CA2282329A1 - Enamine derivatives for use as antioxydants for polymers - Google Patents
Enamine derivatives for use as antioxydants for polymers Download PDFInfo
- Publication number
- CA2282329A1 CA2282329A1 CA002282329A CA2282329A CA2282329A1 CA 2282329 A1 CA2282329 A1 CA 2282329A1 CA 002282329 A CA002282329 A CA 002282329A CA 2282329 A CA2282329 A CA 2282329A CA 2282329 A1 CA2282329 A1 CA 2282329A1
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- enamine
- butyl
- branched
- general formula
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
Abstract
Compounds belonging to the group of enamines consisting of derivatives of .beta.-keto-esters, or .beta.-keto-amides or 1,3-diketones with primary or secondary aliphatic or aromatic amines carrying at least one sterically hindered amine group having general formula (I) in the molecule. The compounds having general formula (I) can be used as antioxidants for organic polymers.
Description
ENAMINE DERIVATIVES FOR USE AS ANTIOXYDANTS FOR POLYIuIERS
The present invention relates to compounds belong-ing to the group of enamines.
More specifically, the present invention relates to compounds belonging to the group of enamines con-sisting of derivatives of Q-keto-esters, or Q-keto-amides or 1,3-diketones with primary or secondary aliphatic or aromatic amines carrying at least one l0 sterically hindered amine group in the molecule, a process for their preparation and their use as artiaxi-dants for organic polymers.
The present invention also relates to the polymer-is compositions stabilized with the above compounds and the end-articles obtained from these compositions.
It is known that organic polymers undergo degrada-tion over a period of time as a result of exposure to atmospheric agents and light and they also easily undergo thermoxidative degradaticn during processing and transformation processes.
The most evident signs of this degradation are, for example, alterations in the mechanical properties of the end-article. To prevent this degradation of the polymeric material, stabilizing compounds are usually introduced into the organic polymers.
The Applicant has now found that compounds belong-ing to the group of enamines consisting of derivatives of ~B-keto-esters, or ,0-keto-amides or 1,3-diketones with primary or secondary, aliphatic or aromatic amines carrying at least one sterically hindered amine group in the molecule, are capable of stabilizing organic polymers to which they are added improving their resistance to thermo-oxidation.
The present invention therefore relates to com-pounds belonging to the group of enamines consisting of derivatives of ~B-keto-esters, or Q-keto-amides or 1,3-diketones with primary or secondary, aliphatic or aromatic amines carrying in the molecule at least one sterically hindered amine group having general formula (I) ,3 Rt--- ( --N--C=CH--C-_ ) m - ~ ~--R' ( I ) wherein:
- m represents an integer from 1 to 3, extremes included;
- n represents an integer from 1 to 4, extremes included;
- R~ represents a triazine having one of the follow-ing general formula (II), (III) or (IV):
\ 'N' /
INY~ ~N (II);
RS N
(III);
N~ N
N\ N (IV);
wherein R5 represents a hydrogen atom; a linear or 20 branched C~-C~8 alkyl group; a -NHR6 amine group or a -SR6 group wherein R6 represents a hydrogen atom or a linear or branched C~-C~$ alkyl group;
- R~ and RZ, the same or different, represent a hydrogen atom; a linear or branched C~-C~8 alkyl 25 group; a linear or branched C2-C8 alkoxyalkyl WO 98/47893 PCTlEP98/02186 group; a CS-C$ cycloalkyl group optionally contain-ing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C~8 aryl group; a C7-C2o arylalkyl _ or alkylaryl group; a group having general formula (V) CH, ~CH~
/y\ (V) R~
wherein R~ represents a hydrogen atom; a linear or branched C~-C~8 alkyl group, said alkyl group optionally substituted with a -NHRg group or an -OR8 group wherein R$ represents a hydrogen atom, a linear or branched C~-Ci8 alkyl group, or a Co-C~$
aryl group; an -ORq group wherein R9 represents a hydrogen atom, or a linear or branched C~-C~$ alkyl group;
- or, R~ and R2 considered jointly with the nitrogen atom, represent a C5-C8 heterocyclic group option-ally containing a second heteratom selected from oxygen, nitrogen and sulfur;
- R3 and R4, the same or different, represent a linear or branched Ci-C~8 alkyl group; a C6-C~8 aryl group; a C~-C2o alkylaryl or arylalkyl group; a linear or branched C~-C$ alkoxyl group;
- or, R4 represents a group having general formula S
(VI):
(VI) R~
wherein RT has the same meanings defined above;
- or, R4 represents an NR~oRt~ group wherein R~o and R~~, the same or different, represent a hydrogen atom; a linear or branched Ci-C~8 alkyl group; a linear or branched C2-Ce alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroa-tom selected from oxygen, nitrogen and sulfur; a C6-C~8 aryl group; a C7-CZO arylalkyl or alkylaryl group; a triazine having one of the following general formulae (II), (III) or (IV):
~N~
'NYC ~N {II);
RS N
{III);
N~ N
RS N
IV
N~ N ( ) wherein RS has the same meanings defined above: a group having general formula (V):
~3 CH;
(V) CH3 ~ CH3 R~
wherein RT has the same meanings defined above;
- or, Rio and Rig considered jointly with the nitrogen atom, represent a CS-C8 heterocyclic group option ally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R4 represents a group having one of the follow ing general formulae (VII), (VIII) or (IX):
i ~z ---OCHz--CH--OR13 (VII):
CrizOR~3 l ---OCHz--C--R~z (VIII) ;
CH20R~3 R~2--CHOR~3 ~ ---OCH2--C--CH20R~3 (IX) ;
CHZOR~3 wherein:
- R~z represents a hydrogen atom; or a linear or branched C~-C~a alkyl group:
- R~3 represents a linear or branched C~-C~$
WO 98/47$93 PCT/EP98/02186 alkyl group; a -COCHZCOCH3 group; or a direct bond;
provided that, when R~ and RZ are different from the group having general formula (V), R4 represents a group having general formula (VI).
The compounds having general formula (I) can be used as antioxidants for organic polymers.
Examples of R~, RZ, RED and R» groups, as well as a hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl, 4-(2,2,6,6-tetramethyl)piperidinyl, 4-(2,2,6,6-tetramethyl)-1-butoxyethylpiperidinyl, 4-(2,2,6,6-tetramethyl)-1-butoxypiperidinyl, 4-(2,2,6,6-tetramethyl)-1-methylpiperidinyl, 3,5-dioctylaminotriazine, 3,5-dibutylaminotriazine, etc.
Examples of C5-C8 heterocyclic groups, when R~ and RZ or Rio and R» are considered jointly with the nitro-gen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazol-idine, etc.
Examples of R3 and R4 groups are: methyl, ethyl, ' propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybu-tyl, etc.
Examples of R4 groups, when R4 represents a group having general formula (VI), are: 4-(2,2,6,6-tetrame-thyl)piperidinoxy, N-methyl-4-(2,2,6,6-tetramethyl)pi-peridinoxy, N-methoxyethyl-4-(2,2,6,6-tetramethyl)pipe-ridinoxy, N-methylaminoethyl-4-(2,2,6,6-tetramethyl)pi-peridinoxy, etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 2, are:
CHZ--O-- ; CH--0-- ;
CH3--CO--CHZ--C=0 O
CHZ
f --O--CH2--C--CH2--O-- ;
O
CH3--CO--CHZ--C=O
etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 3, are:
CHZO--CH3--CHZ--C--CHZO-- ;
O CHZO--/f . CH3--CO--CHZ--C--O--CH2--C--CH20-- ;
CHzO--etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 4 , are : CH20--l --ocH2--c--cHzo-- ;
etc.
Examples of R~ groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, A-hydroxyethyl, p-methoxyethyl, p-butoxyethyl, methylaminoethyl, etc.
Examples of R5, R6, R8, R9, R~Z and R~3 groups, when said groups represent a linear or branched C~-C18 alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.
Specific examples of compounds having general formula (I), which should in no way be considered as limiting the scope of the present invention, are:
CHI CH;
CH;-C=CH-C N-H
CsH~-CH~ CHI
N~ N
~N~
C8H1~-HN NH-CeHp (IA) to CH3-C=CH-CO N-H
~ CH3 CH3 N/\N CH3 CH;
H3 ~ ~ ~ H3 H- -C- ~ N i -C-CH-C ~N-H
C4H9 CaH9 CH
CHI
(IB) CH3 i =CH-C N-CH3 N1 CH3 \CH3 0/ ( I C ) CH3-C=CH-C N- H
NH
CH ~CH3 I (ID) CzHs /I
CH3- i =CH-CO-CH3 CHI ( IE ) i H2 CHI
CaH9 CH3-C=CH-CO-CH3 NH
CH3 ~CH3 CH3 N/ \CH3 ( I F ) O
CHI CHI
C=CF:-C N-CHI-CH2-NH-CH3 NH
CHI
CHj ~I ~CH3 (IG) H
CH3- i =CH-CO-NH N-H
CH3 \CH3 CH3 N CH3 ( I H ) H
CHI
CH3 f =CH-CO-N N-H
CaH9 N N~N CH- CH
s 3 CQH9 N CaH9 (II) -CH3- i -CH-C00-CH2 C
NH
CH3 I 'CH3 CH N CH3 ( I L ) H
CH;-C=CH-COO-CH2- =C= ~-CH2-~~H=COCH;
i 2 ;~ 2 (IM) H
A further object of the present invention relates s to a synthesis process of compounds having general formula (I).
A process for the synthesis of the compounds having general formula (I) of the present invention comprises the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having general formula (X) HNR~ R2 ( X ) wherein R~ and RZ have the same meanings defined above, with 1-3 moles of a A-keto-ester, or a ~3-keto-amide, or a 1,3-diketone having general formula (XI):
( R3--C--Cg2--C-- ) ~--R4 ( XI ) II II
wherein R3, R4 and n have the same meanings defined above.
The above reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature ranging from 60°C
to 160°C, preferably from 115°C to 150°C, at atmospher-is pressure, and for a time ranging from 0.5 to 24 hours, preferably from 3 to 10 hours. Acetic acid can optionally be added as catalyst to this reaction.
During the above reaction, reaction water is released which is separated by azeotropic distillation /~
using an apparatus for the azeotropic distillation, whereas the organic solvent is recycled.
At the end of the reaction, the solvent and possible acetic acid present are removed by distilla-tion thus obtaining a raw product. The desired compound having general formula (I) is purified from the raw product thus obtained by fractionated distillation, operating under vacuum, at a pressure ranging from 0.1 mm/Hg to 50 mm/Hg and a temperature ranging from 40°C
to 200°C. Or, said compound having general formula (I) is separated by crystallization using techniques known in the art.
Examples of primary or secondary, aliphatic or aromatic amines, having general formula (~) which can be used for the purposes of the present invention are:
cyclohexylamine, n-butylamine, tert-butylamine, n-octy-lamine, tert-octylamine, n-octadecylamine, n-dodecylam-ine, benzylamine, 2-methoxyethylamine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2,2,6,6-te-tramethylpiperidine, 4-amino-2,2,6,6-tetramethyl-1-me-thylpiperidine, 4-amino-2,2,6,6-tetramethyl-1-butoxyet-hylpiperidine, 1-amino-3,5-dioctylaminotriazine, etc.
Examples of p-keto-esters or /3-keto-amides, or 1,3-diketones having general formula (XI) are: ethyl r5 aceto-acetate, t-butyl aceto-acetate, octadecyl aceto-acetate, ethyl benzoylacetate, acetyl-acetone, benzoyl-acetone, dibenzoyl methane, p-toluylacetone, 4-(2,2,6,6-tetramethyl)piperidinyl aceto-acetate, N-methyl-4-(2,2,6,6-tetramethyl)piperidinyl aceto-acetate, aceto-acetamide, acetoacetanilide, aceto-acet-4-(2,2,6,6,-tetramethylpiperidine)amide, aceto-acet-(3,5-dibutyltriazine)-1-amide, etc.
The enaminic function of the compounds having general formula (I) synthesized by means of the process described above, is confirmed by NMR spectrometry analysis (obtained using a BRUKER AC 200 spectrometer) executed on samples with a high purity (95% confirmed by gas-chromatography).
Other processes which can be used for the prepara-tion of the compounds having general formula (I) of the present invention, however, are described in literature such as, for example, in Houben-Weyl (1957), Vol. 11/1, pages 172-178.
Organic polymers capable of being stabilized with the compounds of the present invention are:
(1) polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyiso-prene.or polybutadiene; as well as polymers of I
cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be option-ally cross-linked) such as, for example, high density polyethylene (HDPE), low density poly-ethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
The polyolefins such as, for example the mono-olefins cited in the previous paraqraph, preferably polyethylene and polypropylene, can be prepared with various methods known in literature, preferably using the following methods:' (a) radicalic polymerization (generally carried out at a high pressure and high temperature;
(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals generally have one or more ligands such as, far example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be ~r- or a-co-ordinated. These metal complexes can be in free form or supported in substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the I ~' reaction medium. The catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups Ia, IIa and/or IIIa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine or silyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or "single site cata-lyst" (SSC).
