The B. F. Goodrich Company

Pyong N Son

John T Lai

George Kletecka

Robert W Layer

Ronald M Kovach

An oxo-piperazinyl triazine with three piperazinone substituents, each of which has an alkylated N.sup.4 atom ('MPIP-T'), used in an amount no more than 0.2 phr, and without any secondary stabilizer (hence referred to as a 'virgin MPIP-T'), and in particular, without any hindered phenol antioxidant, or phosphorous acid ester, simultaneously provides thermooxidative stability and stability against degradation by UV light along with acceptable melt processability. Further, the virgin MPIP-T allows (i) uninterrupted operation of a die or mold while maintaining the surfaces of the cavities essentially contaminant-free; and, (ii) excellent AO stabilization which is equivalent to that obtained with a premier hindered phenol AO, and superior to that obtained with the premier oligomeric piperidinyl-triazine compound, when each stabilizer is used in the same amounts by weight in a thermoplastic synthetic resinous substrate.

Thermooxidative stabilization of polymers with a N4-alkylated

N-substituted, N-(polysubstituted-4-piperidinyl)-.alpha.-(3,5-dialkyl-4-hydroxyphenyl)-.a lpha., .alpha.-disubstituted acetamide ('3,5-DHPIPA') generates an exceptionally stable hindered acetamide aroxyl radical which is far more stable than the 'blue aroxyl radical' derived from 2,4,6-tri-tert-butyl-phenol, which radical was heretofore adjudged the standard of superior stability and resistance to degradation due to heat, oxygen and light, the compound having been specifically disclosed as a uv-stabilizer. The hindered aroxyl amide radical which is at least ten times more stable than the 'blue aroxyl radical' heretofore deemed stable, may be generated by 3,5-DHPIPA compounds prepared by a peculiarly effective synthesis known as the ketoform reaction. This ketoform reaction is unexpectedly well-adapted to produce the 3,5-DHPIPA compounds which we have been unable to produce by any other synthesis known to us. The stability of the hindered aroxyl amide radical inculcates an organic material in which a 3,5-DHPIPA compound is dispersed, with excellent stability. The use of a combination of 3,5-DHPIPA compounds, or a combination of a 3,5-DHPIPA compound with with known stabilizers, particularly the phosphites and benzophenones, in a small but stabilizing amount, provides especially effective stabilization in polyolefins and a host of other synthetic resinous materials.

N,N-disubstituted,

A staged process is disclosed for forming a tri-substituted triazine ring in which the substituents are cyclic amines referred to as hindered amines. A prior art process for making such amines in a reaction mixture of aqueous and organic phases has been modified to produce a stabilizer with desirable whiteness, at the same time avoiding the loss of the cyclic amine reactant which is water-soluble. Conversion of the amine to yield at least 90% of the tri-substituted product having at least 90% purity allows the reaction to be commercially significant despite the high cost of the reactants. The staged process is preferably conducted in two sequences in two reactors, with an intermediate step in which the aqueous saline and basic solution from the first sequence is withdrawn. In the first sequence, a mono-chloro intermediate ('MCI') is formed at ambient temperature, but below 100.degree. C. to yield a colored solution. Flowing only the organic phase to the second reactor which must be pressurized, allows use of an economical reactor. In the second sequence, preferably in a separate reaction zone, reacting 3 moles of MCI with no more than 3.5 moles of a third amine, yields the tri-substituted product which is formed at below 200.degree. C. but in excess of 125.degree. C. Only a small portion of the molar excess of amine used in the second sequence need be discarded. The time required to run the reaction in two stages is less than required to run it in a single sequence. Further saving in time is effected by using a phase transfer catalyst.

Process for the manufacture of a tri-substituted triazine stabilizer

Excellent stabilization of pigmented polypropylene (PP) fiber against gas fade upon exposure to atmospheric pollutants is obtained with a hindered amine containing a polysubstituted piperazin-2-one (PSP) moiety, for example, a C.sub.2 -C.sub.12 alkylene connecting two PSP moieties, or a trisubstituted triazine ring with three PSP substituents, or a polyalkylene polyamine having pendant substituted oxo-piperazinyl-traizine moieties (PIP-T), that is, having pendant triazine rings substituted with PSP substituents. The stabilizers are unexpectedly effected when used without an antioxidant which produces yellowing, if used. Either pigmented or unpigmented PSP-stabilized PP fibers, and particularly fibers pigmented with white or pastel dyes, and having a non-alkaline 'finish' are especially benefitted. Fibers made from PP stabilized with such a hindered amine, but lacking conventional antioxidants, have improved gas fade resistance, compared to fibers made from PP stabilized with several other commercially available hindered amines tested, including those which contain heterocyclic amines which are not PSPs, and especially those amines containing a hindered phenol moiety.

