The B. F. Goodrich Company

E.i. Dupont De Nemours and Company

Pyong-Nae Son

John T Lai

George Kletecka

Robert W Layer

Charles P Jacobs

Peter Smith

Leonard E Kosinski

Ronald M Kovach

Victor L Ledesma

A branched chain polyalkylene polyamine ('PAPA') having plural amine groups, including a secondary amine group intermediate terminal primary amine groups one of which is hindered, and having at least two carbon atoms between each group, is selectively reductively alkylated with a ketone. The reaction provides a convenient method for selectively reductively alkylating a PAPA having a hindered primary amine group, the method comprising contacting the PAPA with hydrogen and the ketone in the presence of a catalytically effective amount of a Group VIII metal on a catalyst support, at a pressure in the range from about 500-1000 psi and a temperature in the range from about 50.degree. C. to about 200.degree. C. for a period of time sufficient to preferentially alkylate the unhindered amine primary terminal amine group. The alkylation proceeds essentially without alkylating either the sterically hindered terminal primary amine group or the intermediate unhindered secondary amine group.

Process for making alkylated polyalkylenepolyamines by selective

Excellent color stabilization as well as fiber integrity is obtained in bright sunlight at relatively high temperature, in polyolefin (PO) articles pigmented with red, yellow, and orange azo and disazo pigments, by combining the pigment with two `large molecule` primary stabilizers, the first an oxo-piperazinyl-triazine based (PIP-T) hindered amine light stabilizer (HALS), and the second, a 3,5-disubstituted-tert-butyl-4-hydroxybenzoate (3,5-DHBZ). The first contains at least two polysubstituted piperazinone rings in its molecule; the second is a hindered phenol with an ester group in the para- position. Stabilization of the PO's color is obtained for as long as the PO articles themselves are stabilized by the combination of primary stabilizers. With the combination, the pigmented articles are not only thermooxidatively and light-stabilized, but there is exceptionally low color fade. Because fibers may be extruded twice for better distribution of pigment, a small amount, no more than 0.1 phr of secondary melt-stabilizers, may be used. Blue- green- red- orange- and yellow-pigmented PO articles exhibit less than a .+-.3 change in color (color fading) due to degradation of the pigment, over the useful life of the articles, or a period of exposure resulting in absorption of 1240 Kjoules. Such exposure of pigmented articles, deemed equivalent to normal outdoor use over a period of more than 10 years, results in essentially no visible loss of color due to degradation of the pigment.

Multi-component stabilizer system for polyolefins pigmented with azo and

A process for methylating the N.sup.4 atom of a polysubstituted piperazine or piperazin-2-one ('PSP') is effective despite using a much smaller molar excess of formaldehyde and formic acid than dictated by a conventional Eschweiler-Clarke reaction. Particularly in a complex amine in which the PSP substituent is connected to a triazine ring which in turn may be connected to a N atom of an acyclic polyamine, the molar ratio of NH groups:HCHO:HCOOH is in the range from about 1:1:1 to 1:1.5:1.5, the amount of HCHO and HCOOH being sufficient to methylate at least the &gt;NH groups of said PSP substituent if the complex amine contains terminal --NH groups. The same range of molar ratio is maintained when the total number of NH groups to be methylated includes the terminal --NH groups. The effectiveness of the process is attributed to use of an alkylbenzene solvent in which reaction with only a slight excess of HCHO and HCOOH proceeds apace, and in which solvent the methylated product remains dissolved.

Process for methylating a hindered nitrogen atom in an inert non-aqueous

Alkylated polyalkylene polyamines and process for selective alkylation

A stabilizer compound for synthetic resinous materials is a tri-substituted triazine in which each substituent is a N.sup.4 -methylated 2-keto-1,4-diazacyclohexane connected to the triazine ring through an alkylene bridge. This bridge permits efficient methylation of the N.sup.4 atom in every substituent under conditions which yield crystals having at least 90% purity. These crystals may be further purified to at least 95% purity at which purity level they contain less than 500 ppm ash. The stabilization effect of 95% pure compound in a polyacetal is such that, even with an ash content of 50 ppm, it has better stabilization properties than its 99.2% pure precursor (the non-methylated tri-substituted triazine) with an ash content of 10 ppm, as evidenced by lower formaldehyde evolved and better color retention, that is, developing less color in a water white sample after testing at 259.degree. C.