(2) Mixtures of the polymers described under point (1) such as, for example, mixtures of polypropylene with polyisobutylene; mixtures of polypropylene with polyethylene (for example, PP/HDPE, PP/LDFE):
mixtures of different types of polyethylene (for example, LDPE/HDPE).
(3) Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethyl-ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with polypropylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbor-nene; and mixtures of these copolymers with each other or with the polymers cited in paragraph (1) such as, for example, polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinylacetate (EVA) copolymers, LDPE/ethylene-acrylic acid (EAA) copolymers, LLDPE/EVA, LLDPE/EAA, and alternating or ~~random~~ polyalkylene/carbon monoxide copoly-mers and their mixtures with other polymers such as, for example, polyamides.
(4) Hydrocarbon resins (for example, CS-C9) comprising their hydrogenated modifications (for example, adhesive agents) and mixtures with polyalkylene and starch.
The present invention relates to compounds belong-ing to the group of enamines.
More specifically, the present invention relates to compounds belonging to the group of enamines con-sisting of derivatives of Q-keto-esters, or Q-keto-amides or 1,3-diketones with primary or secondary aliphatic or aromatic amines carrying at least one l0 sterically hindered amine group in the molecule, a process for their preparation and their use as artiaxi-dants for organic polymers.
The present invention also relates to the polymer-is compositions stabilized with the above compounds and the end-articles obtained from these compositions.
It is known that organic polymers undergo degrada-tion over a period of time as a result of exposure to atmospheric agents and light and they also easily undergo thermoxidative degradaticn during processing and transformation processes.
The most evident signs of this degradation are, for example, alterations in the mechanical properties of the end-article. To prevent this degradation of the polymeric material, stabilizing compounds are usually introduced into the organic polymers.
The Applicant has now found that compounds belong-ing to the group of enamines consisting of derivatives of ~B-keto-esters, or ,0-keto-amides or 1,3-diketones with primary or secondary, aliphatic or aromatic amines carrying at least one sterically hindered amine group in the molecule, are capable of stabilizing organic polymers to which they are added improving their resistance to thermo-oxidation.
The present invention therefore relates to com-pounds belonging to the group of enamines consisting of derivatives of ~B-keto-esters, or Q-keto-amides or 1,3-diketones with primary or secondary, aliphatic or aromatic amines carrying in the molecule at least one sterically hindered amine group having general formula (I) ,3 Rt--- ( --N--C=CH--C-_ ) m - ~ ~--R' ( I ) wherein:
- m represents an integer from 1 to 3, extremes included;
- n represents an integer from 1 to 4, extremes included;
- R~ represents a triazine having one of the follow-ing general formula (II), (III) or (IV):
\ 'N' /
INY~ ~N (II);
RS N
(III);
N~ N
N\ N (IV);
wherein R5 represents a hydrogen atom; a linear or 20 branched C~-C~8 alkyl group; a -NHR6 amine group or a -SR6 group wherein R6 represents a hydrogen atom or a linear or branched C~-C~$ alkyl group;
- R~ and RZ, the same or different, represent a hydrogen atom; a linear or branched C~-C~8 alkyl 25 group; a linear or branched C2-C8 alkoxyalkyl WO 98/47893 PCTlEP98/02186 group; a CS-C$ cycloalkyl group optionally contain-ing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C~8 aryl group; a C7-C2o arylalkyl _ or alkylaryl group; a group having general formula (V) CH, ~CH~
/y\ (V) R~
wherein R~ represents a hydrogen atom; a linear or branched C~-C~8 alkyl group, said alkyl group optionally substituted with a -NHRg group or an -OR8 group wherein R$ represents a hydrogen atom, a linear or branched C~-Ci8 alkyl group, or a Co-C~$
aryl group; an -ORq group wherein R9 represents a hydrogen atom, or a linear or branched C~-C~$ alkyl group;
- or, R~ and R2 considered jointly with the nitrogen atom, represent a C5-C8 heterocyclic group option-ally containing a second heteratom selected from oxygen, nitrogen and sulfur;
- R3 and R4, the same or different, represent a linear or branched Ci-C~8 alkyl group; a C6-C~8 aryl group; a C~-C2o alkylaryl or arylalkyl group; a linear or branched C~-C$ alkoxyl group;
- or, R4 represents a group having general formula S
(VI):
(VI) R~
wherein RT has the same meanings defined above;
- or, R4 represents an NR~oRt~ group wherein R~o and R~~, the same or different, represent a hydrogen atom; a linear or branched Ci-C~8 alkyl group; a linear or branched C2-Ce alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroa-tom selected from oxygen, nitrogen and sulfur; a C6-C~8 aryl group; a C7-CZO arylalkyl or alkylaryl group; a triazine having one of the following general formulae (II), (III) or (IV):
~N~
'NYC ~N {II);
RS N
{III);
N~ N
RS N
IV
N~ N ( ) wherein RS has the same meanings defined above: a group having general formula (V):
~3 CH;
(V) CH3 ~ CH3 R~
wherein RT has the same meanings defined above;
- or, Rio and Rig considered jointly with the nitrogen atom, represent a CS-C8 heterocyclic group option ally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R4 represents a group having one of the follow ing general formulae (VII), (VIII) or (IX):
i ~z ---OCHz--CH--OR13 (VII):
CrizOR~3 l ---OCHz--C--R~z (VIII) ;
CH20R~3 R~2--CHOR~3 ~ ---OCH2--C--CH20R~3 (IX) ;
CHZOR~3 wherein:
- R~z represents a hydrogen atom; or a linear or branched C~-C~a alkyl group:
- R~3 represents a linear or branched C~-C~$
WO 98/47$93 PCT/EP98/02186 alkyl group; a -COCHZCOCH3 group; or a direct bond;
provided that, when R~ and RZ are different from the group having general formula (V), R4 represents a group having general formula (VI).
The compounds having general formula (I) can be used as antioxidants for organic polymers.
Examples of R~, RZ, RED and R» groups, as well as a hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl, 4-(2,2,6,6-tetramethyl)piperidinyl, 4-(2,2,6,6-tetramethyl)-1-butoxyethylpiperidinyl, 4-(2,2,6,6-tetramethyl)-1-butoxypiperidinyl, 4-(2,2,6,6-tetramethyl)-1-methylpiperidinyl, 3,5-dioctylaminotriazine, 3,5-dibutylaminotriazine, etc.
Examples of C5-C8 heterocyclic groups, when R~ and RZ or Rio and R» are considered jointly with the nitro-gen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazol-idine, etc.
Examples of R3 and R4 groups are: methyl, ethyl, ' propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybu-tyl, etc.
Examples of R4 groups, when R4 represents a group having general formula (VI), are: 4-(2,2,6,6-tetrame-thyl)piperidinoxy, N-methyl-4-(2,2,6,6-tetramethyl)pi-peridinoxy, N-methoxyethyl-4-(2,2,6,6-tetramethyl)pipe-ridinoxy, N-methylaminoethyl-4-(2,2,6,6-tetramethyl)pi-peridinoxy, etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 2, are:
CHZ--O-- ; CH--0-- ;
CH3--CO--CHZ--C=0 O
CHZ
f --O--CH2--C--CH2--O-- ;
O
CH3--CO--CHZ--C=O
etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 3, are:
CHZO--CH3--CHZ--C--CHZO-- ;
O CHZO--/f . CH3--CO--CHZ--C--O--CH2--C--CH20-- ;
CHzO--etc.
Examples of R4 groups, when R4 represents a group having general formula (VII), (VIII) or (IX) and n is 4 , are : CH20--l --ocH2--c--cHzo-- ;
etc.
Examples of R~ groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, A-hydroxyethyl, p-methoxyethyl, p-butoxyethyl, methylaminoethyl, etc.
Examples of R5, R6, R8, R9, R~Z and R~3 groups, when said groups represent a linear or branched C~-C18 alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.
Specific examples of compounds having general formula (I), which should in no way be considered as limiting the scope of the present invention, are:
CHI CH;
CH;-C=CH-C N-H
CsH~-CH~ CHI
N~ N
~N~
C8H1~-HN NH-CeHp (IA) to CH3-C=CH-CO N-H
~ CH3 CH3 N/\N CH3 CH;
H3 ~ ~ ~ H3 H- -C- ~ N i -C-CH-C ~N-H
C4H9 CaH9 CH
CHI
(IB) CH3 i =CH-C N-CH3 N1 CH3 \CH3 0/ ( I C ) CH3-C=CH-C N- H
NH
CH ~CH3 I (ID) CzHs /I
CH3- i =CH-CO-CH3 CHI ( IE ) i H2 CHI
CaH9 CH3-C=CH-CO-CH3 NH
CH3 ~CH3 CH3 N/ \CH3 ( I F ) O
CHI CHI
C=CF:-C N-CHI-CH2-NH-CH3 NH
CHI
CHj ~I ~CH3 (IG) H
CH3- i =CH-CO-NH N-H
CH3 \CH3 CH3 N CH3 ( I H ) H
CHI
CH3 f =CH-CO-N N-H
CaH9 N N~N CH- CH
s 3 CQH9 N CaH9 (II) -CH3- i -CH-C00-CH2 C
NH
CH3 I 'CH3 CH N CH3 ( I L ) H
CH;-C=CH-COO-CH2- =C= ~-CH2-~~H=COCH;
i 2 ;~ 2 (IM) H
A further object of the present invention relates s to a synthesis process of compounds having general formula (I).
A process for the synthesis of the compounds having general formula (I) of the present invention comprises the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having general formula (X) HNR~ R2 ( X ) wherein R~ and RZ have the same meanings defined above, with 1-3 moles of a A-keto-ester, or a ~3-keto-amide, or a 1,3-diketone having general formula (XI):
( R3--C--Cg2--C-- ) ~--R4 ( XI ) II II
wherein R3, R4 and n have the same meanings defined above.
The above reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature ranging from 60°C
to 160°C, preferably from 115°C to 150°C, at atmospher-is pressure, and for a time ranging from 0.5 to 24 hours, preferably from 3 to 10 hours. Acetic acid can optionally be added as catalyst to this reaction.
During the above reaction, reaction water is released which is separated by azeotropic distillation /~
using an apparatus for the azeotropic distillation, whereas the organic solvent is recycled.
At the end of the reaction, the solvent and possible acetic acid present are removed by distilla-tion thus obtaining a raw product. The desired compound having general formula (I) is purified from the raw product thus obtained by fractionated distillation, operating under vacuum, at a pressure ranging from 0.1 mm/Hg to 50 mm/Hg and a temperature ranging from 40°C
to 200°C. Or, said compound having general formula (I) is separated by crystallization using techniques known in the art.
Examples of primary or secondary, aliphatic or aromatic amines, having general formula (~) which can be used for the purposes of the present invention are:
cyclohexylamine, n-butylamine, tert-butylamine, n-octy-lamine, tert-octylamine, n-octadecylamine, n-dodecylam-ine, benzylamine, 2-methoxyethylamine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2,2,6,6-te-tramethylpiperidine, 4-amino-2,2,6,6-tetramethyl-1-me-thylpiperidine, 4-amino-2,2,6,6-tetramethyl-1-butoxyet-hylpiperidine, 1-amino-3,5-dioctylaminotriazine, etc.
Examples of p-keto-esters or /3-keto-amides, or 1,3-diketones having general formula (XI) are: ethyl r5 aceto-acetate, t-butyl aceto-acetate, octadecyl aceto-acetate, ethyl benzoylacetate, acetyl-acetone, benzoyl-acetone, dibenzoyl methane, p-toluylacetone, 4-(2,2,6,6-tetramethyl)piperidinyl aceto-acetate, N-methyl-4-(2,2,6,6-tetramethyl)piperidinyl aceto-acetate, aceto-acetamide, acetoacetanilide, aceto-acet-4-(2,2,6,6,-tetramethylpiperidine)amide, aceto-acet-(3,5-dibutyltriazine)-1-amide, etc.
The enaminic function of the compounds having general formula (I) synthesized by means of the process described above, is confirmed by NMR spectrometry analysis (obtained using a BRUKER AC 200 spectrometer) executed on samples with a high purity (95% confirmed by gas-chromatography).
Other processes which can be used for the prepara-tion of the compounds having general formula (I) of the present invention, however, are described in literature such as, for example, in Houben-Weyl (1957), Vol. 11/1, pages 172-178.
