter cetonas.
[0058] 22. Polímeros reticulados derivados de aldeídos, por um lado, e fenóis, ureias e melaminas, por outro lado, tais como resinas de fenol/ formaldeído, resinas de ureia/formaldeído e resinas de melamina/ formaldeído.
[0059] 23. Resinas alquídicas de secagem e não secagem.
[0060] 24. Resinas de poliéster insaturadas derivadas de copoliésteres de ácidos dicarboxílicos saturados e insaturados com álcoois poli-hídricos e compostos vinílicos como agentes de reticulação, e também modificações contendo halogênio dos mesmos de baixa inflamabilidade.
[0061] 25. Resinas acrílicas reticuláveis derivadas de acrilatos substituídos, por exemplo, acrilatos de epóxi, acrilatos de uretano ou acrilatos de poliéster.
[0062] 26. Resinas alquídicas, resinas de poliéster e resinas de acrilato reticuladas com resinas de melamina, resinas de ureia, isocianatos, isocianuratos, poli-isocianatos ou resinas epóxi.
[0063] 27. Resinas epóxi reticuladas derivadas de compostos glicidílicos alifáticos, cicloalifáticos, heterocíclicos ou aromáticos, por exemplo, produtos de éteres de diglicidila de bisfenol A e bisfenol F, que são reticulados com endurecedores usuais, tais como anidridos ou aminas, com ou sem aceleradores.
[0064] 28. Polímeros naturais tais como celulose, borracha, gelatina e derivados homólogos quimicamente modificados dos mesmos, por exemplo, acetatos de celulose, propionatos de celulose e butiratos de celulose, ou os éteres de celulose tais como metil celulose; bem como as resinas e seus derivados.
[0065] 29. Misturas dos polímeros acima mencionados (polimisturas), por exemplo, PP/EPDM, Poliamida/EPDM ou ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrilatos, POM/termoplástico PUR, PC/termoplástico PUR, POM/acrilato, POM/MBS, PPO/HIPS, PPO/PA 6.6 e copolímeros, PA/HDPE, PA/PP, PA/ PPO, PBT/PC/ABS ou PBT/PET/PC.
[0066] 30. Materiais orgânicos de ocorrência natural e sintéticos que são compostos monoméricos puros ou misturas de tais compostos, por exemplo, óleos minerais, gorduras animais e vegetais, óleos e ceras, ou óleos, gorduras e ceras baseadas em ésteres sintéticos (por exemplo, ftalatos, adipatos, fosfatos ou trimelitatos) e também misturas de ésteres sintéticos com óleos minerais em quaisquer razões em peso, tipicamente aquelas usadas como composições de fiação, bem como emulsões aquosas de tais materiais.
[0067] 31. Emulsões aquosas de borracha natural ou sintética, por exemplo, látex natural ou látices de copolímeros de estireno/butadieno carboxilados.
[0068] Uma poliolefina, uma acrilonitrila/butadieno/estireno, um cloreto de polivinila, um poli(metacrilato de metila), uma poliamida ou um polioximetileno são de interesse especial.
[0069] De acordo com uma forma de realização preferida, o material orgânico é um elastômero termoplástico.
[0070] Exemplos de elastômeros termoplásticos incluem elastômeros termoplásticos de poliolefina e elastômeros termoplásticos de poliestireno do tipo de copolímero em bloco. Os elastômeros termoplásticos de poliolefina compreendem resinas de poliolefina tais como polipropileno e polietileno servindo como segmentos duros e composições de borracha tais como etileno- propileno-dieno-elastômero (EPDM) servindo como segmentos macios. O elastômero termoplástico de poliestireno do tipo de copolímero em bloco compreende poliestireno servindo como segmentos duros e polidienos tais como polibutadieno ou poli-isopreno servindo como segmentos macios.
[0071] Alternativamente, uma mistura dos elastômeros de poliolefina e dos elastômeros de poliestireno pode também ser usada como o elastômero termoplástico da presente invenção. Os métodos para combinar segmentos macios e segmentos duros em elastômeros termoplásticos podem ser divididos, a grosso modo, em mistura simples, implantação por copolimerização e reticulação dinâmica. As combinações de segmentos de elastômeros termoplásticos de poliestireno incluem um copolímero em bloco de estireno-butadieno-estireno (SBS), um copolímero em bloco de estireno- isopreno-estireno (SIS), um copolímero em bloco de estireno-etileno butileno- estireno (SEBS), um copolímero em bloco de estireno-etileno propileno- estireno (SEPS), um polímero hidrogenado de qualquer um dos quatro copolímeros, um polímero hidrogenado de SBR aleatório (HSBR) e uma mistura de polipropileno e um ou mais elementos arbitrários selecionados entre estes polímeros. (SBR = borracha de estireno butadieno)
[0072] É de interesse uma poliolefina termoplástica, em particular polietileno ou polipropileno contendo uma fase de borracha à base de etileno e/ou propileno.
[0073] O composto da fórmula (I) e o antirrisco podem ser usados em várias proporções, dependendo da natureza do material orgânico a ser estabilizado, do uso final e da presença de outros aditivos.
[0074] Em geral, é apropriado usar, por exemplo, 0,01 a 5% em peso de um composto de fórmula (I), em relação ao peso do material orgânico a ser estabilizado, preferivelmente 0,05 a 2%, em particular 0,05 a 1%. Além disso, é apropriado usar, por exemplo, 0,001 a 10% em peso do aditivo antirriscos, em relação ao peso do material orgânico a ser estabilizado, preferivelmente 0,1 a 10% em peso, em particular 0,1 a 6% por peso.
[0075] Os compostos da fórmula (I) e o aditivo antirriscos podem ser adicionados, por exemplo, a materiais poliméricos antes, durante ou após a polimerização ou reticulação dos referidos materiais. Além disso, podem ser incorporados nos materiais poliméricos na forma pura ou encapsulados em ceras, óleos ou polímeros.
[0076] Em geral, os compostos da fórmula (I) e o aditivo antirriscos podem ser incorporados em conjunto ou em forma individual nos materiais orgânicos por vários processos, tais como mistura a seco na forma de pó, ou mistura úmida na forma de soluções ou suspensões ou ainda sob a forma de masterbatch que contém os compostos da fórmula (I) e/ou o aditivo antirrisco em uma concentração de 2,5 a 70%, de preferência de 2,5 a 50%, em especial 2,5 a 25%, em peso; em tais operações, o polímero pode ser usado na forma de pó, grânulos, soluções, suspensões ou na forma de látices.
[0077] Exemplos de processamento das composições de acordo com a presente invenção são: Injeção de moldagem por sopro, extrusão, moldagem por sopro, rotomoldagem, na decoração do molde (injeção nas costas), moldagem por lama, moldagem por injeção, moldagem por coinjeção, moldagem, moldagem por compressão, prensagem, extrusão de película (película fundida; película soprada), fiação de fibra (tecido, não-tecido), estiramento (uniaxial, biaxial), recozimento, estampagem profunda, calandragem, transformação mecânica, sinterização, coextrusão, revestimento, laminação, reticulação (radiação, peróxido, silano), deposição de vapor, soldar em conjunto, cola, vulcanização, termoformação, extrusão de tubos, extrusão de perfis, extrusão de chapas; fundição de chapas, revestimento por rotação, cintagem, formação de espuma, reciclagem/retrabalho, revestimento por extrusão, viscorredução (peróxido, térmica), fusão de fibras fundidas, fiação ligada, tratamento de superfície (descarga de corona, chama, plasma), esterilização (por raios gama, feixes de elétrons), revestimento por gel, extrusão de fita, processo SMC ou plastissol.
[0078] As composições de acordo com a presente invenção podem ser vantajosamente utilizadas para a preparação de vários artigos conformados. Exemplos: I-1) Dispositivos flutuantes, aplicações marítimas, pontões, boias, madeira plástica para convés, cais, barcos, caiaques, remos e reforços de praia.
[0079] I-2) Aplicações automotivas, em particular para-choques, painéis de controle, bateria, revestimento traseiro e frontal, peças moldadas sob o capô, prateleira, porta-malas, revestimentos internos, tampas de air bags, molduras eletrônicas para conexões (luzes), painéis para painéis de controle, vidro de farol, painel de instrumentos, revestimentos exteriores, estofos, luzes automotivas, faróis, luzes de estacionamento, luzes traseiras, luzes de parada, acabamentos interiores e exteriores; painéis de porta; tanque de gasolina; frente de vidro; janelas traseiras; apoio de bancos, painéis exteriores, isolamento de cabos, extrusão de perfis para vedação, revestimento, coberturas de pilares, peças de chassis, sistemas de escape, filtro de combustível/carga, bombas de combustível, tanque de combustível, molduras laterais, topos conversíveis, espelhos exteriores, guarnição exterior, fixadores/fixações, módulo de extremidade frontal, vidro, dobradiças, sistemas de fecho, porta-bagagens/tejadilho, peças prensadas/estampadas, vedantes, proteção contra impacto lateral, amortecedor/isolador de som e teto solar.