Stabilized pigmented polypropylene fiber resistant to gas fade

N-substituted, N-(polysubstituted-4-piperidinyl)-.alpha.-(3,5-dialkyl-4-hydroxyphenyl)-.a lpha.,.alpha.-disubstituted acetamide ('3,5-DHPIPA') generates an exceptionally stable hindered acetamide aroxyl radical which is far more stable than the 'blue aroxyl radical' derived from 2,4,6-tri-tert-butyl-phenol, which radical was heretofore adjudged the standard of superior stability and resistance to degradation due to heat, oxygen and light, the compound having been specifically disclosed as a uv-stabilizer. The hindered aroxyl amide radical which is at least ten times more stable than the 'blue aroxyl radical' heretofore deemed stable, may be generated by 3,5-DHPIPA compounds prepared by a peculiarly effective synthesis known as the ketoform reaction. This ketoform reaction is unexpectedly well-adapted to produce the 3,5-DHPIPA compounds which we have been unable to produce by any other synthesis known to us. The stability of the hindered aroxyl amide radical inculcates an organic material in which a 3,5-DHPIPA compound is dispersed, with excellent stability. The use of a combination of 3,5-DHPIPA compounds, or a combination of a 3,5-DHPIPA compound with known stabilizers, particularly the phosphites and benzophenones, in a small but stabilizing amount, provides especially effective stabilization in polyolefins and a host of other synthetic resinous materials.

N-(substituted)-1-(piperazinealkyl)-.alpha.-(3,5-dialkyl-4-hydroxyphenyl)-. alpha.,.alpha.-disubstited acetamides, are novel compounds prepared by a novel modification of the ketoform process. The compounds are useful as stabilizers for organic materials subject to degradation in an environment in which the materials are exposed to heat, oxidation and light, particularly ultraviolet light. The compounds are especially useful in combination with known secondary stabilizers.

A branched chain polyalkylenepolyamine ('PAPA') amine having plural amine groups including a secondary amine group intermediate terminal primary amine groups and having at least two carbon atoms between each amine group, is reductively alkylated with a ketone to provide a PAPA alkylated only at an unhindered primary amine group. A preselected degree of steric hindrance at amine groups near each end of the chain enables cyclization by the `ketoform synthesis` by reaction with a ketone in such a manner as to form a polysubstituted piperazinone ('PSP') ring which includes N atoms of proximate primary and secondary amine groups of the alkylated PAPA. The PSP so formed may then be reacted with a reactive triazine ring so that a PSP substituent is linked to the triazine ring through a single N atom and at least two C atoms, to form a 2-oxo-piperazinyl-triazine ('PIP-T'). Oligomers of the PIP-T may be prepared. The PIP-T compounds are excellent stabilizers against ultraviolet (uv) light degradation in light-sensitive synthetic resinous materials. In combination with particular hindered phenols PIP-T compounds are found to provide better antioxidant properties than that obtained as the theoretical additive effect of the PIP-T and the hindered phenol, separately.

Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines

A nitroamine is formed from an aliphatic amine reactant + a nitroalkane + an aldehyde with better conversion, and faster, if the aldehyde is added last, and gradually, so as not to form an alkanolamine intermediate with the aldehyde as in the prior art reactions. In particular, a diamine such as ethylene diamine (EDA) has the unique ability, even among diprimary amines, to react with nitroalkane, to form a salt intermediate to which is added an essentially solvent-free aldehyde such as paraformaldehyde to produce a reaction product consisting essentially of a mixture of (i) a mononitrodialkylenediamine with a disubstituted N-adjacent terminal C atom and (ii) a dinitrotrialkylenediamine with each N-adjacent terminal C atom being disubstituted; and the mixture is obtained in an yield of at least 90 mol %.

Synthesis of polyamines and mixture formed thereby, of diprimary

A polyalkylenepolyamine ('PAPA') main chain having pendant substituted 2-oxo-piperazinyl-triazines attached to the N atoms of the PAPA main chain are novel compounds which have highly desirable UV-light stabilizing (UV-S) activity coupled with unexpectedly good thermal stability. These compounds, referred to as 'pendant piperazinyl triazines' or P[PIP-T] for brevity, are used in polymer recipes to formulate a stabilized polymeric composition comprising a light-degradable organic polymer containing an effective amount of a P[PIP-T] sufficient to stabilize the polymer. A P[PIP-T] is especially effective in a polyolefin in which there is from about 0.1 percent by weight (% by wt), to about 5% by wt, and is also effective in a wide variety of pastel colored and/or transparent commercially significant polymers.

Polyalkylenepolyamine having pendant substituted

A particular branched chain polyalkylenepolyamine ('PAPA') having plural amine groups including a secondary amine group intermediate terminal free primary amine groups (that is, neither one is hindered), and having at least two C atoms between each group, may be selectively cyclized with a ketoform reaction to form a polysubstituted piperazinone ('PSP'), with specific directivity. Such PSPs are linked to a triazine nucleus to yield piperazinone-triazine ('PIP-T') compounds which are excellent stabilizers for polyolefins and other light-degradable polymers. Certain acyclic polyalkylenepolyamines may have a PIP-T substituent at each N atom forming pendant PIP-Ts ('P[PIP-T]' for brevity) which are also excellent stabilizers, and like some of the PIP-Ts, some P[PIP-T]s provide photostabilization without noticeably interfering with the color of films and fibers provided by even pastel-colored pigments and dyes.