Organic polymers capable of being stabilized with the compounds of the present invention are:
(1) polymers of mono-olefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyiso-prene.or polybutadiene; as well as polymers of I
cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be option-ally cross-linked) such as, for example, high density polyethylene (HDPE), low density poly-ethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
The polyolefins such as, for example the mono-olefins cited in the previous paraqraph, preferably polyethylene and polypropylene, can be prepared with various methods known in literature, preferably using the following methods:' (a) radicalic polymerization (generally carried out at a high pressure and high temperature;
(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals generally have one or more ligands such as, far example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and/or aryls which can be ~r- or a-co-ordinated. These metal complexes can be in free form or supported in substrates such as, for example activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the I ~' reaction medium. The catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups Ia, IIa and/or IIIa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amine or silyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or "single site cata-lyst" (SSC).
(2) Mixtures of the polymers described under point (1) such as, for example, mixtures of polypropylene with polyisobutylene; mixtures of polypropylene with polyethylene (for example, PP/HDPE, PP/LDFE):
mixtures of different types of polyethylene (for example, LDPE/HDPE).
(3) Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethyl-ene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with polypropylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbor-nene; and mixtures of these copolymers with each other or with the polymers cited in paragraph (1) such as, for example, polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinylacetate (EVA) copolymers, LDPE/ethylene-acrylic acid (EAA) copolymers, LLDPE/EVA, LLDPE/EAA, and alternating or ~~random~~ polyalkylene/carbon monoxide copoly-mers and their mixtures with other polymers such as, for example, polyamides.
(4) Hydrocarbon resins (for example, CS-C9) comprising their hydrogenated modifications (for example, adhesive agents) and mixtures with polyalkylene and starch.
(5) Polystyrene,poly{p-methylstyrene),poly(a-methyl-I °7 styrene).
(6) Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives such as, for exam ple, styrene/butadiene, styrene/acrylonitrile, styrene/alkyi methacrylate, styrene/butadiene/
alkyl acrylate, styrene/butadiene/alkyl methacry-late, styrene/maleic anhydride, styrene/acrylo-nitrile/methylacrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacry-late, a polymer of a diene or an ethy-lene/propylene/diene terpolymer, block polymers of styrene such as, for example, styrene/butadiene/
styrene,styrene/isoprene/styrene,styrene/ethyle-ne/butylene/styrene or styrene/ethylene/propyl-ene/styrene.
alkyl acrylate, styrene/butadiene/alkyl methacry-late, styrene/maleic anhydride, styrene/acrylo-nitrile/methylacrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacry-late, a polymer of a diene or an ethy-lene/propylene/diene terpolymer, block polymers of styrene such as, for example, styrene/butadiene/
styrene,styrene/isoprene/styrene,styrene/ethyle-ne/butylene/styrene or styrene/ethylene/propyl-ene/styrene.
(7) Grafted copolymers of styrene or a-methylstyrene such as, for example, styrene in polybutadiene, styrene in polybutadiene or polybutadiene-acrylo-~nitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methylmethacrylate in polybuta-diene; styrene and malefic anhydride in polybuta-diene; styrene, acrylonitrile and malefic anhydride or maleimide in polybutadiene; styrene and male-WO 98/4'1893 PCT/EP98/02186 imide in polybutadiene: styrene and alkylacrylates or methacrylates in polybutadiene: styrene and acrylonitrile in ethylene/propylene/diene terpoly-mers, styrene and acrylonitrile in polyalkyl 5 acrylates ar polyalkyl methacrylates, styrene and acrylonitrile in acrylate/butadiene copolymers, as well as mixtures of the copolymers listed above with the copolymers cited under point (6) such as, for example, mixtures of known copolymers such as 10 ABS, MBS, ASA or AES:
(8) Polymers containing halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or sulfochlorinated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and 15 copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, poly-vinylidenechloride, polyvinyl fluoride or polyvin-ylidenefluoride: and also their copolymers such 20 as, for example, vinyl chloride/vinylidenechlo-ride, vinyl chloride/vinyl acetate or vinylidene-chloride/vinyl acetate.
(9) Polymers deriving from a,p-unsaturated acids and their derivatives such as, for example, polyacry lates and polymethacrylates, polymethyl methacry ~.r lates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate.
(10) Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for example, acrylonitrile/butadiene copoiy-mers, acrylonitrile/alkylacrylate copolymers, acrylonitrile/alkoxyalkyl acr~~late copolymers or acrylonitrile/vinyl halide copolymers or acryloni-trile/alkyl methacrylate/butadiene terpolymers.
(11) Polymers deriving from unsaturated alcohols and amines, or their acyl or acetal derivatives such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyrral, polyallyl phthalate or polyallyl melamine; and also their copolymers with the olefins listed under point (1) .
(12) Homopolymers and copolymers of cyclic ethers such as, for example, polyalkylene glycols, polyethyl-ene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers.
(13) Polyacetals such as, for example, polyoxymethylene and polyoxymethylenes which contain ethylene oxide as comonomer; polyacetals modified with thermo-WO 98/47893 PCTlEP98/02186 t2 plastic polyurethanes, acrylates or MBS.
(14) Polyphenylene oxides and sulfides and mixtures of polyphenylene oxides with styrene or polyamide polymers.
(15) Polyurethanes deriving from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as the precursors of the above compounds.
(16) Polyamides and copolyamides deriving from diamines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained start-ing from m-xylene diamine and adipic acid; poly-amides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, .poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with poly-olefins, olefinic copolymers, ionomers or elasto-mers chemically bound or grafted; or with polye-thers such as, for example, polyethylene glycol, 2'3 polypropylene glycol or polytetramethylene glycol;
as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide system").
as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide system").
(17) Polyureas, polyimides, polyamide-imides and polybenzoimidazoles.
(18) Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene tereph-thalate,poly-1,4-dimethylolcyclohexane terephtha-late and polyhydroxybenzoates, as well as block copolyether esters deriving from polyethers with hydroxyl-terminated groups; and also polyesters I5 modified with polycarbonates or MBS.
(19) Polycarbonates and polyester carbonates.
(20) Polysulfones, polyethersulfones and polyetherketo-nes.
(21) Cross-linked polymers deriving from aldehydes on .the one hand and from phenols, urea and melamines on the other, such as, for example, phenol/formal-dehyde resins, urea/formaldehyde resins and mela-mine/formaldehyde resins.
(22) Drying or non-drying alkyd resins.
(23) Resins based on unsaturated polyesters deriving z4 from copolyesters of dicarboxyl acids saturated and unsaturated with polyhydric alcohols and vinyl compounds as cross-linking agents, and also the above resins containing halogens and having a good flame-resistance.
(24) Cross-linkable acrylic resins deriving' from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acryla-tes.
(25) Alkyd resins, resins based on polyesters or acrylated resins cross-linked with melamine resins, urea resins, resins based on polyisocyana-tes or epoxy resins.
(26) Cross-linked epoxy resins deriving from polyepoxi des such as, for example, bis-glycidyl ethers or cycloaliphatic diepoxides.
(27) Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins") or their derivatives.
(28) Mixtures of the above polymers ("polyblends") such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/AHS, PVC/MBS, PC/ABS, PBTP/ABS, . PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther-moplastics PUR, PC/thermoplastics PUR, POM/acryla tes, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, 5 PA/HDPE, PA/PP, PA/PPO.
In particular, the compounds having general formula (I) can be used in the stabilization of poly-ols.
The incorporation of the compounds having general 10 formula (I) of the present invention into organic polymers, is carried out according to methods known in the art.
For example, the compounds having general formula (I) can be added to the organic polymers, optionally in 15 the presence of other additives, in the step following their preparation, or immediately before the transfor-oration process.
The compounds having general formula (I) of the present invention are incorporated into the polymer to 20 be stabilized in a quantity ranging from 0.02% to 3% by weight, preferably between 0.05% and 1%.
A further object of the present invention relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds 25 having general formula (I).
As already mentioned above, the compounds having general formula (I) of the present invention can be combined with other conventional additives or their mixtures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example.
1. Antioxidants 1.1 Alkylated monophenols such as, for example:
2,6-di-t-butyl-4-methylphenol;
2-t-butyl-4,6-dimethylphenol:
2,6-di-t-butyl-4-ethylphenol;
2,6-di-t-butyl-4-n-butylphenol;
2,6-di-t-butyl-4-isobutylphenol:
2,6-di-cyclopentyl-4-methylphenol;
2-(a-methylcyclohexyl)-4,6-dimethylphenoi;
2,6-dioctadecyl-4-methylphenol:
2,4,6-tricyclohexylphenol;
2,6-di-t-butyl-4-methoxymethylphenol;
2,6-di-nonyl-4-methylphenol;
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol;
2,4-dimethyl-6-(I'methylhectadec-1'-yl)phenol;
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol: and their mixtures.
1.2 Alkylthiomethylphenols such as, for example:
2,4-dioctylthiomethyl-6-t-butylphenol:
2,4-dioctylthiomethyl-6-methylphenol;
2,4-dioctylthiomethyl-6-ethylphenol;
2,6-didodecylthiomethyl-4-nonylphenol.
1.3 Hydroquinones and alkylated hydroquinones such as, for example:
2,6-di-t-butyl-4-methoxyphenol;
2,5-di-t-butylhydroquinone;
2,5-di-t-amylhydroquinone;
2,6-diphenyl-4-octadecyloxyphenol;
2,6-di-t-butylhydroquinone:
2,5-di-t-butyl-4-hydroxyanisol;
3,5-di-t-butyl-4-hydroxyanisol:
3,5-di-t-butyl-4-hydroxyphenyl stearate;
bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate.
1.4 Tocopherols such as, for example:
a-tocopherol, p-tocophercl, y-tocopherol, 6-tocopherol and their mixtures (Vitamin E).
1.5 Hydroxylated thiodiphenyl ethers such as, for example:
. 2,2'-thiobis-(6-t-butyl-4-methylphenol):
2,2'-thiobis-(4-octylphenol)~
4,4'-thiobis-(6-t-butyl-3-methylphenol)~
4,4'-thiobis-(6-t-butyl-2-methylphenol);
WO 98/4'1893 PCT/EP98/02186 2~
4,4'-thiobis-(3,6-di-sec-amylphenol);
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6 Alkylidene-bisphenols such as, for example:
2,2'-methylenebis-(6-t-butyl-4-methylphenol);
2,2'-methylenebis-(6-t-butyl-4-ethylphenol):
2,2'-methylenebis[4-methyl-6-(a-methylcyc~lohe-xyl)phenol];
2,2'-methylenebis(4-methyl-6-cyclohexylphenol);
2,2'-methylenebis(6-nonyl-4-methylphenol);
2,2'-methylenebis(4,6-di-t-butylphenol);
2,2'-ethylidenebis(4,6-di-t-butylphenol);
2,2'-ethylidenebis(6-t-butyl-4-isobutylphenol);
2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphe-nol]:
2,2'-methylenebis[6-(a, a-dimethylbenzyl)-4-nonyl-phenol];
4,4'-methylenebis(2,6-di-t-butylphenol);
4,4'-methylenebis(6-t-butyl-2-methylphenol);
1,1-bis-(5-t-butyl-4-hydroxy-2-methylphenyl)-butane;
2,6-bis-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;
1,1,3-tris-(5-t-butyl-4-hydroxy-2-methylphenyl)-butane;
1,1-bis--(5-t-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane;
ethyleneglycol bis[3,3-bis(3'-t-butyl-4'-hydroxy-phenyl)butyrate];
bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopen-tadiene;
bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)~-6-t-butyl-4-methylphenyl]terephthalate:
1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane;
2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane;
2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane;
1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)-pentane.
1.7 Benzyl compounds containing G, N or S such as, for example:
3,5,3',5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether;
octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto-acetate;
2o tris(3,5-di-t-butyl-4-hydroxybenzyl)amine;
bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithio-terephthalate;
bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide;
iso-octyl-3,5-di-t-butyl-4-hydroxybenzylmercapto-acetate;
1.8 Hydroxybenzylated malonates such as, for example:
dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxyben-zyl)malonate;
dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylben-5 zyl)malonate;
didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate;
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate.
10 1.9 Aromatic hydroxybenzyl compounds such as, for example:
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene:
1,4-bis-(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-15 tetramethylbenzene;
2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)phenol.
1.10 Triazine compounds such as, for example:
2,4-bis(octylmercapto)-6-(3,5-di-t-butyl-4-hydro-xyaniline)-1,3,5-triazine;
20 2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydro-xyaniline)-1,3,5-triazine;
2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydro-xyphenoxy)-1,3,5-triazine;
2,4,6-tris-(3,5-di-t-butyl-4-hydroxyphenoxy)-25 1,2,3-triazine;
WO 98/47893 pCT/EP98/02186 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocya-nurate;
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylben-zyl)isocyanurate;
2,4,6-tris-(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;
1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)hexahydro-1,3,5-triazine;
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxyben-to zyl)isocyanurate.