[0080] I-3) Dispositivos de circulação rodoviária, em especial postagens de sinais, postes de sinalização rodoviária, acessórios de automóvel, triângulos de sinalização, estojos médicos, capacetes, pneus.
[0081] I-4) Dispositivos para avião, ferrovia, automóvel (carro, moto), incluindo mobiliário.
[0082] I-5) Dispositivos para aplicações espaciais, em particular foguetes e satélites, por exemplo, escudos de reentrada.
[0083] I-6) Dispositivos para arquitetura e design, aplicações de mineração, sistemas acústicos silenciosos, refúgios de rua e abrigos.
[0084] II-1) Aparelhos, estojos e coberturas em geral e aparelhos eletroeletrônicos (computador pessoal, telefone, telefone celular, impressora, televisores, aparelhos de áudio e vídeo), vasos de flores, antena de TV via satélite e dispositivos de painel.
[0085] II-2) Jaquetas para outros materiais, como aço ou têxteis.
[0086] II-3) Dispositivos para a indústria eletrônica, em particular isolamento para plugues, especialmente plugues de computadores, estojos para peças elétricas e eletrônicas, placas impressas e materiais para armazenamento eletrônico de dados, como chips, cartões de cheques ou cartões de crédito.
[0087] II-4) Aparelhos elétricos, em especial máquinas de lavar roupa, máquinas de secar, fornos (fornos micro-ondas), máquinas de lavar louça, misturadores e ferros de passar.
[0088] II-5) Coberturas para luzes (por exemplo, postes de iluminação, abajures).
[0089] II-6) Aplicações em fios e cabos (semicondutores, isolamento e revestimento de cabos).
[0090] II-7) Folhas para condensadores, refrigeradores, dispositivos de aquecimento, condicionadores de ar, encapsulamento de eletrônicos, semicondutores, máquinas de café e aspiradores de pó.
[0091] III-1) Artigos técnicos, tais como roda dentada (engrenagem), encaixes de deslizamento, espaçadores, parafusos, pinos, alças e puxadores.
[0092] III-2) Pá de rotor, ventiladores e palhetas de vento, dispositivos solares, piscinas, coberturas de piscinas, forros de piscinas, tanques de piscinas, armários, divisórias, paredes de ripas, paredes articuladas, tetos, persianas (por exemplo, persianas de rolo), fixações, conexões entre tubos, luvas e correias transportadoras.
[0093] III-3) Artigos sanitários, em especial cabines de chuveiro, assentos sanitários, tampas e pias.
[0094] III-4) Artigos de higiene, em especial fraldas (bebês, incontinência de adultos), artigos de higiene feminina, cortinas de chuveiro, escovas, tapetes, banheiras, banheiros móveis, escovas de dentes e comadres.
[0095] III-5) Tubos (reticulados ou não) para água, águas residuais e produtos químicos, tubos para proteção de fios e cabos, tubos para gás, óleo e esgoto, calhas, tubos de drenagem e sistemas de drenagem.
[0096] III-6) Perfis de qualquer geometria (painéis de janela) e revestimento de parede.
[0097] III-7) Substitutos do vidro, em especial placas extrudadas, envidraçados para edifícios (monolíticos, gêmeos ou multifoliados), aviões, escolas, folhas extrudadas, películas para janela para vidros arquitetônicos, trens, artigos de transporte e artigos sanitários.
[0098] III-8) Chapas (paredes, tábua de corte), revestimento por extrusão (papel fotográfico, tetrapack e revestimento de tubos), silos, sucedâneos de madeira, madeira plástica, compósitos de madeira, paredes, superfícies, móveis, folhas decorativas, revestimentos de pavimentos (aplicações interiores e exteriores), pisos, placas de pato e azulejos.
[0099] III-9) Coletores de entrada e saída.
[00100] III-10) Aplicações e coberturas de cimento, concreto, compósitos, revestimento de parede e revestimentos, corrimãos, balaustradas, bancadas de cozinha, coberturas, telhas, ladrilhos e lonas.
[00101] IV-1) Placas (paredes e tábua de corte), bandejas, grama artificial, astroturf, cobertura artificial para anéis de estádio (atletismo), piso artificial para anéis de estádio (atletismo) e fitas.
[00102] IV-2) Panos tecidos contínuos e fibras curtas, fibras (tapetes/ artigos higiênicos/geotêxteis/monofilamentos; filtros; toalhetes/cortinas (sombras)/aplicações médicas), fibras a granel (aplicações tais como roupas de proteção/vestidos), redes, cordas, cabos, cordas, fios, cordas finas, cintos de segurança, roupas, roupa íntimas, luvas; chuteiras; botas de borracha, vestuário íntimo, vestidos, roupas de banho, roupas esportivas, guarda-chuva (sombrinha, guarda-sol), paraquedas, parapentes, velas, “balloon-silk“, artigos de camping, tendas, colchões de ar, espreguiçadeiras, sacos a granel e bolsas.
[00103] IV-3) Membranas, isolamentos, coberturas e vedações para telhados, túneis, lixões, lagoas, lixeiras, membranas de coberturas de paredes, geomembranas, piscinas, cortinas (sombras)/guarda-sóis, toldos, copas, papel de parede, embalagem de alimentos e embalagem (flexível e sólida), embalagens médicas (flexíveis e sólidas), airbags/cintos de segurança, apoios para braços e cabeça, tapetes, console central, painel de instrumentos, cockpits, porta, módulo de console superior, guarnição de portas, iluminação interior, espelhos interiores, prateleira de bagagens, cobertura de bagagem traseira, assentos, coluna de direção, volante, têxteis e bagageira.
[00104] V-1) Películas (embalagem, despejo, laminação, embalagem de fardos, piscinas, sacos de lixo, papel de parede, película extensível, ráfia, película de dessalinização, baterias e conectores).
[00105] V-2) Películas agrícolas (coberturas de estufa, túnel, cobertura morta, silagem, empacotamento de fardo), especialmente na presença de aplicação intensiva de agroquímicos.
[00106] VI-1) Embalagem e acondicionamento de alimentos (flexíveis e sólidos), BOPP, BOPET, garrafas.
[00107] VI-2) Sistemas de armazenamento, tais como caixas (engradados), malas, baús, caixas de casas, paletes, prateleiras, trilhos, caixas de parafusos, pacotes e latas.
[00108] VI-3) Cartuchos, seringas, aplicações médicas, contêineres para qualquer transporte, cestos de lixo e lixeiras, sacos de lixo, caixas, caixotes de lixo, forros de escaninho, contentor de lixo com rodinhas, recipientes em geral, tanques para água/água usada/produtos químicos/gás/ óleo/gasolina/diesel; revestimento de tanques, caixas, engradados, estojos de bateria, comedouros, dispositivos médicos, tais como êmbolo, aplicações oftálmicas, dispositivos de diagnóstico e embalagem para blisters farmacêuticos.
[00109] VII-1) Revestimento por extrusão (papel fotográfico, tetrapack, revestimento de tubagens), artigos domésticos de qualquer tipo (por exemplo, aparelhos, garrafa térmica/cabide de roupas), sistemas de fixação tais como plugues, braçadeiras de arame e cabo, zíperes, fechos, fechaduras e fechamento por pressão.
[00110] VII-2) Dispositivos de apoio, artigos para o tempo de lazer, tais como esportes e aparelhos de ginástica, esteiras de ginástica, botas de esqui, patins em linha, esquis, big foot, superfícies atléticas (por exemplo, terrenos para tênis); tampas de parafuso, e tampas para garrafas, e latas.
[00111] VII-3) Móveis em geral, artigos de espuma (almofadas, absorvedores de impacto), espumas, esponjas, panos de prato, esteiras, cadeiras de jardim, assentos de estádio, mesas, sofás, brinquedos, kits de construção (pranchas/figuras/bolas), teatros, slides e veículos de brincar.
[00112] VII-4) Materiais para armazenamento de dados ópticos e magnéticos.
[00113] VII-5) Utensílios de cozinha (comer, beber, cozinhar, armazenar).
[00114] VII-6) Caixas para CD's, cassetes e fitas de vídeo; artigos eletrônicos de DVD, material de escritório de qualquer tipo (canetas esferográficas, carimbos e almofadas de tinta, mouse, prateleiras, faixas), garrafas de qualquer volume e conteúdo (bebidas, detergentes, cosméticos, incluindo perfumes) e fitas adesivas.