Substituted oxo-piperazinyl-triazines and UV light stabilized

A branched chain polyalkylenepolyamine ('PAPA') amine having plural amine groups including a secondary amine group intermediate terminal primary amine groups and having at least two carbon atoms between each amine group, is reductively alkylated with a ketone to provide a PAPA alkylated only at an unhindered primary amine group. A preselected degree of steric hindrance at amine groups near each end of the chain enables cyclization by the `ketoform synthesis` by reaction with a ketone in such a manner as to form a polysubstituted piperazinone ('PSP') ring which includes N atoms of proximate primary and secondary amine groups of the alkylated PAPA. The PSP so formed may then be reacted with a reactive triazine ring so that a PSP substituent is linked to the triazine ring through a single N atom and at least two C atoms, to form a 2-oxo-piperazinyl-triazine ('PIP-T'). Oligomers of the PIP-T may be prepared. The PIP-T compounds are excellent stabilizers against ultraviolet (uv) light degradation in light-sensitive synthethic resinous materials.

A branched chain polyalkylenepolyamine ('PAPA') amine having plural amine groups including a secondary amine group intermediate terminal primary amine groups and having at least two carbon atoms between each amine group, is reductively alkylated with a ketone to provide a PAPA alkylated only at an unhindered primary amine group. A preselected degree of steric hindrance at amine groups near each end of the chain enables cyclization by the `ketoform synthesis` by reaction with a ketone in such a manner as to form a polysubstituted piperazinone ('PSP') ring which includes N atoms of proximate primary and secondary amine groups of the alkylated PAPA. The PSP so formed may then be reacted with a reactive triazine ring so that a PSP substituent is linked to the triazine ring through a single N atom and at least two C atoms, to form a 2-oxo-piperazinyl-triazine ('PIP-T'). Oligomers of the PIP-T may be prepared. The PIP-T compounds are excellent stabilizers against ultraviolet (uv) light degradation in light-sensitive synthetic resinous materials.

Novel polysubstituted 2-keto-1,4-diazacycloalkanes are powerful stabilizers for materials subject to ultraviolet (UV) light degradation, particularly for polyolefins. The cyclic 2-keto compounds of this invention have (a) a fixed two-carbon bridge between the N.sup.1 and N.sup.4 atoms of the diaza ring, the remaining portion of the ring having a variable length bridge of two or more carbon atoms, (b) and N-adjacent carbonyl in the fixed two-carbon bridge, and (c) at least one N.sup.4 -adjacent carbon atom of the diaza ring is polysubstituted, that is, has two substituents which may be cyclizable. Compositions containing (a) the polysubstituted 2-keto-1,4-diazacycloalkanes of this invention, and (b) prior art polysubstituted 2-keto-1,4-diazacycloalkanes, exhibit excellent stability to UV light.

Substituted 2-keto-1,4-diazacycloalkanes

Novel compounds have been discovered in which a bis compound of a polysubstituted 2-keto-1,4-diazacycloalkane ('2KDZC') provides a bridge between diisocyanate groups so as to form an oligomeric 2KDZC-urethane ('2K-U' oligomer) having from 2 to about 15 repeating units. The bis compound bridge itself consists essentially of two distally linked polysubstituted 2KDZC moieties, and the 2K-U oligomer formed consists essentially of two 2KDZC moieties linked through their N.sup.1 atoms, which moieties in turn are distally linked to urethane groups through the N.sup.4 atoms of the 2KDZC. Such 2K-U oligomers unexpectedly contain a self-limiting number of 2K-U repeating units which happens to provide 2K-U oligomers which are desirable and highly effective u-v light stabilizers in organic materials. More specifically, this invention provides a novel class of polymeric hindered amine-urethane derivatives, particularly piperazinone bis compounds which may be distally linked to each other in a single step reaction utilizing an appropriately substituted diamine, a haloform such as bromoform or chloroform, in one of several known syntheses for making 2-keto-diazacycloalkanones, some of which syntheses may preferably utilize a phase transfer catalyst. This bis compound may then be hydroxyalkylated and reacted with an appropriate diisocyanate.

2-Keto-diazacycloalkane-urethane oligomers and U-V light stabilized

Novel compositions which are highly stable and resistant to degradation by ultraviolet (UV) light are prepared by dispersing polysubstituted 1,5-diazacycloalkanes in the material subject to degradation, particularly in polyolefins. The cyclic compounds of this invention have (a) a fixed three-carbon bridge between the N.sup.1 and N.sup.5 atoms of the diaza ring, the remaining portion of the ring having a variable length bridge of two or more carbon atoms, (b) an N-adjacent carbon atom of the diaza ring is polysubstituted, that is, has two substituents which may be cyclizable. Monocyclic 1,5-diazacycloalkanes are prepared by reducing the corresponding 2-keto-1,5-diazacycloalkane with metal hydride; bicyclic 1,5-diazacycloalkanes, particularly fused ring bicyclic compounds such as substituted 1,5-decahydrobenzodiazepines are prepared by reaction of a diaminocycloalkane with an unsaturated ketone or acid and reducing with metal hydride.

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Akron, OH, United States of America

Pyong N Son