1.11 Benzylphosphonates such as, for example:
dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphona-te;
diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonatet dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphospho-nate;
dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylpho-sphonate~
calcium salts of monoethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid.
1.12 l~cylaminophenols such as, for example:
4-hydroxylauranilide:
4-hydroxystearanilide;
octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate.
1.13 Esters of /~-(3,5-di-t-butyl-4-hydroxyphenyl)pro-pionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6 hexandiol, 1,9-nonandiol, ethylene glycol, 1,2 propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thioundecanol,3-thiopentadecanol, trimethylhexandiol, trimethyl-olpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxa-bicyclo[2.2. 2]octane.
1.14 Esters of ~B-(5-t-butyl-4-hydroxy-3-methylphe-nyl)propionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy-lolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trio-xabicyclo[2.2.2]octane.
1.15 Esters of A-(3,5-dicyclohexyl-4-hydroxyphenyl)pro-pionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6-he-xandiol, 1,9-nonandiol, ethylene glycol, 1,2-pro-panediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaeryth ritol, tris(hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl)oxamide, 3-thioundecanol, 3-thio pentadecanol, trimethylhexandiol, trimethylol propane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabi cyclo[2.2.2]octane.
1.16 Esters of (3,5-di-t-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6 hexandiol, 1,9-nonandiol, ethylene glycol, 1,2 propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy-lolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trio-xabicyclo[2.2.2]octane.
1.17 Amides of p-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid such as, for example:
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-39.
nyl)hexamethylenediamine;
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)trimethylenediamine;
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)hydrazine.
2. Ultra-violet ray and light stabilizers.
2.1 Derivatives of 2-(2'-hydroxyphenyl)benzotriazoles such as, for example:
2-(2'-hydroxy-5'methylphenyl)benzotriazole;
2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazo-le;
2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazole;
2-[2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phe-nyl]benzotriazole;
2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chloroben-zotriazole;
2-(3'-t-butyl-2'-hydroxy-5'-methylphenyl)-5-chlo-robenzotriazole;
2-(3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl)benzo-.triazole:
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole;
2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole;
2-[3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphe-nyl]benzotriazole;
mixtures of2-[3'-t-butyl-2'-hydroxy-5'-(2-octylo-xycarbonylethyl)phenyl)-5-chorobenzotriazole, 2-[3'-t-butyl-5'-(2-(2-ethylhexyloxy)carbonylethyl)-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phe-nyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzo-triazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-octylo-xycarbonylethyl)phenyl]benzotriazole, 2-[3'-t-butyl-5'-(2-(2-ethylhexyloxy)carbonylethyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and2-[3'-t-butyl-2'-hydroxy-5'-(2-iso-octyloxycarbonylethyl) phenyl]benzotriazole, 2,2'-methylene-bis[4-(1,1,-3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol];
esterification product of 2-[3'-t-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzo-triazole with polyethylene glycol 300;
[R-CHZCH2-C00 ( CH2) 3 ] z wherein R - 3' -t-butyl-4-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.
2.2 Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-trihydroxy-; 2'-hydroxy-4,4'-dimethoxy.
2.3 Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol, bis(4-t-butylbenzoyl)-resor-cinol,dibenzoyl-resorcinol,2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, octadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-t-butyl-phenyl-3,5-di-t-butyl-4-hydroxybenzoate.
2.4 Acrylates such as, for example, ethyl or isoctyl a-cyano-Q,p-diphenylacrylate;methyl a-carbometho xycinnamate, methyl or butyl a-cyano-p-methyl-p methoxycinnamate,methyla-carbomethoxy-p-methoxy-cinnamate, N-(p-carbomethoxy-,0-cyanovinyl)-2-methylindoline.
2.5 Nickel compounds such as, for example, complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phe-nol ] , for example 1: 1 or 1: 2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of .monoalkyl esters of 4-hydroxy-3,5-di-t-butyl-benzyl-phosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazol with or without additional ligands.
2.6 Oxamides such as, for example:
. 4,4'-dioctyloxyoxaniiide;
2,2'-diethoxyoxanilide;
2,2'-dioctyloxy-5,5'-di-t-butoxanilide:
2,2'-didodecyloxy-5,5'-di-t-butoxanilide;
2-ethoxy-2'-ethyloxanilide;
N,N'-bis{3-dimethylaminopropyl)oxamide;
2-ethoxy-5-t-butyl-2'-ethoxanilide and its mix-tures with2-ethoxy-2'-ethyl-5,4'-di-t-butoxanili-de; and mixtures of disubstituted ortho- and para-methoxy anilides and mixtures of disubstituted ortho and para-ethoxy anilides.
2.7 2-(2-hydroxyphenyl)-1,3,5-triazines such as, for example:
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tri-azine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dime-thylphenyl)-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphe-nyl)-1,3,5-triazine;
2,4-bis-(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy)-4,6-bis(4-methylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-3~
dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phe-nyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.
3. "Metal-deactivators" such as, for example:' N,N-diphenyloxamide, N-salicylal-N'-salicyloyl-hydra-zine,N,N'-bis(salicyloyl)hydrazine;N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)o-xalyl dihydrazide, oxanilide, isophthaloyl dihy-drazide, sebacoyl bisphenylhydrazide, N,N'-diace-tyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxal-lyldihydrazide,N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites such as, fcr example:
triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phos-phite, trilauryl phosphite, trioctadecyl phos-phite, distearyl pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butyl-phenyl)pentaerythritol diphosphite, bis(2,5-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritoldiphosphite,bis(2,4-3~
di-t-butyl-6-methylphenyl)Jpentaerythritol diphos-phite, bis[2,4,5-tris(t-butylphenyl)]pentaerythri-tol diphosphite, tristearyl sorbitol triphosphite, tetrakis-(2,4-di-t-butyl-phenyl)-4,4'-diphenylile-nediphosphonite, 5-iso-octyloxy-2,4,8,10-tetra-t-butyl-12H-di-benzo[d,g]-1,3,2-dioxaphosphocine, 5-fluoro-2,4,8,10-tetra-t-butyl-12-methyl-diben-zo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-t-bu-tyl-5-methylphenyl)methylphosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethylphosphite.
5. Agents which are capable of destroying peroxides such as, for example, esters of ~Q-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbama-te, dioctadecyldisulfide pentaerythritol tetrakis (p-dodecylmercapto)propionate.
6. Stabilizers of polyamides such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
7. Basic co-stabilizers such as, for example: mela-mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, deriva-tives of hydrazine, amines, polyamides, polyure-thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimo-nium-pyrocatecholate, tin-pyrocatecholate.
5 8. Nucleating agents such as, for example: 4-t-butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium 10 sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives such as, for example: plastici-zers, lubricants, emulsifying agents, pigments, optical brighteners, flame-retardants (for exam-15 ple, bromides, chlorurates, phosphorates and phos-phorous/halogen mixtures), antistatic agents, blowing agents, thiosynergizing agents such as, for example, dilauryl thiodipropionate or diste-aryl thiodipropionate.
20 il. Benzofuranones and indolinones such as, for ex.:
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-t-butylben-zofuran-2-one;
5,7-di-t-butyl-3-[4-(2-stearoyloxyethoxy)phe-nyl]benzofuran-2-one:
25 3,3~-bis[5,7-di-t-butyl-3-[4-(2-hydroxyethoxy)phe-4!
nyl]benzofuran-2-one]:
5,7-di-t-butyl-3-(4-ethoxyphenyl)benzofuran-2-one:
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-one:
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-t-butyl-benzofuran-2-one:
or those described in U.S. patents 4.325.863, 4.338.244, 5.175.312, 5.216.052, 5.252.643, 4.316.611, 4.316.622, 4.316.876 or in European ZO patent applications 589.839 and 591.102.
In order to verify the stabilizing activity of the compounds having general formula (I) oz the present invention, differential thermal analysis was used, revealing the time necessary for starting up the oxidation reaction of the system.
F'or this purpose a non-stabilized polyol was used, of the type Glendion FG 3502 sold by EniChem S.p.A., and the stabilizer was added at levels of 0.15%.
The oxygen absorption induction time measurement was carried out on the polyol at a temperature of 130°C
and 140°C under a stream of oxygen. The greater the oxygen absorption induction time, the better is the stabilizing system used.
Proof of the good stabilizing capacity cf the compounds having general formula (I) of the present invention was provided by observing the oxygen absorp-tion induction time of the polyol to which the com-pounds having general formula (I) had been added, compared with the stabilizing capacity of the commer-cial product BHT, corresponding to 2,6-di-t-butyl-4-methylphenol, and with the polyol without stabilizers (see Example 7 below).
In addition, the importance of the molecular structure of the compounds having general formula (I) was demonstrated by comparing with an enamine having the formula (Compound Nr. 5, see Example 5 below):
N ~ N-H
CH
which . lacks the structure of the enamine double bond conjugated with the carbonyl double bond which is present, however, in the above compounds having general formula (I); and with an enamine having the forirula (Compound Nr. 6, see Example 6 below):
2 0 ~ CH3--C=CH--COOCHZCH3 C~8H3~--NH
which lacks the sterically hindered amine group.
Some illustrative but non-limiting examples are provided for a better understanding of the present invention and for its embodiment.
' Preparation of R-methoxyethylamine crotonate of 4-. (2,2,6,6-tetramethyl)piperidinyl (Compound Nr. i) having the following formula:
CH3--i =CH
CH3-p-CH2 CH2 -NI-I
24.13 g (0.1 moles) of 2,2,6,6-tetramethyl-4-pi-peridinyl-aceto-acetate, 24 g of toluene, 7.51 g (O.i moles) of 2-methoxyethylamine and 0.23 g of glacial acetic acid, are charged into a 250 ml four-necked reactor, equipped with a stirrer, thermometer and reflux condenser with a water separator.
The reaction mass is maintained under stirring and reflux heated for 4 hours, to a temperature ranging from 115°C to 118°C. During this period there is the formation of reaction water which is separated by azeotropic distillation: 1.5 g of reaction water are separated.
The solvent and acetic acid are removed by distil-lation and the raw residue thus obtained is subjected to fractionated distillation.
This distillation is carried out in a distiller consisting of a 100 ml boiler equipped with a thermome-ter, stirrer, column, condenser and device for the collection of fractions.
A central fraction containing 26.6 g of distilled product corresponding to Compound Nr. 1, is collected from the above distillation, operating under the following conditions:
- temperature at the head: 146'C-151°C;
- temperature of the boiler: 148°C-152°C~
- vacuum: 0.1 mm/Hg.
Compound Nr. 1 thus obtained, analyzed by gas-chromatography (GC), proves to be 97.5% pure, with a yield of about 89.2%.
Compound Nr. 1 is characterized by NMR analysis which confirms its enamine structure.
- 'H-NMR (200 MHz, CDC13-TMS) d (ppm): NH (broad) 8.50 ppm; C=CH (s) 4.34 ppm: the other signals are in accordance with the structure.
The other compounds (Compcunds Nr. 2-11) are prepared analogously to Example 1, of which only the reaction conditions and characteristics are specified.
Preparation of /3-(2,2,6,6,-tetramethylpiperidine-4-amino)ethyl crotonate (Compound Nr. 2) having the following formula: .
~5 CHI-C=CH-COOCH2CH3 NH
CH3 , 'CH3 CH3 N/ \CH3 H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: ethyl aceto-acetate;
26.03 g (0.2 moles).
l0 - Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.3 g - Duration and reaction temperature: 5 hours at 126°C-128°C.
- Distillation range: 118°C-133°C (head): i30°C-144°C (boiler); 0.10 mm/Hg - 0.15 mm/Hg (vacuum).
- Product obtained: 47.5 g.
- GC Purity: 98.9%.
- Yield: 88.4%
- ''H-NMR (200 MHz, CDC13-TMS) 6 (ppm) : NH (d) 8.39 ppm; C=CH (s) 4.35 ppm; the other signals are in accordance with the structure.
EXA1~PLE 3 Preparation of p-(2,2,6,6,-tetramethylpiperidine-4-amino) crotonate of 4-(2,2,6,6-tetramethyl)piperidinyl (Compound Nr. 3) having the following formula:
;. N-H
CH 'CH~
CH
CH
H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonylcompound:2,2,6,6-tetramethyl-4-piperidi nylaceto-acetate; 48.5 g (0.2 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.44 g - Reaction time and temperature: 3.5 hours at 114°C-128'C.
In this case the raw residue obtained is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature. When the crystallization is complete; the product obtained is filtered, washed with toluene and dried.
- Product obtained: 41.4 g.
- GC Purity: 98.9%.
- Yield: 54.4%
WO 98/47893 PG"T/EP98/02186 - 'H-NMR (200 MH2, CDC13-TMS) d (ppm): NH (d) 8.32 ppm; C=CH (s) 4.30 ppm; the other signals are in accordance with the structure.