Alkylated oxo-piperanzinyl-triazine

Certain polysubstituted piperazinones (PSP) having two or three methylene groups linking the N.sup.1 atom of the ring to the N atom of a terminal amine group, are found to be peculiarly prone to decomposition when subjected to elevated temperature after being contacted with water, and sensitive to the amount of base used in the base-induced ketoform reaction which generates the PSP represented by the structure ##STR1## These PSP are therefore produced by a modification of the ketoform reaction under essentially anhydrous conditions, using enough ketone to dissolve the PSP formed and a molar ratio of solid alkali metal hydroxide/diamine reactant in the range from at least 5 but less than 7. The PSP produced is recovered as a solution in the ketone, without contacting the PSP with water. The PSP product obtained after the ketone is distilled, is essentially pure.

Process for desensitizing a 1-(alkylamino)alkyl-polysubstituted

Excellent stabilization of polypropylene (PP) 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 polyalkylene polyamine having pendant substituted oxo-piperazinyltriazine moieties (PIP-T), that is, having pendant triazine rings substituted with PSP substituents. The stabilizers are particularly effective for PP irradiated with high energy gamma-radiation. Irradiated articles made from PP stabilized with such a hindered amine have improved strength and discoloration resistance, compared to articles made from polymer stabilized with several other hindered amines tested, particularly the 2,2,6,6-tetramethyl-4-piperidyl sebacate.

Stabilized gamma-irradiated polypropylene and sterilizable articles

A bis-polysubstituted piperazinone ('bis-PSP') in which two PSP moieties are closely coupled through an ethylene linkage, may be esterified so as to incorporate particular moieties in a macromolecule which may have only one bis-PSP unit, or may be esterified to form an oligomer having plural esterified bis-PSP repeating units. The macromolecule not only exhibits excellent UV-stabilization and antioxidant properties in synthetic resinous materials thus performing a highly effective dual function, but also is resistant to extraction with solvents, particularly polar solvents.

1,2-ethanediyl-bis-2-piperazinone esters, oligomers thereof, and

Novel piperazinones having the formula ##STR1## are useful UV stabilizers and are purified by fractional distillation in the presence of an inorganic base.

Purification of 1-(2-amino-2-alkylpropyl)-3,3,5,5-tetraalkylpiperazinones

Novel hindered 2-keto-1,4-diazacycloalkane-triazine oligomers having the general formula ##STR1## are useful antioxidants and UV stabilizers for various polymers.

Hindered 2-keto-1,4-diazacycloalkane oligomers containing triazine rings

Oligomeric amides having the general structure ##STR1## are useful as stabilizers for polymers and are prepared in a one-step synthesis by reacting a suitable amine with an appropriate ketone and chloroform.

Oligomeric amides as synergists for antioxidants and UV stabilizers

Disclosed are stabilizer compounds of the formula: ##STR1## wherein R.sup.1, R.sup.3 and R.sup.6 are independently selected from the group consisting of alkyl of 1-8 carbon atoms, aryl, cycloalkyl, and alkalene of 2-6 carbon atoms;

Substituted 2-keto-1,4-diazacycloalkanes

Oligomeric alkylenebisphenyl phenylphosphonites, easily prepared by the reaction of phenyldichlorophosphine and certain bis-phenols in the presence of a base, provide enhanced stabilizing activity to hydroxyalkyleneyl isocyanurates when combined to stabilize organic materials subject to degradation. These oligomeric phenylphosphonites are not expensive, resist hydrolysis, do not evaporate from or are leached out of polymers when mixed therewith and provide excellent protection to polymers during processing and result in decreased water carry over of polymer films on leaving a cooling water bath during the film forming process.

Oligomeric phenylphosphonites

Process for the selective reductive alkylation of a cyclic diamine by catalytic condensation of the cyclic diamine with a hetercyclic ketone. In the process described herein, the reaction conditions and catalyst which are selected are directive for the synthesis of the N,N' substituted cyclic diamine. The compounds produced according to this procedure are readily isolated and are effective as UV stabilizers.

High molecular weight piperidine derivatives as UV stabilizers

Novel substituted decahydroquinolines are prepared and used as ultraviolet (UV) light stabilizers for materials subject to UV light degradation, particularly for polyolefins. Compositions containing the decahydroquinoline compounds exhibit excellent stability to UV light.

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Akron, OH, United States of America

Pyong-Nae Son