[00115] VII-7) Calçados (sapatos/solas para sapatos), palmilhas, espadas, adesivos, adesivos estruturais, caixas de alimentos (frutas, legumes, carne, peixe), papel sintético, rótulos para garrafas, sofás, articulações artificiais (humanas), impressão de placas (flexográficas), placas de circuito impresso e tecnologias de exibição.
[00116] VII-8) Dispositivos de polímeros carregados (talco, giz, argila da China (caulim), wollastonita, pigmentos, negro de fumo, TiO2, mica, nanocompósitos, dolomita, silicatos, vidro, amianto).
[00117] É preferido um material de acabamento interior ou exterior automotivo feito de uma composição de acordo com a presente invenção. Os artigos moldados particularmente preferidos são os listados acima em I-2. De interesse também é um material de revestimento para um telhado, assento ou painel de instrumentos.
[00118] Se desejado, um ou mais aditivos convencionais para polímeros sintéticos, tais como antioxidantes, absorventes de UV, estabilizadores de níquel, pigmentos, enchimentos, plastificantes, inibidores de corrosão e desativadores de metal, podem ser adicionados aos materiais orgânicos contendo os compostos da fórmula (I).
[00119] Exemplos de aditivos convencionais são:
[00120] 1.1. Monofenóis alquilados, por exemplo, 2,6-di-terc-butil-4- metilfenol, 2-terc-butil-4,6-dimetilfenol, 2,6-di-terc-butil-4-etilfenol, 2,6-di- terc-butil-4-n-butilfenol, 2,6-di-terc-butil-4-isobutilfenol, 2,6-diciclopentil-4- metilfenol, 2-(α-metilciclo-hexil)-4,6-dimetilfenol, 2,6-dioctadecil-4- metilfenol, 2,4,6-triciclo-hexilfenol, 2,6-di-terc-butil-4-metoximetilfenol, nonilfenóis que são lineares ou ramificados nas cadeias laterais, por exemplo, 2,6-di-nonil-4-metilfenol, 2,4-dimetil-6-(1'-metilundec-1'-il)fenol, 2,4- dimetil-6-(1'-metil-heptadec-1'-il) fenol, 2,4-dimetil-6-(1'-metilpentadec-1'-il) fenol, 2,4- dimetil-6-(1'-metiltridec-1'-il)fenol e misturas dos mesmos.
[00121] 1.2. Alquiltiometilfenóis, por exemplo, 2,4-dioctiltiometil-6- terc-butilfenol, 2,4-dioctiltiometil-6-metilfenol, 2,4-dioctiltiometil-6-etilfenol, 2,6-di-dodeciltiometil-4-nonilfenol.
[00122] 1.3. Hidroquinonas e hidroquinonas alquiladas, por exemplo, 2,6-di-terc-butil-4-metoxifenol, 2,5-di-terc-butil-hidroquinona, 2,5-di-terc- amil-hidroquinona, 2,6-difenil-4-octadeciloxifenol, 2,6-di-terc-butil- hidroquinona, 2,5-di-tert-butil-4-hidroxianisol, 3,5-di-tert-butil-4- hidroxianisol, estearato de 3,5-di-terc-butil-4-hidroxifenila, adipato de bis (3,5-di-terc-butil-4-hidroxifenila).
[00123] 1.4. Tocoferóis, por exemplo, α-tocoferol, β-tocoferol, y- tocoferol, δ-tocoferol e misturas dos mesmos (vitamina E).
[00124] 1.5. Éteres tiodifenílicos hidroxilados, por exemplo, 2,2'-tiobis (6-terc-butil-4-metilfenol), 2,2'-tiobis(4-octilfenol), 4,4'-tiobis(6-terc-butil-3- metilfenol), 4,4'-tiobis(6-terc-butil-2-metilfenol), 4,4'-tiobis(3,6-di-sec- amilfenol), dissulfeto de 4,4'-bis (2,6-dimetil-4-hidroxifenila).
[00125] 1.6. Alquilidenobisfenóis, por exemplo, 2,2'-metilenobis(6- terc-butil-4-metilfenol), 2,2'-metilenobis(6-terc-butil-4-etilfenol), 2,2'- metilenobis[4-metil-6-(α-metilciclo-hexil)fenol], 2,2'-metilenobis(4-metil-6- ciclo-hexilfenol), 2,2'-metilenobis(6-nonil-4-metilfenol), 2,2'-metilenobis (4,6-di-terc-butilfenol), 2,2'-etilidenobis(4,6-di-terc-butilfenol), 2,2'- etilidenobis(6-terc-butil-4-isobutilfenol), 2,2'-metilenobis[6-(α-metilbenzil)-4- nonilfenol], 2,2'-metilenobis[6-(α,α-dimetilbenzil)-4-nonilfenol], 4,4'- metillenobis(2,6-di-terc-butilfenol), 4,4'-metilenobis(6-terc-butil-2- metilfenol), 1,1-bis(5-terc-butil-4-hidroxi-2-metilfenil)butano, 2,6-bis(3-terc- butil-5-metil-2-hidroxibenzil)-4-metilfenol, 1,1,3-tris(5-terc-butil-4-hidroxi-2- metilfenil)butano, 1,1-bis(5-terc-butil-4-hidroxi-2-metil-fenil)-3-n- dodecilmercaptobutano, butirato de bis[3,3-bis(3'-terc-butil-4’-hidroxifenila)] de etileno glicol, bis(3-terc-butil-4-hidroxi-5-metil-fenil)diciclopentadieno, tereftalato de bis[2-(3'-terc-butil-2'-hidroxi-5'-metilbenzil)-6-terc-butil-4- metilfenila], 1,1-bis-(3,5-dimetil-2-hidroxifenil)butano, 2,2-bis(3,5-di-terc- butil-4-hidroxifenil)propano, 2,2-bis(5-terc-butil-4-hidroxi-2-metilfenil)-4-n- dodecilmercaptobutano, 1,1,5,5-tetra-(5-terc-butil-4-hidroxi-2-metilfenil) pentano.
[00126] 1.7. Compostos O-, N- e S-benzila, por exemplo, éter 3,5,3', 5'- tetra-terc-butil-4,4'-di-hidroxidibenzílico, mercaptoacetato de octadecil-4- hidroxi-3,5-dimetilbenzila, mercaptoacetato de tridecil-4-hidroxi-3,5-di-terc- butilbenzila, tris(3,5-di-terc-butil-4-hidroxibenzil)amina, ditioterftalato de bis(4-terc-butil-3-hidroxi-2,6-dimetilbenzila), sulfeto de bis(3,5-di-terc-butil- 4-hidroxibenzila), mercaptoacetato de isooctil-3,5-di-terc-butil-4- hidroxibenzila.
[00127] 1.8. Malonatos hidroxibenzilados, por exemplo, malonato de dioctadecil-2,2-bis(3,5-di-terc-butil-2-hidroxibenzila), malonato de di- octadecil-2-(3-terc-butil-4-hidroxi-5-metilbenzila), malonato de di- dodecilmercaptoetil-2,2-bis(3,5-di-terc-butil-4-hidroxibenzila), malonato de bis[4-(1,1,3,3-tetrametilbutil)fenil]-2,2-bis(3,5-di-terc-butil-4-hidroxibenzila).
[00128] 1.9. Compostos hidroxibenzílicos aromáticos, por exemplo, 1,3,5-tris(3,5-di-tert-butil-4-hidroxibenzil)-2,4,6-trimetilbenzeno, 1,4-bis(3,5- di)-terc-butil-4-hidroxibenzil)-2,3,5,6-tetrametilbenzeno, 2,4,6-tris(3,5-di- terc-butil-4-hidroxibenzil)fenol.
[00129] 1.10. Compostos de triazina, por exemplo, 2,4-bis (octilmercapto)-6-(3,5-di-terc-butil-4-hidroxi-anilino)-1,3,5-triazina, 2- octilmercapto-4,6-bis(3,5-di-terc-butil-4-hidroxianilino)-1,3,5-tri-razazina, 2- octilmercapto-4,6-bis(3,5-di-terc-butil-4-hidroxifenoxi)-1,3,5-triazina, 2,4,6- tris(3,5-di-terc-butil-4- hidroxifenoxi)-1,2,3-triazina, isocianurato de 1,3,5- tris(3,5-di-terc-butil-4-hidroxibenzila), isocianurato de 1,3,5-tris(4-terc-butil- 3-hidroxi-2,6-dimetilbenzila), 2,4,6-tris(3,5-di-terc-butil-4-hidroxifeniletil)- 1,3,5-triazina, 1,3,5-tris(3,5-di-terc-butil-4-hidroxi-fenilpropionil)-hexa-hidro- 1,3,5-triazina, isocianurato de 1,3,5-tris(3,5-diciclo-hexil-4-hidroxibenzila).