- Melting point: 151°C.
Preparation of 2-(2,2,6,6-tetramethylpiperidine-4-amino)-2-pentane-9-one (Compound Nr. 4) having the following formula:
CH=-C=CH-COCH:
CH: ~ i ~ NCH:
CH
H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
62.5 g (0.4 moles).
- Carbonyl compound: acetylacetone; 40.05 g (0.4 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.6 g - 'Reaction water separated: 7.2 g - Reaction time and temperature: 4 hours at 120°C-138 ° C.
In this case the raw residue obtained is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 71 g.
- GC Purity: > 99%.
- Yield: 83.6%
- 'H-NMR (200 MHz, CDC13-TMS) d (ppm) : NH (d) 10.48 ppm; C=CH (s) 4.60 ppm; the other signals are in accordance with the structure.
- Melting point: 103°C.
Preparation of 4-piperidino-2,2,6,6-tetramethyl-1,2,-5,6-tetrahydropyridine (Compound Nr. 5) having the following formula:
CH; CH3 N ~ N-H
Compound Nr. 5 is synthesized operating according to the procedure described by M. Dagonneau et al. in "Synthesis" (1984), page 902. The product obtained has a purity > 99%.
Preparation of J3-octadecylamino ethyl crotonate (Com-pound Nr. 6) having the following formula:
CH3--C=CH--COOCH2-CH3 ' C1sH37--NH
- Amine: octadecylamine; 53.9 g (0.2 moles).
- Carbonyl compound: ethyl acetoacetate; 26.03 g (0.2 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.5 g - Reaction time and temperature: 1 h 45' at 118°C-130°C.
The product is isolated as boiler residue after distillation under vacuum of the solvent and acetic acid.
- Product obtained: 75 g.
- GC Purity: 98.2%.
- Yield: 98.3%
- ~H-NMR (200 MHz, CDC13-TMS) 8 (ppm}: NH (broad) 8.53 ppm; C=CH (s} 4.40 ppm; the other signals are in accordance with the structure.
- Melting point: 40.5°C.
Preparation of (3-(2,2,6,6-tetramethylpiperidine-4-amino)t-butyl arotonate (Compound Nr. 7) having the following formula:
H3 C -.C-CH-COOC'CH3 NH
H3 C ~N 'CH3 - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
10 - Carbonyl compound: t-butyl aceto-acetate;
31.64 g (0.2 moles).
- Solvent:~toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.2 g 15 - Reaction time and temperature: 5 hours at 122°C-123°C.
- Distillation range: 142°C-162'C (head); 146°C-183°C (boiler); 0.10 mm/Hg - 0.15 mm/Hg (vacuum).
- Product obtained: 37.1 g.
20 - 'GC Purit~~: 91.6%.
- Yield: 62.6%
- Melting point: 86.7°C (solid at room temperature).
Preparation of (3-(2,2,6,6-tetramethylpiperidine-4-25 amino)octadecyl crotonate (Compound Nr. e) having the following formula:
H3 C-C=~-W a Ha ~
NH
C ~3 H3 C N ~3 - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
13.22 g (0.085 moles).
- Carbonyl compound: octadecyl aceto-acetate; 30 g (0.085 moles).
- Solvent: toluene; 25 g.
- Catalyst: acetic acid; 0.15 g - Reaction water separated: 1.21 g - Reaction time and temperature: 3 h 45' at 132°C-138°C.
In this case the raw reaction mass is not subject-ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera-ture. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 21.7 g.
- GC Purity: 99%.
- Yield: 51.8%
- Melting point: 53.7°C.
Preparation of 1-phenyl-1-(2,2,6,s-tetramethylpiperi-dine-4-amino)-2-benzoyl-ethylene (Compound Nr. 9) having the following formula:
-C=CH-NH
H
3C f a - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
38.57 g (0.247 moles).
- Carbonyl compound: dibenzoyl methane; 44.85 g (0.2 moles) .
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.9 g - Reaction water separated: 4.8 g - Reaction time and temperature: 22 h at 159°C-163°C.
In this case the raw reaction mass is not subject-ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera-ture. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 32.25 g.
- GC Purity: 92%.
- Yield: 44.5%
wo ~4~s93 pc~rriErr9sroms6 - Melting point: 99°C.
Preparation of ~-(2,2,6,6-tetramethyl-piperidine-4 ' amino)anilide crotonate (Compound Nr. io) having the following formula:
H3 ~.' r C~.i3 l0 ~C N
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: aceto-acetanilide: 35.44 g (0.2 moles) .
- Solvent: methanol; 100 g.
- Catalyst: acetic acid; 0.4 g - Reaction water separated: in this case the reac-tion water is not separated.
- Reaction time and temperature: 13 h at 20"C-26'C.
In this case the raw reaction mass is not subject ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera ture. When the crystallization is complete, the product obtained is filtered, washed with n-pentane and dried.
- Product obtained: 54.34 g.
S
- GC Purity: > 97%.
- Yield: 86.1%
- Melting point: 188°C.
Preparation of 1-methyl-1-(2,2,6,6,-tetramethyl-piperi-dine-4-amino)-2-benzoyl-ethylene (Compound Nr. 11) having the following formula:
H3 C_ C, ~'F~ -CO---~~
NH
to H3 C ~/ CH3 H3 C ~ N CHs H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: benzoylacetone; 32.44 g {0.2 moles) .
- Solvent: toluene; 100 g.
- Catalyst: acetic acid; 0.4 g - Reaction water separated: 3.2 g - Reaction time and temperature: 6 h at 118°C-120°C.
In this case the raw reaction mass is not subject ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera ture. When the crystallization is complete, the product obtained is filtered, washed with n-pentane and dried.
- Product obtained: 50.2 g.
- GC Purity: > 98.5%.
- Yield: 83.5%
5 - Melting point: 112°C.
Stabilizing activity test of the Compounds having general formula (I) on polyol.
The oxidation kinetics of the polyol stabilized 10 with Compounds 1-11 prepared as described in Examples 1-11 above, are observed by differential thermal analysis at 130°C and at 140°C.
Inside the measurement capsule, the systems analyzed are brought in 5 minutes to the test tempera-15 ture under nitrogen. Oxygen is then passed (7 ml/h) and the oxidation kinetics are observed in relation to the heat developed during the process. The induction time is calculated in the intersection point with the time axis of the tangent at the oxidation curve at 1 mW as 20 illustrated in Figure 1: the abscissa indicates the time in minutes, the ordinate the trend of the heat developed in mW.
The addition of the polyol is obtained by mixing the polyol with the products to be analyzed, Compounds 25 1-11 and 2,6-di-t-butyl-4-methylphenol (BHT), in a S
quantity equal to 0.15%, the mixture being stirred until complete dissolution of the products used is obtained.
A non-stabilized polyol of the type Glendion FG
3501 produced and sold by EniChem S.p.A., is used as polyol.
Table 1 indicates the induction times in minutes of the oxygen absorption during the thermo-oxidation of the polyol at 130°C and at 140°C.
T~BLG 1 ~nti:.xidanta I:.duction tine Induction time i~
at 130C (min.) at 140C (min.) Polyol as it is 5 --Compound n 1 > 60 20.4 Compound n 2 > 60 20.7 Compound n 3 > 60 20.3 Compound n 4 > 60 21.2 Compound n 5 5.5 ~ -_ Compound n 6 ~ 5 --Compound n 7 > 60 20.5 Compound n 8 45.5 18.2 Compound n 9 > 60 23.0 Compound n 10 > 60 25.0 Compound n 11 > 60 23.5 BHT 29.3 9.7 The results shown in Table 1 clearly demonstrate a~;~~~lc~~~~ s~~~E-~ 57.
that, when the compounds having general formula (I), Compounds 1-4 and 7-11, are used, the oxygen absorption induction times in the thermo-oxidation of the polyol are considerably higher than those obtained by using BHT.
In addition, these results show that the com-pounds, such as Compound Nr. 5, in which tetramethylpi-peridine is present but not the enamine double bond conjugated with the carbonyl double bond, they are not capable of stabilizing the polyol. The same result is obtained using Compound Nr. 6 in which there is the enamine double bond conjugated with the carbonyl double bond but not tetramethylpiperidine.
~' . f', ~ ; a .
~~v ~.~,~.._
In particular, the compounds having general formula (I) can be used in the stabilization of poly-ols.
The incorporation of the compounds having general 10 formula (I) of the present invention into organic polymers, is carried out according to methods known in the art.
For example, the compounds having general formula (I) can be added to the organic polymers, optionally in 15 the presence of other additives, in the step following their preparation, or immediately before the transfor-oration process.
The compounds having general formula (I) of the present invention are incorporated into the polymer to 20 be stabilized in a quantity ranging from 0.02% to 3% by weight, preferably between 0.05% and 1%.
A further object of the present invention relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds 25 having general formula (I).
As already mentioned above, the compounds having general formula (I) of the present invention can be combined with other conventional additives or their mixtures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example.
1. Antioxidants 1.1 Alkylated monophenols such as, for example:
2,6-di-t-butyl-4-methylphenol;
2-t-butyl-4,6-dimethylphenol:
2,6-di-t-butyl-4-ethylphenol;
2,6-di-t-butyl-4-n-butylphenol;
2,6-di-t-butyl-4-isobutylphenol:
2,6-di-cyclopentyl-4-methylphenol;
2-(a-methylcyclohexyl)-4,6-dimethylphenoi;
2,6-dioctadecyl-4-methylphenol:
2,4,6-tricyclohexylphenol;
2,6-di-t-butyl-4-methoxymethylphenol;
2,6-di-nonyl-4-methylphenol;
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol;
2,4-dimethyl-6-(I'methylhectadec-1'-yl)phenol;
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol: and their mixtures.
1.2 Alkylthiomethylphenols such as, for example:
2,4-dioctylthiomethyl-6-t-butylphenol:
2,4-dioctylthiomethyl-6-methylphenol;
2,4-dioctylthiomethyl-6-ethylphenol;
2,6-didodecylthiomethyl-4-nonylphenol.
1.3 Hydroquinones and alkylated hydroquinones such as, for example:
2,6-di-t-butyl-4-methoxyphenol;
2,5-di-t-butylhydroquinone;
2,5-di-t-amylhydroquinone;
2,6-diphenyl-4-octadecyloxyphenol;
2,6-di-t-butylhydroquinone:
2,5-di-t-butyl-4-hydroxyanisol;
3,5-di-t-butyl-4-hydroxyanisol:
3,5-di-t-butyl-4-hydroxyphenyl stearate;
bis(3,5-di-t-butyl-4-hydroxyphenyl)adipate.
1.4 Tocopherols such as, for example:
a-tocopherol, p-tocophercl, y-tocopherol, 6-tocopherol and their mixtures (Vitamin E).
1.5 Hydroxylated thiodiphenyl ethers such as, for example:
. 2,2'-thiobis-(6-t-butyl-4-methylphenol):
2,2'-thiobis-(4-octylphenol)~
4,4'-thiobis-(6-t-butyl-3-methylphenol)~
4,4'-thiobis-(6-t-butyl-2-methylphenol);
WO 98/4'1893 PCT/EP98/02186 2~
4,4'-thiobis-(3,6-di-sec-amylphenol);
4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl)disulfide.
1.6 Alkylidene-bisphenols such as, for example:
2,2'-methylenebis-(6-t-butyl-4-methylphenol);
2,2'-methylenebis-(6-t-butyl-4-ethylphenol):
2,2'-methylenebis[4-methyl-6-(a-methylcyc~lohe-xyl)phenol];
2,2'-methylenebis(4-methyl-6-cyclohexylphenol);
2,2'-methylenebis(6-nonyl-4-methylphenol);
2,2'-methylenebis(4,6-di-t-butylphenol);
2,2'-ethylidenebis(4,6-di-t-butylphenol);
2,2'-ethylidenebis(6-t-butyl-4-isobutylphenol);
2,2'-methylenebis[6-(a-methylbenzyl)-4-nonylphe-nol]:
2,2'-methylenebis[6-(a, a-dimethylbenzyl)-4-nonyl-phenol];
4,4'-methylenebis(2,6-di-t-butylphenol);
4,4'-methylenebis(6-t-butyl-2-methylphenol);
1,1-bis-(5-t-butyl-4-hydroxy-2-methylphenyl)-butane;
2,6-bis-(3-t-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol;
1,1,3-tris-(5-t-butyl-4-hydroxy-2-methylphenyl)-butane;
1,1-bis--(5-t-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane;
ethyleneglycol bis[3,3-bis(3'-t-butyl-4'-hydroxy-phenyl)butyrate];
bis(3-t-butyl-4-hydroxy-5-methylphenyl)dicyclopen-tadiene;
bis[2-(3'-t-butyl-2'-hydroxy-5'-methylbenzyl)~-6-t-butyl-4-methylphenyl]terephthalate:
1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane;
2,2-bis(3,5-di-t-butyl-4-hydroxyphenyl)propane;
2,2-bis(5-t-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane;
1,1,5,5-tetra(5-t-butyl-4-hydroxy-2-methylphenyl)-pentane.
1.7 Benzyl compounds containing G, N or S such as, for example:
3,5,3',5'-tetra-t-butyl-4,4'-dihydroxydibenzyl ether;
octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto-acetate;
2o tris(3,5-di-t-butyl-4-hydroxybenzyl)amine;
bis(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)dithio-terephthalate;
bis(3,5-di-t-butyl-4-hydroxybenzyl)sulfide;
iso-octyl-3,5-di-t-butyl-4-hydroxybenzylmercapto-acetate;
1.8 Hydroxybenzylated malonates such as, for example:
dioctadecyl-2,2-bis(3,5-di-t-butyl-2-hydroxyben-zyl)malonate;
dioctadecyl-2-(3-t-butyl-4-hydroxy-5-methylben-5 zyl)malonate;
didodecylmercaptoethyl-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate;
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate.
10 1.9 Aromatic hydroxybenzyl compounds such as, for example:
1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene:
1,4-bis-(3,5-di-t-butyl-4-hydroxybenzyl)-2,3,5,6-15 tetramethylbenzene;
2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)phenol.
1.10 Triazine compounds such as, for example:
2,4-bis(octylmercapto)-6-(3,5-di-t-butyl-4-hydro-xyaniline)-1,3,5-triazine;
20 2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydro-xyaniline)-1,3,5-triazine;
2-octylmercapto-4,6-bis(3,5-di-t-butyl-4-hydro-xyphenoxy)-1,3,5-triazine;
2,4,6-tris-(3,5-di-t-butyl-4-hydroxyphenoxy)-25 1,2,3-triazine;
WO 98/47893 pCT/EP98/02186 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)isocya-nurate;
1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylben-zyl)isocyanurate;
2,4,6-tris-(3,5-di-t-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;
1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)hexahydro-1,3,5-triazine;
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxyben-to zyl)isocyanurate.
1.11 Benzylphosphonates such as, for example:
dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphona-te;
diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonatet dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphospho-nate;
dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylpho-sphonate~
calcium salts of monoethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid.
1.12 l~cylaminophenols such as, for example:
4-hydroxylauranilide:
4-hydroxystearanilide;
octyl-N-(3,5-di-t-butyl-4-hydroxyphenyl)carbamate.
1.13 Esters of /~-(3,5-di-t-butyl-4-hydroxyphenyl)pro-pionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6 hexandiol, 1,9-nonandiol, ethylene glycol, 1,2 propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,3-thioundecanol,3-thiopentadecanol, trimethylhexandiol, trimethyl-olpropane, 4-hydroxymethyl-1-phospho-2,6,7-trioxa-bicyclo[2.2. 2]octane.
1.14 Esters of ~B-(5-t-butyl-4-hydroxy-3-methylphe-nyl)propionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy-lolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trio-xabicyclo[2.2.2]octane.
1.15 Esters of A-(3,5-dicyclohexyl-4-hydroxyphenyl)pro-pionic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6-he-xandiol, 1,9-nonandiol, ethylene glycol, 1,2-pro-panediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaeryth ritol, tris(hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl)oxamide, 3-thioundecanol, 3-thio pentadecanol, trimethylhexandiol, trimethylol propane, 4-hydroxymethyl-1-phospho-2,6,7-trioxabi cyclo[2.2.2]octane.
1.16 Esters of (3,5-di-t-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols such as, for example:
methanol, ethanol, octanol, octadecanol, 1,6 hexandiol, 1,9-nonandiol, ethylene glycol, 1,2 propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy-lolpropane, 4-hydroxymethyl-1-phospho-2,6,7-trio-xabicyclo[2.2.2]octane.
1.17 Amides of p-(3,5-di-t-butyl-4-hydroxyphenyl)-propionic acid such as, for example:
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-39.
nyl)hexamethylenediamine;
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)trimethylenediamine;
N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropio-nyl)hydrazine.
2. Ultra-violet ray and light stabilizers.
2.1 Derivatives of 2-(2'-hydroxyphenyl)benzotriazoles such as, for example:
2-(2'-hydroxy-5'methylphenyl)benzotriazole;
2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazo-le;
2-(5'-t-butyl-2'-hydroxyphenyl)benzotriazole;
2-[2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phe-nyl]benzotriazole;
2-(3',5'-di-t-butyl-2'-hydroxyphenyl)-5-chloroben-zotriazole;
2-(3'-t-butyl-2'-hydroxy-5'-methylphenyl)-5-chlo-robenzotriazole;
2-(3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl)benzo-.triazole:
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole;
2-(3',5'-di-t-amyl-2'-hydroxyphenyl)benzotriazole;
2-[3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphe-nyl]benzotriazole;
mixtures of2-[3'-t-butyl-2'-hydroxy-5'-(2-octylo-xycarbonylethyl)phenyl)-5-chorobenzotriazole, 2-[3'-t-butyl-5'-(2-(2-ethylhexyloxy)carbonylethyl)-2'-hydroxyphenyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phe-nyl]-5-chlorobenzotriazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl]benzo-triazole, 2-[3'-t-butyl-2'-hydroxy-5'-(2-octylo-xycarbonylethyl)phenyl]benzotriazole, 2-[3'-t-butyl-5'-(2-(2-ethylhexyloxy)carbonylethyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and2-[3'-t-butyl-2'-hydroxy-5'-(2-iso-octyloxycarbonylethyl) phenyl]benzotriazole, 2,2'-methylene-bis[4-(1,1,-3,3-tetramethylbutyl)-6-benzotriazol-2-yl-phenol];
esterification product of 2-[3'-t-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzo-triazole with polyethylene glycol 300;
[R-CHZCH2-C00 ( CH2) 3 ] z wherein R - 3' -t-butyl-4-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.
2.2 Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-trihydroxy-; 2'-hydroxy-4,4'-dimethoxy.
2.3 Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol, bis(4-t-butylbenzoyl)-resor-cinol,dibenzoyl-resorcinol,2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, octadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-t-butyl-phenyl-3,5-di-t-butyl-4-hydroxybenzoate.
2.4 Acrylates such as, for example, ethyl or isoctyl a-cyano-Q,p-diphenylacrylate;methyl a-carbometho xycinnamate, methyl or butyl a-cyano-p-methyl-p methoxycinnamate,methyla-carbomethoxy-p-methoxy-cinnamate, N-(p-carbomethoxy-,0-cyanovinyl)-2-methylindoline.
2.5 Nickel compounds such as, for example, complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phe-nol ] , for example 1: 1 or 1: 2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of .monoalkyl esters of 4-hydroxy-3,5-di-t-butyl-benzyl-phosphonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazol with or without additional ligands.
2.6 Oxamides such as, for example:
. 4,4'-dioctyloxyoxaniiide;
2,2'-diethoxyoxanilide;
2,2'-dioctyloxy-5,5'-di-t-butoxanilide:
2,2'-didodecyloxy-5,5'-di-t-butoxanilide;
2-ethoxy-2'-ethyloxanilide;
N,N'-bis{3-dimethylaminopropyl)oxamide;
2-ethoxy-5-t-butyl-2'-ethoxanilide and its mix-tures with2-ethoxy-2'-ethyl-5,4'-di-t-butoxanili-de; and mixtures of disubstituted ortho- and para-methoxy anilides and mixtures of disubstituted ortho and para-ethoxy anilides.
2.7 2-(2-hydroxyphenyl)-1,3,5-triazines such as, for example:
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tri-azine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dime-thylphenyl)-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphe-nyl)-1,3,5-triazine;
2,4-bis-(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy)-4,6-bis(4-methylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-3~
dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phe-nyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine.
3. "Metal-deactivators" such as, for example:' N,N-diphenyloxamide, N-salicylal-N'-salicyloyl-hydra-zine,N,N'-bis(salicyloyl)hydrazine;N,N'-bis(3,5-di-t-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)o-xalyl dihydrazide, oxanilide, isophthaloyl dihy-drazide, sebacoyl bisphenylhydrazide, N,N'-diace-tyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxal-lyldihydrazide,N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites such as, fcr example:
triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phos-phite, trilauryl phosphite, trioctadecyl phos-phite, distearyl pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-t-butyl-phenyl)pentaerythritol diphosphite, bis(2,5-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritoldiphosphite,bis(2,4-3~
di-t-butyl-6-methylphenyl)Jpentaerythritol diphos-phite, bis[2,4,5-tris(t-butylphenyl)]pentaerythri-tol diphosphite, tristearyl sorbitol triphosphite, tetrakis-(2,4-di-t-butyl-phenyl)-4,4'-diphenylile-nediphosphonite, 5-iso-octyloxy-2,4,8,10-tetra-t-butyl-12H-di-benzo[d,g]-1,3,2-dioxaphosphocine, 5-fluoro-2,4,8,10-tetra-t-butyl-12-methyl-diben-zo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-t-bu-tyl-5-methylphenyl)methylphosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethylphosphite.
5. Agents which are capable of destroying peroxides such as, for example, esters of ~Q-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbama-te, dioctadecyldisulfide pentaerythritol tetrakis (p-dodecylmercapto)propionate.
6. Stabilizers of polyamides such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
7. Basic co-stabilizers such as, for example: mela-mine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, deriva-tives of hydrazine, amines, polyamides, polyure-thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimo-nium-pyrocatecholate, tin-pyrocatecholate.
5 8. Nucleating agents such as, for example: 4-t-butyl-benzoic acid, adipic acid, diphenylacetic acid.
9. Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium 10 sulfate, metal oxides and hydroxides, carbon black, graphite.
10. Other additives such as, for example: plastici-zers, lubricants, emulsifying agents, pigments, optical brighteners, flame-retardants (for exam-15 ple, bromides, chlorurates, phosphorates and phos-phorous/halogen mixtures), antistatic agents, blowing agents, thiosynergizing agents such as, for example, dilauryl thiodipropionate or diste-aryl thiodipropionate.
20 il. Benzofuranones and indolinones such as, for ex.:
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-t-butylben-zofuran-2-one;
5,7-di-t-butyl-3-[4-(2-stearoyloxyethoxy)phe-nyl]benzofuran-2-one:
25 3,3~-bis[5,7-di-t-butyl-3-[4-(2-hydroxyethoxy)phe-4!
nyl]benzofuran-2-one]:
5,7-di-t-butyl-3-(4-ethoxyphenyl)benzofuran-2-one:
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-one:
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-t-butyl-benzofuran-2-one:
or those described in U.S. patents 4.325.863, 4.338.244, 5.175.312, 5.216.052, 5.252.643, 4.316.611, 4.316.622, 4.316.876 or in European ZO patent applications 589.839 and 591.102.
In order to verify the stabilizing activity of the compounds having general formula (I) oz the present invention, differential thermal analysis was used, revealing the time necessary for starting up the oxidation reaction of the system.
F'or this purpose a non-stabilized polyol was used, of the type Glendion FG 3502 sold by EniChem S.p.A., and the stabilizer was added at levels of 0.15%.
The oxygen absorption induction time measurement was carried out on the polyol at a temperature of 130°C
and 140°C under a stream of oxygen. The greater the oxygen absorption induction time, the better is the stabilizing system used.
Proof of the good stabilizing capacity cf the compounds having general formula (I) of the present invention was provided by observing the oxygen absorp-tion induction time of the polyol to which the com-pounds having general formula (I) had been added, compared with the stabilizing capacity of the commer-cial product BHT, corresponding to 2,6-di-t-butyl-4-methylphenol, and with the polyol without stabilizers (see Example 7 below).
In addition, the importance of the molecular structure of the compounds having general formula (I) was demonstrated by comparing with an enamine having the formula (Compound Nr. 5, see Example 5 below):
N ~ N-H
CH
which . lacks the structure of the enamine double bond conjugated with the carbonyl double bond which is present, however, in the above compounds having general formula (I); and with an enamine having the forirula (Compound Nr. 6, see Example 6 below):
2 0 ~ CH3--C=CH--COOCHZCH3 C~8H3~--NH
which lacks the sterically hindered amine group.
Some illustrative but non-limiting examples are provided for a better understanding of the present invention and for its embodiment.
' Preparation of R-methoxyethylamine crotonate of 4-. (2,2,6,6-tetramethyl)piperidinyl (Compound Nr. i) having the following formula:
CH3--i =CH
CH3-p-CH2 CH2 -NI-I
24.13 g (0.1 moles) of 2,2,6,6-tetramethyl-4-pi-peridinyl-aceto-acetate, 24 g of toluene, 7.51 g (O.i moles) of 2-methoxyethylamine and 0.23 g of glacial acetic acid, are charged into a 250 ml four-necked reactor, equipped with a stirrer, thermometer and reflux condenser with a water separator.