[00130] 1.11. Benzilfosfonatos, por exemplo, dimetil-2,5-di-terc-butil- 4-hidroxibenzilfosfonato, dietil-3,5-di-terc-butil-4-hidroxibenzilfosfonato, di- octadecil-3,5-di-terc-butil-4-hidroxibenzilfosfonato, dioctadecil-5-terc-butil- 4-hidroxi-3-metilbenzilfosfonato, o sal de cálcio do éster monoetílico do ácido 3,5-di-terc-butil-4-hidroxibenzilfosfônico.
[00131] 1.12. Acilaminofenóis, por exemplo, 4-hidroxilauranilida, 4- hidroxiestearanilida, N-(3,5-di-terc-butil-4-hidroxifenil)carbamato de octila.
[00132] 1.13. Ésteres do ácido β-(3,5-di-terc-butil-4-hidroxifenil) propiônico com álcoois mono- ou poli-hídricos, por exemplo, com metanol, etanol, n-octanol, i-octanol, octadecanol, 1,6-hexanodiol, 1,9-nonanodiol, etileno glicol, 1,2-propanodiol, neopentil glicol, tiodietileno glicol, dietileno glicol, trietileno glicol, pentaeritritol, isocianurato de tris(hidroxietila), N,N'- bis(hidroxietil)oxamida, 3-tiaundecanol, 3-tiapentadecanol, trimetil- hexanodiol, trimetilolpropano, 4-hidroximetil-1-fosfa-2,6,7-trioxabiciclo [2.2.2]octano.
[00133] 1.14. Ésteres do ácido β-(5-terc-butil-4-hidroxi-3-metilfenil) propiônico com álcoois mono- ou poli-hídricos, por exemplo, com metanol, etanol, n-octanol, i-octanol, octadecanol, 1,6-hexanodiol, 1,9-nonanodiol, etileno glicol, 1,2-propanodiol, neopentil glicol, tiodietileno glicol, dietileno glicol, trietileno glicol, pentaeritritol, isocianurato de tris(hidroxietila), N,N'- bis(hidroxietil)oxamida, 3-tiaundecanol, 3-tiapentadecanol, trimetil- hexanodiol, trimetilolpropano, 4-hidroximetil-1-fosfa-2,6,7-trioxabiciclo [2.2.2]octano; 3,9-bis[2-{3-(3-terc-butil-4-hidroxi-5- metilfenil)propioniloxi}- 1,1-dimetiletil]-2,4,8,10-tetraoxaspiro[5.5]undecano .
[00134] 1.15. Ésteres do ácido β-(3,5-diciclo-hexil-4-hidroxifenil) propiônico com álcoois mono- ou poli-hídricos, por exemplo, com metanol, etanol, octanol, octadecanol, 1,6-hexanodiol, 1,9-nonanodiol, etileno glicol, 1,2-propanodiol, neopentil glicol, tiodietileno glicol, dietileno glicol, trietileno glicol, pentaeritritol, isocianurato de tris(hidroxietila), N,N'- bis(hidroxietil)oxamida, 3-tiaundecanol, 3-tiapentadecanol, trimetil- hexanodiol, trimetilolpropano, 4-hidroximetil-1-fosfono-2,6,7-trioxabiciclo [2.2.2]octano.
[00135] 1.16. Ésteres do ácido 3,5-di-terc-butil-4-hidroxifenil acético com álcoois mono- ou poli-hídricos, por exemplo, com metanol, etanol, octanol, octadecanol, 1,6-hexanodiol, 1,9-nonanodiol, etileno glicol, 1,2- propanodiol, neopentil glicol, tiodietileno glicol, dietileno glicol, trietileno glicol, pentaeritritol, isocianurato de tris(hidroxietila), N,N'- bis(hidroxietil)oxamida, 3-tiaundecanol, 3-tiapentadecanol, trimetil- hexanodiol, trimetilolpropano, 4-hidroximetil-l-fosfino-2,6,7-trioxabiciclo [2.2.2]octano.
[00136] 1.17. Amidas de ácido β-(3,5-di-terc-butil-4-hidroxifenil) propiônico, por exemplo, N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionil) hexametilenodiamida, N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionil) trimetilenodiamida, N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionil) hidrazida, N,N'-bis[2-(3-[3,5-di-terc-butil-4-hidroxifenil]propioniloxi)etil] oxamida (Naugard®XL-1, fornecida por Uniroyal).
[00137] 1.18. Ácido ascórbico (vitamina C)
[00138] 1.19. Antioxidantes amínicos, por exemplo, N,N'-di-isopropil- p-fenilenodiamina, N,N'-di-sec-butil-p-fenilenodiamina, N,N'-bis(1,4- dimetilpentil)-p-fenilenodiamina, N,N'-bis(1-etil-3-metilpentil)-p- fenilenodiamina, N,N'-bis(1-metil-heptil)-p-fenilenodiamina, N,N'-diciclo- hexil-p-fenilenodiamina, N,N'-difenil-p-fenilenodiamina, N,N'-bis(2-naftil)-p- fenilenodiamina, N-isopropil-N'-fenil-p-fenilenodiamina, N-(1,3-dimetilbutil) -N'-fenil-p-fenilenodiamina, N-(1-metil-heptil)-N'-fenil-p-fenilenodiamina, N-ciclo-hexil-N'-fenil-p-fenilenodiamina, 4-(p-toluenossulfamoil) difenilamina, N,N'-dimetil-N,N'-di-sec-butil-p-fenilenodiamina, difenilamina, N-alildifenilamina, 4-isopropoxidifenil-amina, N-fenil-1-naftilamina, N-(4- tert-octilfenil)-1-naftilamina, N-fenil-2-naftilamina, difenilamina octilada, por exemplo, p,p'-di-terc-octildifenilamina, 4-n-butilaminofenol, 4- butirilaminofenol, 4-nonanoilaminofenol, 4-dodecanoilaminofenol, 4- octadecanoilaminofenol, bis(4-metoxifenil)amina, 2,6-di-terc-butil-4- dimetilaminometilfenol, 2,4'-diaminodifenilmetano, 4,4'- diaminodifenilmetano, N,N,N',N'-tetra metil-4,4'-diaminodifenilmetano, 1,2- bis[(2-metilfenil)amino]etano, 1,2-bis(fenilamino)propano, (o-tolil) biguanida, bis[4-(1',3'-dimetilbutil)fenil]amina, N-fenil-1-naftilamina terc- octilada, uma mistura de terc-butil/terc-octildifenilaminas mono e dialquiladas, uma mistura de nonildifenilaminas mono e dialquiladas, uma mistura de dodecildifenilaminas mono- e dialquiladas, uma mistura de isopropil/iso-hexil-difenilaminas mono e dialquiladas, uma mistura de terc- butildifenilaminas mono e dialquiladas, 2,3-di-hidro-3,3-dimetil-4H-1,4- benzotiazina, fenotiazina, uma mistura de terc-butil/terc-octilfenotiazinas mono e dialquiladas, uma mistura de terc-octil-fenotiazinas mono- e dialquiladas, N-alilfenotiazina, N,N,N', N'-tetrafenil-1, 4-diaminobut-2-eno. 2. Absorvedores de UV e estabilizadores de luz
[00139] 2.1. 2-(2'-Hidroxifenil)benzotriazóis, por exemplo, 2-(2'- hidroxi-5'-metilfenil)-benzotriazol, 2-(3',5'-di-terc-butil-2'-hidroxifenil) benzotriazol, 2-(5'-terc-butil-2'-hidroxifenil)benzotriazol, 2-(2'-hidroxi-5'- (1,1,3,3-tetrametilbutil)fenil)benzotriazol, 2-(3',5'-di-terc-butil-2'-hidroxifenil) -5-cloro-benzotriazol, 2-(3'-terc-butil-2'-hidroxi-5'-metilfenil)-5-cloro- benzotriazol, 2-(3'-sec-butil-5'-terc-butil-2'-hidroxifenil)benzotriazol, 2-(2'- hidroxi-4'-octiloxifenil)benzotriazol, 2-(3',5'-di-terc-amil-2'-hidroxifenil) benzotriazol, 2-(3',5'-bis-(α,α-dimetilbenzil)-2'-hidroxifenil)benzotriazol, 2- (3'-terc-butil-2'-hidroxi-5'-(2-octiloxicarboniletil)fenil)-5-cloro-benzotriazol, 2-(3'-terc-butil-5'-[2-(2-etil-hexiloxi)-carboniletil]-2'-hidroxifenil)-5-cloro- benzotriazol, 2-(3'-terc-butil-2'-hidroxi-5'-(2-metoxicarboniletil)fenil)-5- cloro-benzotriazol, 2-(3'-terc-butil-2'-hidroxi-5'-(2-metoxicarboniletil)fenil) benzotriazol, 2-(3'-tert)-butil-2'-hidroxi-5'-(2-octiloxicarbonilmetil)fenil) benzotriazol, 2-(3'-terc-butil-5'-[2-(2-etil-hexiloxi)carbonil-etil]-2'-hidroxi fenil)benzotriazol, 2-(3'-dodecil-2'-hidroxi-5'-metilfenil)benzotriazol, 2-(3'- terc-butil-2'-hidroxi-5'-(2-iso-octiloxicarboniletil)fenilbenzotriazol, 2,2'- metileno-bis[4-(1,1,3,3-tetrametilbutil)-6-benzotriazol-2-ilfenol]; o produto de transesterificação de 2-[3'-terc-butil-5'-(2-metoxicarboniletil)-2'-hidroxifenil] -2H-benzotriazol com polietileno glicol 300; ^_CH2CH_CO^CH2CHj|_ , em que R = 3'-terc-butil-4'-hidroxi-5'-2H-benzotriazol-2-ilfenila, 2-[2'-hidroxi-3'- (α,α-dimetilbenzil)-5'-(1,1,3,3-tetrametilbutil)-fenil]benzotriazol; 2-[2'- hidroxi-3'-(1,1,3,3-tetrametilbutil)-5'-(α,α-dDimetilbenzil)-fenil]benzotriazol.
[00140] 2.2. 2-Hidroxibenzofenonas, por exemplo, os derivados de 4- hidroxi, 4-metoxi, 4-octiloxi, 4-deciloxi, 4-dodeciloxi, 4-benziloxi, 4,2',4'-tri- hidroxi e 2'-hidroxi-4,4'-dimetoxi.
[00141] 2.3. Ésteres de ácidos benzoicos substituídos e não substituídos, por exemplo, salicilato de 4-terc-butil-fenila, salicilato de fenila, salicilato de octilfenila, dibenzoíl rosorcinol, bis(4-terc-butilbenzoil) resorcinol, benzoil resorcinol, 3,5-di-terc-butil-4-hidroxibenzoato de 2,4-di- terc-butilfenila, 3,5-di-terc-butil-4-hidroxibenzoato de hexadecila, 3,5-di-terc- butil-4-hidroxibenzoato de octadecila, 3,5-di-terc-butil-4-hidroxibenzoato de 2-metil-4,6-di-terc-butilfenila.
[00142] 2.4. Acrilatos, por exemplo, α-ciano-β,β-difenilacrilato de etila, α-ciano-β,β-difenanilacrilato de iso-octila, α-carbometoxicinamato de metila, α-ciano-β-metil-p-metoxicinamato de metila, α-ciano-β-metil-p- metoxicinamato de butila, α-carbometoxi-p-metoxicinamato de metila, N- (β- carbometoxi-β-cianovinil)-2-metilindolina, tetra(α-ciano-β,β-di-fenilacrilato de neopentila.
[00143] 2.5. Compostos de níquel, por exemplo, complexos de níquel de 2,2'-tio-bis[4-(1,1,3,3-tetrametil-butil)fenol], tais como o complexo 1:1 ou 1:2, com ou sem ligantes adicionais tais como n-butilamina, trietanolamina ou N-ciclo-hexildietanolamina, dibutilditiocarbamato de níquel, sais de níquel dos ésteres monoalquílicos, por exemplo, o éster metílico ou etílico do ácido 4-hidroxi-3,5-di-terc-butilbenzilfosfônico, complexos de níquel de cetoximas, por exemplo, de 2-hidroxi-4-metilfenilundecilcetoxima, complexos de níquel de 1-fenil-4-lauroil-5-hidroxipirazol, com ou sem ligantes adicionais.
[00144] 2.6. Aminas estereoquimicamente impedidas, por exemplo, 1,6-hexanodiamina N,N'-bis(1-propiloxi-2,2,6,6-tetrametil-4-piperidinil)- N,N'-bis-2-[4,5-bis-(N-n-butil-N'-1-propiloxi-2,2,6,6-tetrametil-4-piperidinil) -1,3,5-triazina] de 1,6-hexanodiamina, N,N'-bis(2,2,6,6-tetrametil-4- piperidinil)-N,N'-bis-2-[4,5-bis-(N-n-butil-N'-2,2,6,6-tetrametil-4-piperidinil)- 1,3,5-triazina] de 1,6-hexanodiamina, éster bis(1-undeciloxi-2,2,6,6- tetrametil-4-piperidil) do ácido carbônico, sebacato de bis(2,2,6,6-tetrametil- 4-piperidila), succinato de bis (2,2,6,6-tetrametil-4-piperidila), produtos de reação de ácido alcanóico (C=18,20,22,24, cadeia normal) e 1,2,2,6,6- pentametilpiperidin-4-ol, que consiste em docosanoato de 1,2,2,6,6- pentametilpiperidina-4-ila como um componente principal (80% ou mais), sebacato de bis(1,2,2,6,6-pentametil-4-piperidila), carbonato de bis(1- undecanoxi-2,2,6,6-tetrametilpiperidin-4-ila) (Reg. CAS No. [705257- 84-7], sebacato de bis(1-octiloxi-2,2,6,6-tetrametil-4-piperidila), n-butil-3,5-di-terc- butil-4-hidroxibenzilmalonato de bis (1,2,2,6,6- pentametil-4-piperidila), o condensado de 1-(2-hidroxietil)-2,2,6,6-tetrametil-4-hidroxipiperidina e ácido succínico, condensados lineares ou cíclicos de N,N'-bis(2,2,6,6-tetrametil-4- piperidil)hexametilenodiamina e 4-terc-octilamino-2,6-di-cloro-1,3,5-triazina, nitrilotriacetato de tris(2,2,6,6-tetrametil-4-piperidila), tetracarboxilato de tetraquis(2,2,6,6-tetra-metil-4-piperidil)-1,2,3,4-butano, 1,1'-(1,2-etanodiil)- bis(3,3,5,5-tetrametilpiperazinona), 4-benzoil-2,2,6,6-tetrametilpiperidina, 4- esteariloxi-2,2,6,6-tetrametilpiperidina, malonato de bis(1,2,2,6,6- pentametilpiperidil)-2-n-butil-2-(2-hidroxi-3,5-di-terc-butilbenzila), 3-n-octil- 7,7,9,9-tetrametil-1,3,8-triazaspiro[4.5] decano-2,4-diona, sebacato de bis(1- octiloxi-2,2,6,6-tetrametilpiperidila), succinato de bis(1-octiloxi-2,2,6,6- tetrametilpiperidila), condensados lineares ou cíclicos de N,N'-bis (2,2,6,6- tetrametil-4-piperidil)hexametileno-diamina e 4-morfolino-2,6-dicloro-1,3,5- triazina, o condensado de 2-cloro-4,6-bis(4-n-butilamino-2,2,6,6- tetrametilpiperidil)-1,3,5-triazina e 1,2-bis(3-aminopropilamino)etano, o condensado de 2-cloro-4,6-di-(4-n-butilamino-1,2,2,6,6-pentametilpiperidil)- 1,3,5-triazina e 1,2-bis (3-aminopropilamino)etano, 8-acetil-3-dodecil-7,7,9,9- tetrametil-1,3,8-triazaspiro[4,5]decano-2,4-diona, 3-dodecil-1-(2,2,6,6- tetrametil-4-piperidil)pirrolidina-2,5-diona, 3-dodecil-1-(1,2,2,6,6-pentametil- 4-piperidil)pirrolidina-2,5-diona, uma mistura de 4-hexadeciloxi- e 4- esteariloxi-2,2,6,6-tetrametilpiperidina, um condensado de N,N'-bis (2,2,6,6- tetrametil-4-piperidil)hexametilenodiamina e 4-ciclo-hexilamino-2,6-dicloro- 1,3,5-triazina, um condensado de 1,2-bis(3-aminopropilamino)etano e 2,4,6- tricloro-1,3,5-triazina assim como 4-butilamino-2,2,6,6-tetrametilpiperidina (Reg. CAS N° [136504-96-6]); um condensado de 1,6-hexanodiamina e 2,4,6- tricloro-1,3,5-triazina, bem como N,N-dibutilamina e 4-butilamino-2,2,6,6- tetrametilpiperidina (Reg. CAS. N° [192268-64-7]); N-(2,2,6,6-tetrametil-4- piperidil)-n-dodecilsuccinimida, N-(1,2,2,6,6-pentametil-4-piperidil)-n- dodecilsuccinimida, 2-undecil-7,7,9,9-tetrametil-1-oxa-3,8-diaza-4-oxo- espiro-[4,5]decano, um produto da reação do 7,7,9,9-tetrametil-2- cicloundecil-1-oxa-3,8-diaza-4-oxo-espiro-[4,5]decano e epicloridrina, 1,1-bis (1,2,2,6,6-pentametil-4-piperidiloxicarbonil)-2-(4-metoxifenil)eteno, N,N'- bis-formil-N,N'-bis(2,2,6,6-tetrametil-4-piperidil)hexametilenodiamina, um diéster de ácido 4-metoximetilenomalônico com 1,2,2,6,6-pentametil-4- hidroxipiperidina, poli[metilpropil-3-oxi-4-(2,2,6,6-tetrametil-4-piperidil)] siloxano, um produto de reação de copolímero de ácido maleico anidrido-α- olefina com 2,2,6,6-tetrametil-4-aminopiperidina ou 1,2,2,6,6-pentametil-4- aminopiperidina, 2,4-bis[N-(1-ciclo-hexiloxi-2,2,6,6-tetrametilpiperidina-4-il) -N-butilamino]-6-(2-hidroxietil)amino-1,3,5-triazina, 1-(2-hidroxi-2- metilpropoxi)-4-octadecanoiloxi-2,2,6,6-tetrametilpiperidina, 5-(2-etil- hexanoil)oximetil-3,3,5-trimetil-2-morfolinona, Sanduvor (Clariant; Reg. CAS N° 106917-31-1], aminoéter HALS/Polymer Hostavin NOW Pills XP (Clariant; Reg. CAS N° [942926-88-7], 5-(2-etil-hexanoil)oximetil-3,3,5- trimetil-2-morfolinona, o produto da reação de 2,4-bis[(l-ciclo-hexiloxi- 2,2,6,6-piperidina-4-il)butilamino]-6-cloro-s-triazina com N,N'-bis(3- aminopropil)etilenodiamina), 1,3,5-tris(N-ciclo-hexil-N-(2,2,6,6- tetrametilpiperazin-3-ona-4-il)amino)-s-triazina 1,3,5-tris(N-ciclo-hexil-N- (1,2,2,6,6- pentametilpiperazin-3-ona-4-il)-amino) -s-triazina,
[00145] 2.7 Derivados de benzoxazinona, tais como, por exemplo, 2,2'- (1,4-fenileno)bis[4H-3,1-benzoxazin-4-ona] (CAS No. 018600-59-4).
[00146] 2.8. Oxamidas, por exemplo, 4,4'-dioctiloxoxanilida, 2,2'- dietoxioxanilida, 2,2'-dioctiloxi-5,5'-di-terc-butoxanilida, 2,2'-didodeciloxi- 5,5'-di-terc-butoxanilida, 2-etoxi-2'-etiloxaniida, N,N'-bis(3- dimetilaminopropil)oxamida, 2-etoxi-5-terc-butil-2'-etoxianilida e sua mistura com 2-etoxi-2'-etil-5,4'-di-terc-butoxanilida, misturas de oxanilidas dissubstituídas em o- e p-metóxi e misturas de oxanilidas dissubstituídas em o- e p-etóxi.
[00147] 2.9. 2-(2-Hidroxifenil) -1,3,5-triazinas, por exemplo, 2,4,6-tris (2-hidroxi-4- octiloxifenil)-1,3,5-triazina, 2-(2-hidroxi-4-octiloxifenil)-4,6-bis (2,4-dimetilfenil)-1,3,5-triazina, 2-(2,4-di-hidroxifenil)-4,6-bis(2,4- dimetilfenil)-1,3,5-triazina, 2,4-bis(2-hidroxi-4-propiloxifenil)-6-(2,4- dimetilfenil)-1,3,5-triazina, 2-(2-hidroxi-4-octiloxifenil)-4,6-bis(4-metilfenil)- 1,3,5-triazina, 2-(2-hidroxi-4-dodeciloxifenil)-4,6-bis(2,4-dimetilfenil)-1, 3,5- triazina, 2-(2-hidroxi-4-trideciloxifenil)-4,6-bis(2,4-dimetilfenil)-1,3,5- triazina, 2-[2-hidroxi-4-(2-hidroxi-3-butiloxipropoxi)fenil]-4,6-bis(2,4- dimetil)-1,3,5-triazina, 2-[2- hidroxi-4- (2-hidroxi-3-octiloxipropiloxi)fenil]- 4,6-bis(2,4-dimetil)-1,3,5-triazina, 2-[4-(dodeciloxi/trideciloxi-2- hidroxipropoxi)-2-hidroxifenil]-4,6-bis(2,4-dimetilfenil) -1,3,5-triazina, 2-[2- hidroxi-4-(2-hidroxi-3-dodeciloxipropoxi)fenil]-4,6-bis(2,4-dimetilfenil)- 1,3,5-triazina, 2- (2-hidroxi-4-hexiloxi)fenil-4,6-difenil-1,3,5-triazina, 2-(2- hidroxi-4-metoxifenil)-4,6-difenil-1,3,5-triazina, 2,4,6-tris[2-hidroxi-4-(3- butoxi-2-hidroxipropoxi)fenil]-1,3,5-triazina, 2-(2-hidroxifenil)-4-(4- metoxifenil)-6-fenil-1,3,5-triazina, 2-{2-hidroxi -4-[3-(2-etil-hexil-1-oxi)-2- hidroxipropiloxi]fenil}-4,6-bi (2,4-di-metilfenil)-1,3,5-triazina, 2,4-bis(4- [2- etil-hexiloxi]-2-hidroxifenil)-6-(4-metoxifenil)-1,3,5-triazina, 2-(4,6-bis- bifenil-4-il-1, 3,5-triazin-2-il)-5-(2-etil- (n)-hexiloxi)fenol.
[00148] 3. Desativadores de metal, por exemplo, N,N'-difeniloxamida, hidrazina de N-salicilal-N'-saliciloíla, hidrazina de N,N'-bis(saliciloila), hidrazina de N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionila), 3- salicioilamino-1,2,4-triazol, di-hidrazida de bis(benzilideno)oxalila, oxanilida, di-hidrazida de isoftaloíla, bifenil-hidrazida de sebacoíla, di-hidrazida de N,N'-diacetiladipoíla, N,N'-bis di-hidrazida de (saliciloil)oxalila, di-hidrazida de N,N'-bis(saliciloil)tiopropionila.
[00149] 3a. Formamidinas, por exemplo, etoxicarbonilfenil)-N'-etil-N'- fenilformidina.
[00150] 4. Fosfitos e fosfonitos, por exemplo, fosfito de trifenila, fosfitos de difenilalquila, fosfitos de fenildialquila, fosfitos de tris(nonilfenila), fosfitos de trilaurila, fosfito de trioctadecila, difosfito de distearil-pentaeritritol, fosfito de tris(2,4-di-terc-butilfenila), difosfito de di- isodecil-pentaeritritol, difosfito de bis (2,4-di-terc-butilfenil)pentaeritritol, difosfito de bis(2,4-di-cumilfenil)pentaeritritol, difosfito de bis (2,6-di-terc- butil-4-metilfenil)pentaeritritol, difosfito de diisodeciloxi-pentaeritritol, difosfito de bis(2,4-di-terc-butil-6-metilfenil)-pentaeritritol, difosfito de bis(2,4,6-tris(terc-butilfenil)-pentaeritritol, trifosfito de triestearil sorbitol, 4,4'-bifenileno difosfonito de tetraquis(2,4-di-terc-butilfenila), 6-isooctiloxi- 2,4,8,10-tetra-terc-butil-12H-dibenz [d , g] -1,3,2-dioxafosfocina, fosfito de bis(2,4-di-terc-butil-6-metilfenil)metila, fosfito de bis(2,4-di-terc-butil-6- metilfenil)etila, 6-fluoro-2,4,8,10-tetra-terc-butil-12-metil-dibenz[d, g]-1,3,2- dioxafosfocina, fosfito de 2,2',2''-nitrilo[trietiltris(3,3',5,5'-tetra-terc-butil-1,1'- bifenil-2,2'-diila)], fosfito de 2-etil-hexil(3,3',5,5'-tetra-terc-butil-1,1'-bifenil- 2,2'-dila), 5-butil-5-etil-2-(2,4,6-tri-terc-butilfenoxi)-1,3,2-dioxafospirano, ácido de fósforo, 2,4-bis(1,1-dimetilpropil)fenila misturado com triésteres de 4-(1,1-dimetil)fenila (Reg. CAS No. [939402-02-5], ácido de fósforo, éster de trifenila, polímero com alfa-hidro-ômega-hidroxipoli[oxi(metil-1,2- etanodiila)], ésteres de alquila-C10-16 (Reg. CAS No. [ 1227937-46-3].
[00151] Os seguintes fosfitos são especialmente preferidos: Fosfito de tris(2,4-di-terc-butilfenila) (Irgafos®168, BASF SE), fosfito de tris(nonilfenila), ácido de fósforo misturado com 2,4-bis(1,1- dimetilpropil)fenil e triésteres de 4-(1,1-dimetilpropil)fenila (Reg. CAS 939402-02-5), polímero de éster de trifenila do ácido fosforoso com ésteres de alquila-C10-16 de alfa-hidro-ômega-hidroxipoli[oxi(metil-1,2-etanodiila) (Reg. CAS No. 1227937-46-3).
[00152] 5. Hidroxilaminas, por exemplo, N, N-dibenzil-hidroxilamina, N,N-dietil-hidroxilamina, N,N-dioctil-hidroxilamina, N,N-dilauril- N,N-ditetradecil-hidroxilamina, N,N-di-hexadecil- N,N-dioctadecil-hidroxilamina, N-hexadecil-N-octadecil- N-heptadecil-N-octadecil-hidroxilamina, N,N-dialquil- hidroxilamina derivada de amina de sebo hidrogenada.
[00153] 6. Óxidos de amina, por exemplo, óxido de N,N-dibenzil- hidroxilamina, óxido de N,N-dietil-hidroxilamina, óxido de N,N-dioctil- hidroxilamina, óxido de N,N-dilauril-hidroxilamina, óxido de N,N- ditetradecil-hidroxilamina, óxido de N,N-di-hexadecil-hidroxilamina, óxido de N-dioctadecil-hidroxilamina, óxido de N-hexadecil-N-octadecil- hidroxilamina, óxido de N-heptadecil-N-octadecil-hidroxilamina, óxido de N,N-dialquil-hidroxilamina derivada de amina de sebo hidrogenada.
[00154] 7. Nitronas, por exemplo, N-benzil-alfa-fenilnitrona, N-etil- alfa-metilnitrona, N-octil-alfa-heptilnitrona, N-lauril-alfa-undecilnitrona, N- tetradecil-alfa-tridecilnitrona, octadecil-alfa-heptadecilnitrona, ocatadecil-alfa-pentadecilnitrona, octadecil-alfa-hexadecilnitrona, derivados de nitrona a partir de derivados de N,N-dialquil-hidroxilamina de amina de sebo hidrogenada.
[00155] 8. Tiosinergistas, por exemplo, tiodipropionato de dilaurila, tiodipropionato de dimistrila, tiodipropionato de diestearila, tetraquis[3- (dodeciltio)propionato] de pentaeritritol ou dissulfeto de diestearila.
[00156] 9. Removedores de peróxido, por exemplo, ésteres de ácido β- tiodipropiônico, por exemplo, os ésteres laurílicos, estearílicos, miristílicos ou tridecílicos, mercaptobenzimidazol ou o sal de zinco de 2-mercapto benzimidazol, dibutilditiocarbamato de zinco, dissulfureto de dioctadecila, tetrakis(β-dodecilmercapto)propionato de pentaeritol.
[00157] 10. Estabilizadores de poliamida, por exemplo, sais de cobre em combinação com iodetos e/ou compostos de fósforo e sais de manganês divalente.
[00158] 11. Coestabilizadores básicos, por exemplo, melamina, polivinilpirrolidona, dicianodiamida, cianurato de trialila, derivados da ureia, derivados da hidrazina, aminas, poliamidas, poliuretanos, sais de metais alcalinos e sais de metais alcalino-terrosos de ácidos graxos superiores, por exemplo, estearato de cálcio, estearato de zinco, beenato de magnésio, estearato de magnésio, ricinoleato de sódio e palmitato de potássio, pirocatecolato de antimônio ou pirocatecolato de zinco, zeólitos, hidrotalcitas, hidrocalumitas.
[00159] 12. Agentes de nucleação, por exemplo, substâncias inorgânicas, tais como talco, óxidos metálicos, tais como dióxido de titânio ou óxido de magnésio, fosfatos, carbonatos ou sulfatos de, preferencialmente, metais alcalino-terrosos; compostos orgânicos, tais como ácidos mono- ou policarboxílicos e os sais dos mesmos, por exemplo, ácido 4-terc- butilbenzóico, ácido adípico, ácido difenilacético, succinato de sódio ou benzoato de sódio; compostos poliméricos, tais como copolímeros iônicos (ionômeros). Especialmente preferidos são 1,3:2,4-bis(3',4'- dimetilbenzilideno)sorbitol, 1,3:2,4-di(parametil-dibenzilideno)sorbitol, e 1,3: 2,4-di(benzilideno)sorbitol.
[00160] 13. Agentes de enchimento e reforço, por exemplo, carbonato de cálcio, silicatos, fibras de vidro, fibras de carbono, esferas de vidro, amianto, talco (preferencialmente com um tamanho de partícula de 0,01 a 20 μm), caulim, mica, sulfato de bário, óxidos de metal e hidróxidos, negro de fumo, grafite, farinha de madeira e farinhas ou fibras de outros produtos naturais, fibras sintéticas.
[00161] 14. Outros aditivos, por exemplo, plastificantes, lubrificantes, emulsionantes, pigmentos, aditivos reológicos, catalisadores, agentes de controle de fluxo, branqueadores ópticos, agentes à prova de fogo, agentes antiestáticos e agentes de sopro.
[00162] 15. Benzofuranonas e indolinonas, por exemplo, as divulgadas nos documentos US 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 ou 3-[4-(2-acetoxietoxi) fenil]-5,7-di-terc-butilbenzofuran-2-ona, 5,7-di-terc-butil-3-[4-(2- estearoiloxietoxi)fenil]-benzofuran-2-ona, 3,3'-bis[5,7-di-terc-butil-3-(4-[2- hidroxietoxi]fenil)benzofuran-2-ona], 5,7-di-terc-butil-3-(4-etoxifenil) benzofuran-2-ona, 3-(4-acetoxi-3,5-di-metilfenil)-5,7-di-terc-butilbenzofuran- 2-ona, 3-(3,5-dimetil-4-pivaloiloxifenil)-5,7-di-terc-butilbenzofuran-2-ona, 3- (3,4-dimetilfenil)-5,7-di-tert-butilbenzofuran-2-ona, 3-(2,3-dimetilfenil)-5,7- di-terc-butilbenzofuran-2-ona, 3-(2-acetil-5-isooctilfenil)-5- isooctilbenzofuran-2-ona.
[00163] Antioxidantes fenólicos são preferidos. De interesse são aqueles listados acima no item 1. De particular interesse são os antioxidantes fenólicos e estabilizadores de processo, tais como tetraquis [3,5-di-terc-butil- 4-hidroxifenilpropionato] de pentaeritritol, propionato de octadecil-3-(3,5- di- terc-butil-4-hidroxifenila), 1,3,5-tris(3,5-di-terc-butil-4-hidroxibenzil)-2,4,6- trimetilbenzeno, N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionil) hexametileno-diamida, isocianurato de 1,3,5-tris[3,5-di-terc-butil-4- hidroxibenzila], 2,4-di-t-butilfenil-3,5-di-t-butil-4-hidroxibenzoato, malonato de bis(1,2,2,6,6-pentametilpiperidin-4-il)-butil(3,5-di-t-butil-4- hidroxibenzila)) e fosfito de tris[2,4-di-terc-butilfenila].
[00164] Outros aditivos preferidos são o tetraquis[3-(dodeciltio) propionato] de pentaeritritol e o estearato de cálcio.
[00165] Pigmentos tais como TiO2 e negro de fumo são ainda mais preferidos. Enchimentos tais como o talco também são de interesse.
[00166] Aditivos preferidos são também estabilizadores de luz de amina estericamente impedida e/ou absorvedores de UV, em particular os listados acima sob o item 2.
[00167] A mistura de aditivos de acordo com a presente invenção é de preferência aplicada em conjunto com um antioxidante fenólico, de preferência o tetraquis[3,5-di-terc-butil-4-hidroxifenilpropionato] de pentaeritritol, um fosfito, preferivelmente fosfito de tris[2,4-di-terc- butilfenila], um eliminador de ácido, preferencialmente estearato de Ca, e negro de fumo e talco.
[00168] A razão em peso do composto da fórmula (I) para o aditivo convencional é, por exemplo, 1:100 a 100:1, preferivelmente 1:100 a 10:1, em particular 1:10 a 10:1.
[00169] Outro objetivo da presente invenção é um método para estabilizar um material orgânico contra a degradação induzida por luz, calor ou oxidação com floração reduzida, que compreende incorporar no referido material orgânico pelo menos um composto da fórmula (I) e pelo menos um aditivo antirrisco.
[00170] Os exemplos abaixo ilustram a invenção em maior detalhe. Todas as percentagens e partes mencionadas no presente pedido são em peso, salvo indicação em contrário.
[00171] 78,3% em peso de poliolefina termoplástica (Daplen® EE013 AE da Borealis; Índice de fluidez: 11 g/10 min (ISO 1133); Densidade: 905 kg/m3 (ISO 1183)), 20% em peso de talco, 1,5% em peso de negro de fumo, 0,1% em peso de fosfito de tris (2,4-di-terc-butilfenila), 0,05% em peso de estearato de cálcio e 0,05% em peso de tetraquis(3-(3,5-di-terc-butil-4- hidroxifenil)propionato de pentaeritritol).
[00172] Outros aditivos, conforme descrito abaixo, são incorporados com o mesmo método que para a formulação de base. Em todos os casos, a percentagem em peso da poliolefina termoplástica é ajustada para que a soma de todos os ingredientes dê 100%.
[00173] A formulação de base é pré-misturada em um misturador de alta velocidade. Esta mistura é combinada com os aditivos adicionais listados nas Tabelas 1 a 3 num misturador de alta velocidade e depois combinada em uma extrusora de parafuso duplo Berstorff® ZE 25x32D a 230°C. A formulação completa é então moldada por injeção em uma máquina de moldagem por injeção Engel HL65. As placas moldadas por injeção (60 mm x 60 mm x 2 mm) são expostas a intemperismo artificial de acordo com a norma internacional DIN EN ISO 105-B06 (luz Xenon, irradiância 1,20 W/ (m2nm) @ 420 nm, temperatura de bulbo seco 65°C, umidade relativa 30% +/- 5%). Os parâmetros medidos são desvio de cor (escala de cinza e Delta E*) e brilho a 60°. Os resultados estão listados nas Tabelas 1, 2 e 3. Tabela 1: Escala de cinza (valores altos são desejados) Tabela 2: Delta E (valores baixos são desejados) Tabela 3: Brilho a 60° (valores altos são desejados)
[00174] Os resultados mostrados acima revelam claramente que a combinação de Composto (A) mais erucamida provê uma melhor retenção das propriedades da poliolefina termoplástica testada e melhor resistência a riscos do que o Composto (A) ou apenas erucamida.
[00175] As placas moldadas por injeção que são preparadas como descrito no Exemplo 1 são expostas a intemperismo artificial (luz Xenon, irradiância 40 W/m2 @ 300-400 nm, temperatura de bulbo seco 45°C, umidade relativa 20% +/- 10%). A aderência da superfície das amostras expostas é avaliada após várias durações de exposição e classificada de acordo com a escala mostrada abaixo: 1 Sem aderência
[00176] 2 Luz exsudando mas sem aderência 3 Leve aderência 4 Aderência 5 Forte aderência 6 Superfície gomosa 7 Superfície cerosa
[00177] Os resultados estão listados na Tabela 4. Tabela 4: Ac erência (val ores b >aixos são desejados)
[00178] Este exemplo mostra que a combinação de Composto (A) mais erucamida provê uma superfície que não mostra aderência ao longo do tempo de exposição.
[00179] As placas moldadas por injeção que são preparadas em analogia com o Exemplo 1 são colocadas em um forno de ar quente com aquecimento por convecção de ar forçado a 150°C. As amostras são inspecionadas periodicamente. O critério é fragilização, avaliado por inspeção visual. Os resultados estão listados na Tabela 5. Tabela 5: Estabilidade térmica à longo prazo (valores altos são desejados)
Claims (14)
1. Mistura aditiva, caracterizada pelo fato de que contém (A) pelo menos um composto da fórmula (I) em que R1 e R2, independentemente um do outro, são hidrogênio, alquila-C1-C22, -O, -OH, -CH2CN, alcóxi-C1-C18, alcóxi-C2-C18 substituído por -OH; cicloalcóxi-C5-C12, alquenila-C3-C6, alquenilóxi-C3-C6, fenilalquila- C7-C9 não substituída ou substituída na fenila por 1, 2 ou 3 alquila-C1-C4; ou acila-C1-C8; e R3 e R4, independentemente um do outro, são alquila-C1-C22 ou um grupo da fórmula (Ia) em que R0 tem um dos significados de R1 e R2, e (B) pelo menos um aditivo antirrisco, em que o aditivo antirrisco é erucamida, oleamida ou estearamida.
2. Mistura aditiva de acordo com a reivindicação 1, caracterizada pelo fato de que RI e R2, independentemente um do outro, são hidrogênio, alquila-C1-C8, alcóxi-C1-C18 ou ciclo-hexilóxi; e R3 e R4, independentemente um do outro, são alquila-C1-C6.
4. Composição, caracterizada pelo fato de que contém um material orgânico susceptível a degradação induzida por luz, calor ou oxidação, de preferência um polímero termoplástico, e uma mistura aditiva de como definida na reivindicação 1.
5. Composição de acordo com a reivindicação 4, caracterizada pelo fato de que o material orgânico é uma poliolefina, um acrilonitrila/ butadieno/estireno, um cloreto de polivinila, um polimetacrilato de metila, uma poliamida ou um polioximetileno.
6. Composição de acordo com a reivindicação 4, caracterizada pelo fato de que o material orgânico é uma poliolefina termoplástica, de preferência um polietileno ou polipropileno termoplástico.
7. Composição de acordo com qualquer uma das reivindicações 4 a 6, caracterizada pelo fato de que contém adicionalmente um antioxidante fenólico e/ou um fosfito fenólico.
8. Composição de acordo com a reivindicação 7, caracterizada pelo fato de que o antioxidante fenólico é o tetraquis[3,5-di-terc-butil-4- hidroxifenilpropionato] de pentaeritritol, propionato de octadecil-3-(3,5-di- terc-butil-4-hidroxifenila), 1,3,5-tris(3,5-di-terc-butil-4-hidroxibenzil)-2,4,6- trimetilbenzeno, N,N'-bis(3,5-di-terc-butil-4-hidroxifenilpropionil) hexametileno-diamida ou isocianurato de 1,3,5-tris[3,5-di-terc-butil-4- hidroxibenzila], benzoato de 2,4-di-t-butilfenil-3,5-di-t-butil-4-hidróxi ou malonato de bis(1,2,2,6,6-pentametilpiperidin-4-il)-butil(3,5-di-t-butil-4- hidroxibenzila), e o fosfito fenólico é fosfito de tris[2,4-di-terc-butilfenila].
9. Composição de acordo com qualquer uma as reivindicações 4 a 8, caracterizada pelo fato de que contém adicionalmente um estabilizador de luz de amina estericamente impedida diferente do composto de fórmula (I) como definido na reivindicação 1 e/ou um absorvente de UV.
10. Composição de acordo com a reivindicação 9, caracterizada pelo fato de que o absorvente de UV é selecionado do grupo que consiste em 2-(2'-hidroxifenil)benzotriazóis, 2-hidroxibenzofenonas, oxamidas e 2-(2-hidroxifenil)-1,3,5-triazinas.
11. Composição de acordo com qualquer uma das reivindicações 4 a 10, caracterizada pelo fato de que contém adicionalmente um enchimento e/ou um pigmento, de preferência talco e/ou negro de fumo.
12. Artigo, caracterizado pelo fato de que é feito de uma composição como definida em qualquer uma das reivindicações 4 a 11.
13. Artigo de acordo com a reivindicação 12, caracterizado pelo fato de que é um material de acabamento interior ou exterior para automóveis, de preferência um material de revestimento para um teto, assento ou painel de instrumentos.
14. Método para estabilizar um material orgânico contra a degradação induzida por luz, calor ou oxidação, caracterizado pelo fato de que compreende a incorporação no referido material orgânico de uma mistura aditiva como definida na reivindicação 1.
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US20220282064A1 (en) * | 2019-07-30 | 2022-09-08 | Basf Se | Stabilizer composition |
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JP7374420B2 (ja) * | 2019-12-24 | 2023-11-07 | 公立大学法人 滋賀県立大学 | 樹脂組成物、樹脂成形体、および樹脂成形体の製造方法 |
JP2023553074A (ja) * | 2020-12-09 | 2023-12-20 | ビーエーエスエフ ソシエタス・ヨーロピア | 添加物混合物 |
EP4259710A1 (en) * | 2020-12-09 | 2023-10-18 | Basf Se | An organic material based shaped article |
WO2023076351A1 (en) * | 2021-10-29 | 2023-05-04 | Dow Toray Co., Ltd. | Silicone rubber composition for textile coating and silicone rubber-coated textile |
WO2024042178A1 (en) * | 2022-08-25 | 2024-02-29 | Unilever Ip Holdings B.V. | A detergent sheet |
WO2024042176A1 (en) * | 2022-08-25 | 2024-02-29 | Unilever Ip Holdings B.V. | A detergent sheet |
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