The reaction mass is maintained under stirring and reflux heated for 4 hours, to a temperature ranging from 115°C to 118°C. During this period there is the formation of reaction water which is separated by azeotropic distillation: 1.5 g of reaction water are separated.
The solvent and acetic acid are removed by distil-lation and the raw residue thus obtained is subjected to fractionated distillation.
This distillation is carried out in a distiller consisting of a 100 ml boiler equipped with a thermome-ter, stirrer, column, condenser and device for the collection of fractions.
A central fraction containing 26.6 g of distilled product corresponding to Compound Nr. 1, is collected from the above distillation, operating under the following conditions:
- temperature at the head: 146'C-151°C;
- temperature of the boiler: 148°C-152°C~
- vacuum: 0.1 mm/Hg.
Compound Nr. 1 thus obtained, analyzed by gas-chromatography (GC), proves to be 97.5% pure, with a yield of about 89.2%.
Compound Nr. 1 is characterized by NMR analysis which confirms its enamine structure.
- 'H-NMR (200 MHz, CDC13-TMS) d (ppm): NH (broad) 8.50 ppm; C=CH (s) 4.34 ppm: the other signals are in accordance with the structure.
The other compounds (Compcunds Nr. 2-11) are prepared analogously to Example 1, of which only the reaction conditions and characteristics are specified.
Preparation of /3-(2,2,6,6,-tetramethylpiperidine-4-amino)ethyl crotonate (Compound Nr. 2) having the following formula: .
~5 CHI-C=CH-COOCH2CH3 NH
CH3 , 'CH3 CH3 N/ \CH3 H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: ethyl aceto-acetate;
26.03 g (0.2 moles).
l0 - Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.3 g - Duration and reaction temperature: 5 hours at 126°C-128°C.
- Distillation range: 118°C-133°C (head): i30°C-144°C (boiler); 0.10 mm/Hg - 0.15 mm/Hg (vacuum).
- Product obtained: 47.5 g.
- GC Purity: 98.9%.
- Yield: 88.4%
- ''H-NMR (200 MHz, CDC13-TMS) 6 (ppm) : NH (d) 8.39 ppm; C=CH (s) 4.35 ppm; the other signals are in accordance with the structure.
EXA1~PLE 3 Preparation of p-(2,2,6,6,-tetramethylpiperidine-4-amino) crotonate of 4-(2,2,6,6-tetramethyl)piperidinyl (Compound Nr. 3) having the following formula:
;. N-H
CH 'CH~
CH
CH
H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonylcompound:2,2,6,6-tetramethyl-4-piperidi nylaceto-acetate; 48.5 g (0.2 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.44 g - Reaction time and temperature: 3.5 hours at 114°C-128'C.
In this case the raw residue obtained is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature. When the crystallization is complete; the product obtained is filtered, washed with toluene and dried.
- Product obtained: 41.4 g.
- GC Purity: 98.9%.
- Yield: 54.4%
WO 98/47893 PG"T/EP98/02186 - 'H-NMR (200 MH2, CDC13-TMS) d (ppm): NH (d) 8.32 ppm; C=CH (s) 4.30 ppm; the other signals are in accordance with the structure.
- Melting point: 151°C.
Preparation of 2-(2,2,6,6-tetramethylpiperidine-4-amino)-2-pentane-9-one (Compound Nr. 4) having the following formula:
CH=-C=CH-COCH:
CH: ~ i ~ NCH:
CH
H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
62.5 g (0.4 moles).
- Carbonyl compound: acetylacetone; 40.05 g (0.4 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.6 g - 'Reaction water separated: 7.2 g - Reaction time and temperature: 4 hours at 120°C-138 ° C.
In this case the raw residue obtained is not subjected to fractionated distillation as the end-product crystallizes in the reaction medium at room temperature. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 71 g.
- GC Purity: > 99%.
- Yield: 83.6%
- 'H-NMR (200 MHz, CDC13-TMS) d (ppm) : NH (d) 10.48 ppm; C=CH (s) 4.60 ppm; the other signals are in accordance with the structure.
- Melting point: 103°C.
Preparation of 4-piperidino-2,2,6,6-tetramethyl-1,2,-5,6-tetrahydropyridine (Compound Nr. 5) having the following formula:
CH; CH3 N ~ N-H
Compound Nr. 5 is synthesized operating according to the procedure described by M. Dagonneau et al. in "Synthesis" (1984), page 902. The product obtained has a purity > 99%.
Preparation of J3-octadecylamino ethyl crotonate (Com-pound Nr. 6) having the following formula:
CH3--C=CH--COOCH2-CH3 ' C1sH37--NH
- Amine: octadecylamine; 53.9 g (0.2 moles).
- Carbonyl compound: ethyl acetoacetate; 26.03 g (0.2 moles).
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.5 g - Reaction time and temperature: 1 h 45' at 118°C-130°C.
The product is isolated as boiler residue after distillation under vacuum of the solvent and acetic acid.
- Product obtained: 75 g.
- GC Purity: 98.2%.
- Yield: 98.3%
- ~H-NMR (200 MHz, CDC13-TMS) 8 (ppm}: NH (broad) 8.53 ppm; C=CH (s} 4.40 ppm; the other signals are in accordance with the structure.
- Melting point: 40.5°C.
Preparation of (3-(2,2,6,6-tetramethylpiperidine-4-amino)t-butyl arotonate (Compound Nr. 7) having the following formula:
H3 C -.C-CH-COOC'CH3 NH
H3 C ~N 'CH3 - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
10 - Carbonyl compound: t-butyl aceto-acetate;
31.64 g (0.2 moles).
- Solvent:~toluene; 50 g.
- Catalyst: acetic acid; 0.3 g - Reaction water separated: 3.2 g 15 - Reaction time and temperature: 5 hours at 122°C-123°C.
- Distillation range: 142°C-162'C (head); 146°C-183°C (boiler); 0.10 mm/Hg - 0.15 mm/Hg (vacuum).
- Product obtained: 37.1 g.
20 - 'GC Purit~~: 91.6%.
- Yield: 62.6%
- Melting point: 86.7°C (solid at room temperature).
Preparation of (3-(2,2,6,6-tetramethylpiperidine-4-25 amino)octadecyl crotonate (Compound Nr. e) having the following formula:
H3 C-C=~-W a Ha ~
NH
C ~3 H3 C N ~3 - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
13.22 g (0.085 moles).
- Carbonyl compound: octadecyl aceto-acetate; 30 g (0.085 moles).
- Solvent: toluene; 25 g.
- Catalyst: acetic acid; 0.15 g - Reaction water separated: 1.21 g - Reaction time and temperature: 3 h 45' at 132°C-138°C.
In this case the raw reaction mass is not subject-ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera-ture. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 21.7 g.
- GC Purity: 99%.
- Yield: 51.8%
- Melting point: 53.7°C.
Preparation of 1-phenyl-1-(2,2,6,s-tetramethylpiperi-dine-4-amino)-2-benzoyl-ethylene (Compound Nr. 9) having the following formula:
-C=CH-NH
H
3C f a - Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
38.57 g (0.247 moles).
- Carbonyl compound: dibenzoyl methane; 44.85 g (0.2 moles) .
- Solvent: toluene; 50 g.
- Catalyst: acetic acid; 0.9 g - Reaction water separated: 4.8 g - Reaction time and temperature: 22 h at 159°C-163°C.
In this case the raw reaction mass is not subject-ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera-ture. When the crystallization is complete, the product obtained is filtered, washed with toluene and dried.
- Product obtained: 32.25 g.
- GC Purity: 92%.
- Yield: 44.5%
wo ~4~s93 pc~rriErr9sroms6 - Melting point: 99°C.
Preparation of ~-(2,2,6,6-tetramethyl-piperidine-4 ' amino)anilide crotonate (Compound Nr. io) having the following formula:
H3 ~.' r C~.i3 l0 ~C N
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: aceto-acetanilide: 35.44 g (0.2 moles) .
- Solvent: methanol; 100 g.
- Catalyst: acetic acid; 0.4 g - Reaction water separated: in this case the reac-tion water is not separated.
- Reaction time and temperature: 13 h at 20"C-26'C.
In this case the raw reaction mass is not subject ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera ture. When the crystallization is complete, the product obtained is filtered, washed with n-pentane and dried.
- Product obtained: 54.34 g.
S
- GC Purity: > 97%.
- Yield: 86.1%
- Melting point: 188°C.
Preparation of 1-methyl-1-(2,2,6,6,-tetramethyl-piperi-dine-4-amino)-2-benzoyl-ethylene (Compound Nr. 11) having the following formula:
H3 C_ C, ~'F~ -CO---~~
NH
to H3 C ~/ CH3 H3 C ~ N CHs H
- Amine: 4-amino-2,2,6,6-tetramethylpiperidine;
31.25 g (0.2 moles).
- Carbonyl compound: benzoylacetone; 32.44 g {0.2 moles) .
- Solvent: toluene; 100 g.
- Catalyst: acetic acid; 0.4 g - Reaction water separated: 3.2 g - Reaction time and temperature: 6 h at 118°C-120°C.
In this case the raw reaction mass is not subject ed to fractionated distillation as the end-product crystallizes in the reaction medium at room tempera ture. When the crystallization is complete, the product obtained is filtered, washed with n-pentane and dried.
- Product obtained: 50.2 g.
- GC Purity: > 98.5%.
- Yield: 83.5%
5 - Melting point: 112°C.
Stabilizing activity test of the Compounds having general formula (I) on polyol.
The oxidation kinetics of the polyol stabilized 10 with Compounds 1-11 prepared as described in Examples 1-11 above, are observed by differential thermal analysis at 130°C and at 140°C.
Inside the measurement capsule, the systems analyzed are brought in 5 minutes to the test tempera-15 ture under nitrogen. Oxygen is then passed (7 ml/h) and the oxidation kinetics are observed in relation to the heat developed during the process. The induction time is calculated in the intersection point with the time axis of the tangent at the oxidation curve at 1 mW as 20 illustrated in Figure 1: the abscissa indicates the time in minutes, the ordinate the trend of the heat developed in mW.
The addition of the polyol is obtained by mixing the polyol with the products to be analyzed, Compounds 25 1-11 and 2,6-di-t-butyl-4-methylphenol (BHT), in a S
quantity equal to 0.15%, the mixture being stirred until complete dissolution of the products used is obtained.
A non-stabilized polyol of the type Glendion FG
3501 produced and sold by EniChem S.p.A., is used as polyol.
Table 1 indicates the induction times in minutes of the oxygen absorption during the thermo-oxidation of the polyol at 130°C and at 140°C.
T~BLG 1 ~nti:.xidanta I:.duction tine Induction time i~
at 130C (min.) at 140C (min.) Polyol as it is 5 --Compound n 1 > 60 20.4 Compound n 2 > 60 20.7 Compound n 3 > 60 20.3 Compound n 4 > 60 21.2 Compound n 5 5.5 ~ -_ Compound n 6 ~ 5 --Compound n 7 > 60 20.5 Compound n 8 45.5 18.2 Compound n 9 > 60 23.0 Compound n 10 > 60 25.0 Compound n 11 > 60 23.5 BHT 29.3 9.7 The results shown in Table 1 clearly demonstrate a~;~~~lc~~~~ s~~~E-~ 57.
that, when the compounds having general formula (I), Compounds 1-4 and 7-11, are used, the oxygen absorption induction times in the thermo-oxidation of the polyol are considerably higher than those obtained by using BHT.
In addition, these results show that the com-pounds, such as Compound Nr. 5, in which tetramethylpi-peridine is present but not the enamine double bond conjugated with the carbonyl double bond, they are not capable of stabilizing the polyol. The same result is obtained using Compound Nr. 6 in which there is the enamine double bond conjugated with the carbonyl double bond but not tetramethylpiperidine.
~' . f', ~ ; a .
~~v ~.~,~.._
Claims (29)
1. An enamine derived from a .beta.-keto-ester, .beta.-keto-amine or 1,3-diketone, and a primary or secondary, aliphatic or aromatic amine, wherein the enamine comprises at least one sterically hindered amine group, and has one of the following general formulae (Ia) or (Ib):
wherein:
- m is an integer ranging from 1 to 3, - n is an integer ranging from 1 to 4, - R1 and R2 are the same or different, and represent a hydrogen atom; a linear or branched C1-C18 alkyl group;
a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group, a C7-C20 arylalkyl or alkylaryl group; a group having the general formula (V):
wherein R7 represents a hydrogen atom; a linear or branched C1-C18 alkyl group, said alkyl group being optionally substituted with a -NHR8 group or a -OR8 group wherein R8 represents a hydrogen atom, a linear or branched C1-C18 alkyl group, or a C6-C18 aryl group; a -OR9 group wherein R9 represents a hydrogen atom, or a linear or branched C1-C18 alkyl group;
- or R1 and R2, jointly with the nitrogen atom, represent a C5-C8 heterocyclic group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R1 is a triazine having one of the general formulae (II), (III) or (IV):
wherein R5 represents a hydrogen atom; a linear or branched C1-C18 alkyl group; a -NHR6 amine group or a -SR6 group wherein R6 represents a hydrogen atom or a linear or branched C1-C18 alkyl group;
- R3 and R4 are the same or different, and are a linear or branched C1-C18 alkyl group; a C6-C18 aryl group; a C7-C20 alkylaryl or arylalkyl group; a linear or branched C1-C8 alkoxy group;
- or R4 is a NR10R11 group wherein R10 and R11 are the same or different, and represent a hydrogen atom; a linear or branched C1-C18 alkyl group; a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group; a C7-C20 aryl-alkyl or alkylaryl group; a triazine having one of the following general formulae (II), (III) or (IV):
wherein R5 has the same meanings as defined above; a group having the general formula (V):
wherein R7 has the same meaning as defined above; or R10 and R11, jointly with the nitrogen atom, represent a C5-C8 heterocyclic group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R4 represents a group having one of the following general formulae (VII), (VIII) or (IX):
wherein R12 represents a hydrogen atom; or a linear or branched C1-C18 alkyl group; and R13 represents a linear or branched C1-C18 alkyl group; a -COCH2COCH3 group;
provided that at least one of R1 or R2 have the general formula (V).
wherein:
- m is an integer ranging from 1 to 3, - n is an integer ranging from 1 to 4, - R1 and R2 are the same or different, and represent a hydrogen atom; a linear or branched C1-C18 alkyl group;
a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group, a C7-C20 arylalkyl or alkylaryl group; a group having the general formula (V):
wherein R7 represents a hydrogen atom; a linear or branched C1-C18 alkyl group, said alkyl group being optionally substituted with a -NHR8 group or a -OR8 group wherein R8 represents a hydrogen atom, a linear or branched C1-C18 alkyl group, or a C6-C18 aryl group; a -OR9 group wherein R9 represents a hydrogen atom, or a linear or branched C1-C18 alkyl group;
- or R1 and R2, jointly with the nitrogen atom, represent a C5-C8 heterocyclic group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R1 is a triazine having one of the general formulae (II), (III) or (IV):
wherein R5 represents a hydrogen atom; a linear or branched C1-C18 alkyl group; a -NHR6 amine group or a -SR6 group wherein R6 represents a hydrogen atom or a linear or branched C1-C18 alkyl group;
- R3 and R4 are the same or different, and are a linear or branched C1-C18 alkyl group; a C6-C18 aryl group; a C7-C20 alkylaryl or arylalkyl group; a linear or branched C1-C8 alkoxy group;
- or R4 is a NR10R11 group wherein R10 and R11 are the same or different, and represent a hydrogen atom; a linear or branched C1-C18 alkyl group; a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group; a C7-C20 aryl-alkyl or alkylaryl group; a triazine having one of the following general formulae (II), (III) or (IV):
wherein R5 has the same meanings as defined above; a group having the general formula (V):
wherein R7 has the same meaning as defined above; or R10 and R11, jointly with the nitrogen atom, represent a C5-C8 heterocyclic group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur;
- or R4 represents a group having one of the following general formulae (VII), (VIII) or (IX):
wherein R12 represents a hydrogen atom; or a linear or branched C1-C18 alkyl group; and R13 represents a linear or branched C1-C18 alkyl group; a -COCH2COCH3 group;
provided that at least one of R1 or R2 have the general formula (V).
2. The enamine of claim 1, wherein R1, R2, R10 and R11 are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, metoxyethyl, 4-(2,2,6,6-tetramethyl)piperidinyl, 4-(2,2,6,6-tetrametyl)-1-butoxyethylpiperidinyl,4-(2,2,6,6-tetramethyl)-1-butoxypiperidinyl, 4-(2,2,6,6-tet-ramethyl)-1-methylpiperidinyl,3,5-dioctylamirotriazine,and 3,5-dibutylaminotriazine.
3. The enamine of claim 1, wherein the C5-C8 heterocyclic groups, in case R1 and R2 or R10 and R11, jointly with the nitrogen atom form a heterocyclic group, are selected from the group consisting of morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, and benzothiazolidine.
4. The enamine of claim 1, wherein R3 and R4 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl, oxyethyl, and oxybutyl.
5. The enamine of claim 1, wherein n is 2 and R4 is selected from the group comprising moieties with the following general formula:
6. The enamine of claim 1, wherein n is 3 and R4 is selected from the group of moieties represented by the following general formula:
7. The enamine of claim 1, wherein n is 4 and R4 is a moiety having the formula:
8. The enamine of claim 1, wherein R7 is selected from the group consisting of methyl, ethyl, propyl, butyl, ethoxy, butoxy, .beta.-hydroxyethyl, .beta.-methoxyethyl, .beta.-butoxyethyl, and methylaminoethyl:
9. The enamine of claim 1, wherein R5, R6, R8, R9, R12, and R13 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, and octyl.
10. The enamine of claim 1, consisting of .beta.-(2,2,6,6-tetrame-thylpiperidine-4-amino)ethyl crotonate.
11. The enamine of claim 1, consisting of 2-(2,2,6,6-tetrame-thylpiperidine-4-amino)-2-pentene-4-one.
12. The enamine of claim 1, consisting of .beta.-(2,2,6,6-tetrame-thylpiperidine-4-amino)t-butyl crotonate.
13. The enamine of claim 1, consisting of .beta.-(2,2,6,6-tetrame-thylpiperidine-4-amino)octadecyl crotonate.
14. The enamine of claim 1, consisting of 1-phenyl-1-(2,2,6,6-tetramethylpiperidine-4-amino)-2-benzoyl-ethylene.
15. The enamine of claim 1, consisting of .beta.-(2,2,6,6-tetrame-thylpiperidine-4-amino)anilide crotonate.
16. The enamines of claim 1, consisting of 1-methyl-1-(2,2,6,6-tetramethylpiperidine-4-amino)-2-benzoyl ethylene.
17. A process for the synthesis of the enamines of claim 1 comprising the reaction of 1-4 moles of a primary or secondary, aliphatic or aromatic amine, having the general formula (X):
HNR1R2 (X) wherein R1 and R2 have the same meanings as defined above, with 1-3 moles of a .beta.-keto-ester, a .beta.-keto-amide, or a 1,3-diketone having the general formula (XI):
wherein R3, R4 and n have the same meanings as defined above, in the presence of an inert organic solvent, at a temperature ranging from 60°C to 160°C, at atmospheric pressure, and for a time ranging from 0.5 to 24 hours.
HNR1R2 (X) wherein R1 and R2 have the same meanings as defined above, with 1-3 moles of a .beta.-keto-ester, a .beta.-keto-amide, or a 1,3-diketone having the general formula (XI):
wherein R3, R4 and n have the same meanings as defined above, in the presence of an inert organic solvent, at a temperature ranging from 60°C to 160°C, at atmospheric pressure, and for a time ranging from 0.5 to 24 hours.
18. The process of claim 17, wherein the organic solvent is a hydrocarbon.
19. The process of claim 18, wherein the hydrocarbon is toluene.
20. The process of claim 17, wherein the reaction temperature is between 115°C and 150°C.
21. The process of claim 17, wherein the reaction time is between 3 and 10 hours.
22. The process of claim 17, wherein acetic acid is added as a catalyst.
23. The process of claim 17, wherein the primary or secondary, aliphatic or aromatic amine having the general formula (X) as selected from the group consisting of cyclohexylamine, n-butylamine, tert-butylamine, n-octylamine, tert-octyl-amine, n-octadecylamine, n-dodecylamine, benzylamine, 2-me-thoxyethylainine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-2,2,6,6-tet-ramethyl-1-methylpiperidine, 4-amino-2,2,6,6-tetramethyl-1-butoxyethylpiperidine, and 1-amino-3,5-dioctylaminotriazine.
24. The process of claim 17, wherein the .beta.-keto-esters, .beta.-keto-amides, or 1,3-deketones having the general formula (XI) are selected from the group consisting of ethyl aceto-acetate, t-butyl aceto-acetate, octadecyl aceto-acetate, ethyl benzoylacetate, acetylacetone, benzoylacetone, dibenzoyl methane, p-toluylacetone, 4-(2,2,6,6-tetramethyl)piperidi-nylaceto-acetate, N-methyl-4-(2,2,6,6)-tetramethyl)piperi-dinylaceto-acetate, aceto-acetamide, acetoacetanylide, aceto-acet-4-(2,2,6,6-tetramethylpiperidine)amide, and aceto-acet-(3,5-dibutyltriazine)-1-amide.
25. A polymeric composition containing an organic polymer and an effective quantity of one or more of the compounds of claim 1.
26. The polymeric composition of claim 25, wherein the compounds having the general formula (Ia) or (Ib) are combined with other stabilizers.
27. The polymeric composition of claim 26, wherein the organic polymer is selected from polyols.
28. An end-article obtained from the processing of the polymeric compositions of any of the claims 25-27.
29. Use of an enamine according to any of the claims 1-16 as antioxidant for organic polymers.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI97A000902 | 1997-04-18 | ||
| IT97MI000902 IT1291599B1 (en) | 1997-04-18 | 1997-04-18 | COMPOUNDS BELONGING TO THE ENAMINE CLASS AND THEIR USE AS ANTIOXIDANTS FOR ORGANIC POLYMERS |
| PCT/EP1998/002186 WO1998047893A1 (en) | 1997-04-18 | 1998-04-16 | Enamine derivatives for use as antioxydants for polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2282329A1 true CA2282329A1 (en) | 1998-10-29 |
Family
ID=11376941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002282329A Abandoned CA2282329A1 (en) | 1997-04-18 | 1998-04-16 | Enamine derivatives for use as antioxydants for polymers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0975626A1 (en) |
| JP (1) | JP2001523238A (en) |
| CA (1) | CA2282329A1 (en) |
| IT (1) | IT1291599B1 (en) |
| WO (1) | WO1998047893A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10124332A1 (en) | 2001-05-18 | 2002-11-21 | Basf Ag | Cosmetic or pharmaceutical preparations containing enaminotriazines as light stabilizers and new enaminotriazines |
| WO2003096991A2 (en) | 2002-05-17 | 2003-11-27 | Othera Pharmaceuticals, Inc. | Amelioration of the development of cataracts and other opthalmic diseases |
| US7825134B2 (en) | 2003-05-19 | 2010-11-02 | Othera Holding, Inc. | Amelioration of cataracts, macular degeneration and other ophthalmic diseases |
| US8188166B2 (en) * | 2005-07-29 | 2012-05-29 | Aoc, Llc | Unsaturated polyester resin compositions with improved weatherability |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS557861B2 (en) * | 1972-10-04 | 1980-02-28 | ||
| DE2612314A1 (en) * | 1976-03-23 | 1977-09-29 | Bayer Ag | PIPERIDE DERIVATIVES AS LIGHT PROTECTION AGENTS |
| DE2849444A1 (en) * | 1978-11-15 | 1980-05-29 | Hoechst Ag | Piperidyl ester(s) of beta-amino crotonic acid - for stabilisation of polymers against light, heat and oxygen |
| CH666028A5 (en) * | 1985-08-27 | 1988-06-30 | Vladimir Ivanovich Paramonov | 2,2,6-6-TETRAMETHYLPIPERIDYLAMIDES OF SUBSTITUTED CARBONIC ACIDS AND THE LIGHT-RESISTANT POLYMER BLENDS STABILIZED WITH THEM. |
| IT1217742B (en) * | 1988-05-31 | 1990-03-30 | Ciba Geigy Spa | POLYAMINES PARTIALLY REPLACED WITH PIPERIDIN TRIAZINE |
-
1997
- 1997-04-18 IT IT97MI000902 patent/IT1291599B1/en active IP Right Grant
-
1998
- 1998-04-16 WO PCT/EP1998/002186 patent/WO1998047893A1/en not_active Application Discontinuation
- 1998-04-16 CA CA002282329A patent/CA2282329A1/en not_active Abandoned
- 1998-04-16 EP EP98922711A patent/EP0975626A1/en not_active Withdrawn
- 1998-04-16 JP JP54495498A patent/JP2001523238A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998047893A1 (en) | 1998-10-29 |
| ITMI970902A1 (en) | 1998-10-18 |
| IT1291599B1 (en) | 1999-01-11 |
| EP0975626A1 (en) | 2000-02-02 |
| JP2001523238A (en) | 2001-11-20 |
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| WO2000008096A1 (en) | Stabilizing mixture having a melting point lower than that of the highest melting component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |