CA1195329A - Alkylated polyalkylenepolyamines substituted oxo- piperazinyltriazines and uv light stabilized compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
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.

Description

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ALKYLATED POLYALKYLENEPOLYAMINES, SUBSTITUTED OXO-PIPERAZINYL-TRIAZINES
AND UV LIGHT STABILIZED COMPOSITIONS
BACKGROUND OF 1'HE INVENTION
Organic materials, whether natural or synthetic, are conventionally protected against degradation by ultraviolet (UV) light by incorporating a UV
light stabilizer in the material. Many classes of compounds are known to be useful UY light stabilizers, some being more effective than others. Particul-arly effective 2-keto-diazacyeloalkanes which provide stabilized compositions 10 resistant to degradation by UV light, include the 2-keto-1,4-diazacycloalkanes disclosed in U.S. Patent No. 4,190,571; and, the 2-keto-1,5-diazacycloalkanes disclosed in U.S. Patent No. 4,207,228. Other 2-keto-diazacycloalkanes useful as U~ light stabilizers are diselosed in U.S. Patent Nos. 3,319,234;
3,9209659; and 3,928,330 which teach substituted piperazinediones. Cycloalk-15 anes useful as UV light stabilizers are disclosed in Ger. Offen. 2,315,042;
Japanese Patents Nos~ 7,453,571 and 7,453,5~2.
The compounds of this invention belong to a well-recognized chemical elass of ultraviolet light stabilizers. They are multi-ringed triaæine derivatives. Compounds of this class include piperidinyl-triazine derivatives 20 such as are disclosed in U.S. Patent No. 4,263,434 (hereafter "'434" for brevity) and French Patent No. 2181 059, each of which describe the preparation of monoaza ring substituents linked to a triazine ring, and teach the particular use of these derivatives as light stabilizers in polyolefins.
However, the compounds of the French patent are known to have 25 poor resistance to extraction with an aqueous solvent which appears to be a characteristic of this class of compounds. The compounds of the '434 patent are known to have overcome, for the most part, such a disadvantage, presumably because of the particular linking of the piperidinyl substituents to the triazine ring. In addition to the different linking ~O~ ps9 compared with 30 those of the French compounds, the '434 compounds include a single piperazine ring substituent, not part OI a repeating unit, which is direetly bonded to the triazine ring, that is, without any linking groups. Moreover, though substituted piperazinones are known to be eflectiYe s~abilizers, there is no suggestion that linl;ing such a piperazinone throug}l at least a three-35 atom chain o~ one N (nitrogen) atom and at least two C (carbon) atoms to a ~f~Q, ~. L~35~

triazine ring, might impart compositions containing such distally linkedpiperazinone substituents exceptional properties, including ~astness to extra-ction with aqueous solutions.
The concept of structurally changing the nature of the linking group 5 in multi-ringed triazine deri~atives, arld changing the struGture of rings to which the triazine ring is linked, initiated the search for effective triazine-based ~ompounds. The heretofore unknown effectiveness of (a) reductive alkylation of a branched chain polyalkylenepolyamine ("PAPA") with a ketone, and (b) the ketoform reaction to preferentially cyclize proximate primary and 10 secondary amine groups in alkyla~ed PAPA which contain a stericaLly tailored hindered primary amine group which is nevertheless reactive, permitted the implementation of the concept. Testing the compounds as stabilizers in various synthetic resins, and particularly in polyolefins, proved that a substituted piperazinone linked to a triazine ring through one N atom and at 15 least two C atoms (hsnce "distally linked"), yields effective stabilizers.
The present invention is particularly directed to ~a) novel alkylated PAPA, (b) a novel synthesis for the alkylated PAPA, (c) novel uv light stabilizers classed as hindered amine-triazines, more specifically 2-oxo-piperazinyl-triazine ("PIP-T") derivatives, (d) novel syntheses for the PIP-T
20 derivatives, and (e) novel compositions in which 2-020-piperazinyl-triazine derivatives are incorporated. The novel PIP-T compounds have at least one substituted piperazinone substituent which is distally linked to a triazine ring, and when, in addition7 a piperidinyl, piperazinyl or other substituent is directly linked to the triazine ring, the piperidinyl, piperazinyl or other 25 substituent may become part of a repeating unit. It is to this difference in structure to which the effectiveness of these compounds is attributed.
The reductive alkylation of polyalkylenepolyamines ("PAPA") is well known and described with numerous examples in the chapter entitled "Preparation of Amines by Reductive Alkylation" by W. S Emerson in 30 Reactions, Vol 4, John Wiley & Sons, New York, N.Y. However there is no teaching that reductive alkylation may result in alkylation only at a particular primary amino group to the exclusion of all other amino groups, such result being obtained with a PAPA only by hindering one of the two primary amine groups and reacting with a ketone.

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The synthesis of the novel stabilizers of this invention is facilitated by the peculiar action of certain onium salts in an aqueous alkaline mediurn, which action facilitates the interaction of an amine nucleophilic agent such as a primary or secondary amine7 with chloroform or other trichloromethide 5 generat;ng agent, and a ketone or aromatic aldehyde. The organic onium salts of nitrogen, phosphorus and sulfur are weU known. They are ionized in aqueous solutions to form stable eations. Certain onium salts have provided the basis for phase transfer catalysis in a wide variety of reactions, a recent and comprehensive review of which is contained in Angewandte Chemie, 10 International Edition in English9 16 493-558 (August 1977). Discussed therein are various anion transfer reactions where the onium salt exchanges its original anion for other anions in the aqueous phase. These ion pairs can then enter a water immiscible, organic liquid phase, making it possible to carry out chemistry there with the transported anion, including OH ions. Many 15 reactions involving water immiscible solutions of various simple organic molecules have been described. Though the use of phase transfer catalysts facilitate the cyclization of an appropriately sterically hindered branched chain amine having proximate primary and secondary amine groups amsngst plural amine groups in the chain, the reaction has also been found to proceed, 20 though relatively slowly, by simply using a large excess of the ketone or aromatic aldehyde either of which is the the essential carbonyl containing compound which contributes the carbonyl group to the 2-position of the diazacycloalkane ring.
A phase transfer catalyzed reaction known as the "ketoform 25 reaction" is diselosed in U.S. Patent No. 4,167,5129 which proceeds by virtue of a phase transfer catalyzed reaction mechanism in which an amine, a haloform and a carbonyl containing ("carbonyl") compound are separate reactantsO This reaction is illustrated in one particular example by the reaction of a N,N'-alkyl substituted ethylene diamine with acetone and chloroform; and, in 30 another example, with o-phenylene diamine reacted with cyclohexanone and chloroform. The reaction product in each example is a 2-keto-1,4-diazacycloalkane .
Though both ketones and aldehydes are taught as being effective reactants in the ketoform reac~ion, it has now been diseovered that only 35 ketones are effective in the cyclization of a PAPA. Accordingly, our present 3,.~

invention extends the use of the ketoform reaction to novel alkylated PAPA.
A more detailed teaching of the ketoform synthesis will be found in an ar~icle titled "Hindered Amines. Novel Synthesis of 1,3,3,5,5-Pentasubstit-uted 2-Piperazinones" by John T. Lai in J. Org. Chem. 45, 754 (1980).
It has been discovered that the reaction OI a branched chain polyalkylenepolyamine ("PAPA") havin~ plural amine groups including a secondary amine group intermediate terminalL primary amine groups one of which is hindered, and having at least two carbon atorms between each group, may be selectively reductively alkylated with a ketone in an unexpectedly 1() quite different manner from the known reaction of a PAPA with an aldehyde wherein the PAPA has no hindered amine group.
It is therefore a general object of this inventîon to provide a process for selectively reductively alkylating a PAPA having Q hindered primary amine group, comprising contacting said PAPA with hydrogen and a ketone in l 5 the presence of a catalytically effective amount of a ~,roup vm metal on a catalyst supportS at a pressure in the range from about 100-1000, suitably 500~1000, psi a~d a temperature in the range from about 50C to abo~t 200C for a period o~ time su~icient t~t preferentially alkylate the unhindered primary terminal amine grDup, essentially ~ithout al~ylatin~
either the sterically hindered terminal primary amine group or the inte~medlate secondary amine grouP.
It is therefore a specific object of this inYentiOn to provide selectively reductively alkylated PA.PA which may then be cyclized by th~
Icnown"ketoform synthesis'! Such cyclization is preferably effected using a 25 readily availa~le monoketone such as a lower a1iphatic ketone having from 3 to about 20 carbon atoms, or a cycloaliphatic ketone~ and chloroform which provides the c3rbonyl group in the polysubstituted piperazinone ('tPSP") formed. By selectihg the substiuents in the PAPA, the molecular weight of the PSP may be tailored. One or more such PSPs are found to be essential reactants for the preparation of tailored stabilizers and stabilized compositi-ons of ~hisinventionO
It has further been discovered th~t when a P~P is distally linked, through at le~t a three atom chain of serially linked 1 ~one) N and 2 (two) C
atoms, to a triazine ring, the novel compoun~s so formed are found to be 35 exceptionally well-suited for use as stabilizers in synthel:ic resinous materials .~ ~

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subject to degradation by uv light:
It is therefore a general object of this invention to provide a novel class of hindered amine-triazine derivatives useful as ultraviolet (uv) light stabilizers for polyolefins and other light-degradable polymers, which s derivatives are characterized by (a) having at least one substituted piperazinone distally linked to a triazine ring, and (b) improved resistance to extraction from such polymers in prolonged contact with an aqueous solution.
It is also a general ob3ect of this invention to provide a simple and elegant process for making a distally linked 2-oxo-piperazinyl-triazine ('1PIP-l0 Ti' for brevity~ from a particular class of alkylated PAPA, namely a N-(alkyl)-N'-(aminoalkyl/aryl/aralkyl/cycloalkyl)-l,p-alkanediamine, wherein "p" is the number of methylene C atoms (hereafter "2AAD'1 for brevity), and a triazine compound reactive therewith. The process comprises reductively alkylating a particular class of PAP~, such as a N'-~aminoalkyl/aryl/aralkyl/cycloalkyl)-15 l,p-alkanediamine (hereafter "2AD" for brevity) with a ketone in the presenceof a Group VIII metal hydrogenation catalyst and a solvent for the reactants, by carrying out the reaction under elevated temperature and pressure to produce the 2AAD compound; separating the solvent from the reaction mass;
adding chlo~oform and a ketone, preferably in the presence of a phase 2û transfer catalyst; and, carrying out the reaction to produce a PSP ~Nhich is recovered. The PSP is then reacted with cyanuric chloride or other reactive triazine cornpound. In a particular preferred embodiment of the invention, a PSP is produced from 2AD using a ketone as a reactant to produce 2AAD; and then, again using a ketone as a reactant, to cyclize the 2AAD. The PSP is 25 then coupled with a triazine ring-containing compound to provide at least one distally linked PSP substituent on the triazine ring.
DETAILED DESCRIPTION OF PREFERRED ~MBODIME~TS
The basic structure of the stabilizer compounds prepared by the synthesis described herein, is a substituted triazine ring, to at least one 30 carbon atom of which, is attached a substituted piperazinone by means of a linking group containing a nitrogen atom and at least two carbon atoms. The substituted piperazinone is preferably substituted at both the 3 and 5 positions with alkyl substituents, and the piperazinone substituent is thereforereferred to as being 'polysubstituted'. A polysubstituted piperazinone is ;~..L~3~

linked to a triazine ring as described, to produce a 2-oxo-piperazinyl-triazine ("PIP-TI') which is the stabilizer of this invention, and which may be represented by the following formula (I):

~1~N~ M ~ (I) wherein, n is an integer in the range from 1 to about 10, said compound having ~unctional end groups selected from H, OH and Cl when n is ~reater than l;
Xis a substituent having the following formula (II):

( CH2)p- NRl-~ N~O
Rs7~N~R2 (II) 10 wherein3 Rl represents alkyl having from 1 to about 24 carbon atoms3 cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, azaalkyl having from 1 to about 24 carbon atoms, and azacycioalkyl having from 6 to about 20 carbon atoms;
R2, R3, R4 and R5 independently represent alkyl having from 1 to about 24 carbon atoms;
p represents an integer in the range from 2 to about 10;
Y may be the same as X or M;
M may be Z or Z', wherein Z represents a radical selected from the group consisting of Cl, ~ Me N/~\N R N/--\O NHR N~ 6 1 ~3 NHAr --N and - N~>
~Ar ~.,",~) .

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R6, R7 represent alkyl having from 2 to about 24 carbon atoms;
Ar represents aryl, aralkyl, phenyl, Me is methyl R16 repre-sents alkyl having from 1 to about 24 carbon atoms, cyclo-alkyl having from 5 to about 7 carbon atoms; or NR16 repre-sents an amine where R16 is selected from phenyl and aralkyl having from 7 to about 20 carbon atoms so that NR16 is represented by the structure N ~ ~-(C H ~

wherein Rg is alkyl, and the combined number of alkyl carbon atoms and alkylene carbon atoms p' is in the range of From 1 to 14; Z' represents a radical selected From the group consisting of:

- N~J~ - NH(CH2)pNH -Cl H3 ~H3 -NH- CH- CH2(0CH2CH)X- NH - - N.H(CH2~m-NH - ~CH~)m- NH -- HNCH2C~2- N - CH CH NH -~1 ~Z
Z

3 ~ 3;~
- 7a -- N ~ 2 p ~ O ~ M
M ~ Me Me Me e Me ~ Me ~ Me --O ~ C ~ ---wherein Me is methyl, x represents an integer in the range from 1 to about 50; m represents an integer in the range from

2 to about 4; and, when n = 1, Y and M may be the same as X.
5Particular monomeric PIP-T compounds of this invention may be represented by the following formula (III):

v~ (III) X N X

wherein, X has the same connotation as hereinabove.

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Other monomeric PIP-T compounds of this invention may be represented by the following formula (IV):

~N (IV) X N z wherein, X and Z have the same connotation as hereinabove.
Particular PIP-T bis-compounds of this invention may be represented by the following formula (V):

X~ X

~)~Z' _~ ~N (V) X~--N N~<X

wherein, X and Z' have the same connotation as hereinabove.
Still other PIP-T compounds are oligomers of the substituted 10 triazine ring, and may be represented by the following formula (Vl):
X

N~ ~' t 'V~' wherein, an oligomer is terminated with functional end groups seleeted from H, OH and Cl, and X, Z' and n have the same connotation as hereinabove.
In monomeric PIP-T compounds, Z and Z' each includes a terminal functional group selected from H, lower alkyl having from 1 to about 5 carbon atoms, and hydroxyalkyl having from 1 toabout5 carbon atoms.

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- 8~ -In one particular embodiment X is a radical designated PSP4, wherein PSP~ represents:

Me Me ~ Me ,~CH - N - CH2- CH2- N ~ - H , Me I ~ Me . Me wherein Me is methyl.

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g It is especially significant that these relatively high molecular weight compounds contain a substituted piperazinone moiety distally linked to a substituted triazine moiety, in each of which moieties, namely the substituted piperazinone, the substituted triazine, and the link therebetween, 5 groups may be independently substituted with other groups to produce stabilizers having not only desirable uv light stabilizing properties, but also heat stablizing properties complemented with suitable solubility and dispers-ability. The substituted piperazinones together with the linking substituent are also referred to herein as polysubstituted piperazinones ("PSP" for 1 0 brevity).
The substituted PIP-T compounds are generally oils or high rnelting crystalline solids soluble in acetone, diethyl ether, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform9 lower primary alcohols having from 1 to about 5 carbon atoms such as methanol, ethanol and propanol, aromatic 15 hydrocarbons such as benzene and toluene, but much less soluble in aliphatic hydrocarbons such as hexane. Substituted PIP-T compounds are generally insoluble in water; they range in eolor from white to dark brown when pure.
The amount of stabilizer employed will vary with the particular material to be stabilized and also the substituted PIP-T employed. Generally 20 however, for effective uv light stabilization OI organic materials, an amountof the PIP-T used is in the ran~e from about O.Oûl percent to about 10 percent by weight (% by weight) based on the weight of organic material. In typical stabili~ed composi~ons theamount of substituted PIP-T used is in the range from about 0.01 to about 5% by weight.
Compositions of this invention are synthetic resinous materials wnich have been stabilized to combat the deleterious effects of uv light, thermal or oxidative degradation such as are usually evidenced by discolorat-ion andtor embrittlement. These compcsitions generally benefit from the inclusion of additional, secondary stabilizers to achieve even greater stability30 against a combination of actinic light, heat and oxygen. Therefore, in conjunction with the stabilizers of this invention, compositions may include stabilizers against degradation by heat and/or oxygen which secondary stabilizers may be present in the range from about 0.1 part to about 10 parts by weight, and preferably from about 0.2 part to about 5 parts by weight per 35 lûO parts by weig}rt of the organic continuous phase. Several types of known ~. L4~S~

UV secondary stabilizers may be used, such as those disclosed in U.S.Patents Nos~ 3,325,448; 3,769,259; 3,920,659; 3,962,255; 3,966,7l1; 3,971,757; inter alia.
Organic materials which may be stabilized against uv light, thermal 5 and oxidative degradation, include copolymers of butadiene with acrylic acid, alkyl acrylates or methacrylates, polyiso~rene, polychloroprene, and the like;
polyurethanes; vinyl polymers known as PVC resins such as polyvinyl chloride, copolymers of vinyl chloride with vinylidene chloride, copolymers of vinyl halide with butadiene, styrene, vinyl esters, and the like; polyamides l0 such as those derived from the reaction of hexamethylene diamine with adipic or sebacic acid; epoxy resins such as those obtained from the condensation of epichlorohydrin ~vith bisphenols? and the like; ABS resins, polystyrene, polyacrylonitrile, polymethacrylates, poly-carbonates, varnish, phenol-form-aldehyde resins, polyepoxides, polyesters, and polyolefin homo- and copoly-15 mers such as polyethylene, polypropylene, ethylene-propylene polymers, ethylene-propylenediene polymers, ethylene-vinyl acetate polymers, and the like. The substituted PIP-T compounds can also be used to stabilize mixtures and blends of polymeric materials such as ABS resin blends, PVC and polymethacrylate blends, and blends of polyolefin homopolymers and copoly-2~ mers such as blends of polypropylene in epdm polymers.
~ ost particularly substituted PIP-T compounds of this invention having at least one 3,3,5,5-tetraalkyl piperazinone distally linked to a triazine ring, most preferably with additional substituents at one or both of the remaining substitutable positions on the triazine ring, are especially useful as25 uv-light-stabilizers for synthetic resinous materials which are at least partially permeable to visible light, and particularly for those which are transparent thereto, such as the polyvinylaromatics and polyolefins.
Many known compounding ingredients may be used along with the substituted PIP-T stabilizers in the compositions. Such ingredients include 30 metal oxides such as zinc, calcium and magnesium oxide, fatty acids such as stearic and lauric acid, and salts thereof such as cadmium, zinc and sodium stearate and lead oleatet fillers such as cPlcium and magnesium carbonate~
ealcium and barium sulfates, aluminum silicates~ asbestos, and the like, plasticizers and extenders such as dialkyl and diaryl organic acids like 35 diisobutyl, diisooctyl, diisodecyl, and dibenzyl oleates~ stearates, sebacates, ~ ~S3~9 azelates, phthalates, and the like; ASTM type 2 petroleum oils, paraffinic oils, castor oil, tall oil, glycerin, and the like.
Particularly desirable secondary stabilizers are one or more antioxi-dants used in the range from about 0.1 part to about 20 parts by weight, preferably from about 0.2 part to-about 5 parts by weight per 100 parts by weight of the material. Of the types of antioxidants to be used, are phosphite, phosphate, sulfide and phenolic antioxidants, the last being preferred. Most preferred are phenolic antioxidants such as 2,6-di-t-butyl paracresol; 2,2'-methylene-bis-(6-t-butyl-phenol); 2,2'-thiobis-(~-methyl-6-t-butyl-phenol); 2,2'-methylene-bis-(6-t-butyl-4-ethyl~phenol); 4,4'-butylene-bis-~6-t-butyl-m-cresol); 2-(4-hydroxy-3,5-di-t-butylanilino)-4,6-bis-(octylthio)-1.3,5-triazine; hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyl-s~triazine; hexahydro-1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate;
tetrakismethylene-3-(3',5~-di-t-butyl-4~-hydroxyphenyl)propionate methane;
and other antioxidant synergists such as distearyl thiodipropionate; dilauryl thiodipropionate; tri(nonylphenyl) phosphite; tin thioglycolate; and particularly ;~f commer*ially available antioxidants such as Goodrite6~) 3114, and 3125, Irganox 1010, 1035, 1076 and 1093. Other ingredients such as pigments, tackifiers, flame retardants, fungicides, and the like may also be added.
The substituted PIP-T stabilizers? and the other compounding ingredients if used, ean be admixed with organic materials using known mixing techniques and equipment such as internal mi~ing kettles, a Banbury mixer, a Henschel mixer, a two-roll miU, an extruder mixer, Ol` o~her standard equipment, to yield a composition which may be extruded, pressed, 25 blowmolded or the like into film, fiber or shaped articles. Usual mixing tirnes and temperatures can be employed which may be determined with a little trial and error for any particular composition. The objective is to obtain intirmate and uniform mixing of the eomponents. A favorable mixing procedure to use when adding a substituted PIP~T to an organic material is 30 either to dissolve or suspend the compound in a liyuid such as haxane or benzer~e before adding it, or to add the PIP-T directly to the polymeric organic material whether the PIP-T is in the form of a powder or oil) or to extruder-mix the PIP-T and the polymeric material prior to forming the product.

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The uv stability of a particular composi~ion con~aining a polymeric material and a substituted PIP-T can be evalutated by exposing a prepared sample of the composition to Xenon or carbon arc light in a Weather-O-meter operating at a temperature, for example, about 140F (60C). Degradation of the 5 sample can be followed by periodically measuring tensile strength left, and the hydroperoxide absorption band at 3460 cm 1 or carbonyl absorption band at 1720 cm 1 using an IR spectrophotometer. The rapid formation of carbonyl indicates failure of the sample. The test procedure is well known, and is published in the text Photode~dation, Photo-oxidation and Photostab-10 ilization ~y~ by Ranby and Rabek, John Wiley & Sons, N.Y., N.Y.(1975), at pages 129 et seq., and is disclosed in U.S. Patent No~ 3,909,493.
Failure of the sample is also checked by visual signs of cracking when the sample is bent 180.
Samples of the compositions can also be checked for oxidative and 15 thermal stability by measuring the time to discoloration and/or embrittle-ment of the sample after aging in an air circulating oven at 140C, and other standard ASTM tests such as tensile strength tests.
The method for making the PIP-T compounds of this invention starts with the preparation of a 2AAD compound or other alkylated PAPA, by 20 reductive alkylation of a 2AD or otller PAPA compound in the presence of a ketone reactant. Though reductive alkylation is a well known reaction, particularly for the preparation of amines, as taught for example in Chapter 3 entitled "The Preparation of Amines by Reductive Alkylation" by Emerson, William S., referred to hereinbefore, no PAPA with one hindered primary 25 amine was alkylated. It is surprising that the reductive alkylation reaction carried out on a PAPA with a ketone and a Group VUI metal catalyst, or other known metal reductive alkylation catalyst, selectively provides alkylation at the 1-N atom of the amine being alkylated, without alkylating any other amine group.
The 2AD compound, such as for example, N-(2-amino-2-methylprop-yl3-1,2-ethanediamine, is conveniently prepared from readily available raw materials by any method well known in the artO
In a second step, the 2AAD compound is used as a reactant in a ketoform reaction in the presence of an excess of a carbonyl-containing 35 compound, preferably accelerated with an onium catalyst, to yield a PSPO In l r 3;29 ~.

the third step, the PSP obtained is coupled with a triazine compound reactive therewith, most preferably cyanuric chloride, or an oligomer of fl substituted triazine having a reactive functional end group through which the triazine compound is coupled with the PSP, so as to produce the PIP-T compound.
5 Preparation of 2AAD compound:
In a typical reaction, the 2AAD compound is prepared from N-(2-amino-2-methylpropyl)-1,2-ethanediamine and a ketone selected to provide the desired steric hindrance in the 2AAD compound, as illustrated in the following example 1.
Example 1 Preparation of N-(2-butyl)-N'-(2-amino-2-methylpropyl)-1,2-ethanecliamine having the follovring structure:
Me / Me (lA) ~qe--C--C~2-NH-cH2-cH2 NH CH~cH -Me A mixture of 146 g (1.1 moles) of N-(2-amino-2-methylpropyl~1,2-15 ethanediamine, 84.4 g (1.17 moles) of 2-butanone, 300 ml methanol, and 3.0 g of 1096 platinum on carbon were reacted in a 1 liter autoclave at 80C under 800 pounds per square inch (psi) hydrogen pressure. After two hours the reaction mixture was cooled, then filtered to remove the catalyst. The filtrate was stripped to give 205.3 g of water-white clear liquid which was 20 fractionally distilled under reduced pressure. The desired product recovered was found to weigh 144.5 g (69.5% yield), and has a boiling point (b. p.) of 62-64C/0.15 mm Hg.
The structure written hereinabove is supported by both proton nuclear magnetic resonance (nmr), and field desorption (FD) mass spectrosco-25 pic data.
In an analogous manner, other dialkyl substituents may be substitut-ed at the N position. For example, N-(4-methyl-2-pentyl)-NI-(2-amino-2-methylpropyl)-1,2-ethanediamine may be prepared from N-(2-amino-2-meth-ylpropyl~1,2-ethanediamine and 4-methyl-2-pentanone by reductive alkylat-30 ion in propanoL The compound is obtained in excellent yield and is found tohave a b. p. of 100-109C/0.3 mm Hg.
A13cylated PAPA in general, and the 2AAD compounds in particular, are useful for the curing of epoxy resins, and also as fungicides.

The foregoing selective reductive alkylation process may be effect-ively practiced with any PAPA having the general structure:
Ra /C~
`C' NH - (CH2)p- N~2 wherein, ~H2 Ra and Rb independently represent alkyl having from 1 to 24 carbon atoms, aralkyl having from 7 to about 20 carbon atoms;
Ra or Rb may be cycloahcyl; or, Ra and Rb together when cyclized may be cycloalkyl having from 5 to about 7 carbon atoms; and, p has the same connotation as hereinabove.
When the process is practiced with a lower aliphatic ketone having from about 3 to about 20 carbon atoms, or a cycloaliphatic ketone having from 5 to about 20 carbon atoms and hydrogenation is effected over a Group VIII metal on a suitable catalyst support at a pressure in the range from about 500 psi to about 1000 psi and a temperature in the range from about 50C to about 200 C, no reaction product is isolated which is alkylated at either the intermediate amine group or the hindered terminal amine group.
Preparation of N-(2-propyl)-N'-(2-amino-2-methylpropyl)-1,2-ethanediamine also identified alternatively as N1-(2-N-isopropylaminoethyl)-2-methyl-1,2-propanediamine, having the following structure:
Me ~Me 20 (lB) Me - I - CH2 - NH - CH2 - CH2 - NH - CH
NH2 Me In a stirred autoclave place a mixture of 146 g of N-(2-amino-2-methylpropyl)-1,2-ethanediamine, 64 g acetone, 250 ml of methanol~ and 20 g Raney's nickel, and hydrogenate the mixture under 1500 psi H2 pressure in the autoclave heated and maintained at 150C. After about 5 hr the reaction 25 mixture is cooled, filtered to remove the catalyst, and concentrated. The desired product is obtained in 80% pure form which may be distilled at 90 95C/8 mm to yield a colorless oil. The pure product boils at 96-98C/8 mm of Hg.
The structure written above is supported by both proton nuclear 30 magnetic resonance (nmr), and field desorption (FD) mass spectroscopic data.

Also in an analogous manner, a cycloalkyl, an aryl or aralkyl substituent may be substituted at the N position as for example, by preparing ~-cyclohexyl N'-(2-amino-2-methylpropyl)-1,2-ethanediamine havin~ the foll-owing structure:
Me~ A
(lC) Me~ C- C~2- NH - CH2- CH2- NH~

5 The desired compound is obtained by reacting N-(2-amino-2-methylpropyl)-1,2-ethanediamine with cyclohexanone in methanol in the presence of 10% Pt on carbon by hydrogenation at 80C under 800 psi. The desired eompound is obtained by fractionation at reduced pressure and has a b p of 96-10~C at 0.7mm Hg.
10 Pre~aration of polysubstituted piperazinone ("PSP"):
In a typical reaction, the PSP is prepared by the ketoform synthesis more fully described in U.S. Patent No. 4,167,512, the disclosure of which is incorporated by reference thereto as if fully set forth herein. This synthesis is generally carried out with 1,2-diamines which are reacted with a saturated 15 or unsaturated monoketonè and certain aromatic aldehydes such as benzal-dehyde, along with a haloform reactant, in an organic solvent for the reactants, in the presence of aqueous or solid alkali and a phase transfer catalyst. Though the phase transfer catalyst accelerates the reaction, it is now found to proceed quite well even in the absence of the phase transfer 20 catalyst, provided the carbonyl reactant is a ketone and it is present in large excess. By large excess we refer to an amount in the range from 2 to 2û
times the theoretical amount required. The reaction with a ketone proceeds at room temperature or below, though it may also be earried out at elevated temperatures, depending upon the particular other reactants present. A
25 preferred temperature range is from about -10C to about 30C.
The ketoEorm synthesis as now practiced in the present invention is likewise carried out preferably in the same relatively low temperature range, preferably in the presence of a phase transfer catalyst and an alkali metal hydroxide, and chloroform. However, it differs from the prior art synthesis in 30 that only a ketone will provide a recoverable amount of eyclized PSP.

3;~

Preferred ketones are aliphatic monoketones having from 3 to about 12 carbon atoms, and cyclic monoketones having from about 6 to flbout 8 carbon atoms. I\~ost preferred are the lower aliphatic ketones such as acetone including those having up to about 12 carbon atoms, and the cycloaliphatic 5 ketones such as cyclohexanone which may be substituted. By 'recoverable amount' I refer to more than a trace amount, and particularly to an amount which can be recovered in typical laboratary equipment without undue difficulty.
A particular PSP is conv~niently synthesized from a 2AAD compound 10 as illustrated in the following example 2.
Example 2 Preparation of 1-[2-(2--butylamino)ethyl]-3,3,5,5-tetramethyl-2-piperazinone having the following structure:
/Me CH2~ CH"- NH - CH
(2A) ~ ~ CH - Me 71~N~ Me Me H Me In a 1 liter three-necked flask were placed 131.1 g (0.7 mole) of N-(2-butyl)-N'-(2-amino-2-methylpropyl)-1,2-ethanediamine, 101.6 g (1.75 moles) of acetone, 100.2 g (0.84 mole) of chloroform, 200 ml dichloromethane, and 7.9 g of 18-Crown-6 polyether phase transfer catalyst. To this cooled mixture was added 224 g of S0% aqueous sodium hydroxide solution dropwise over a period 20 of about 5 hours. After allowing the reaction to proceed overnight at about ---4C the reaction temperature was gradually raised to 5C and maintained atthis temperature for an additional 5 hours. After ~he usual worlc-up, the organic layer u as stripped and distilled (b. p. 115-120C/0.25 mm Hg) to collect 71.5 g of very light straw colored syrup which was at lest 98% pure as 25 shown by gas chromatography.
The structure written hereinabove was conIirmed by proton nmr and FD spectroscopic data.

3~

In an analogous manner, by reaction with N-(1,3-dimethylbutyl)-N'-(2-amino-2-methylpropyl)-1,2-ethanediamine, acetone and chloroform, prefer-ably in the presence of an effective amount of a phase transfer catalyst sufficient to produce the desired PSP compound, a compound having the 5 following structure is obtained:
Me /Me (2B) ~ ~f Me M~ I~Me The reaction occurs overnight at 3C and the reaction mass is worked up to produce about a 50% yield of the product which has a b p of 131-3C/0.5 mm Hg.
Also in an analogous manner, by reaction with N-(2-amino-2-methylpropyl)-N'-(cyclohexyl)-1,2-ethanediamine, acetone and chloroform in methylene chloride, a PSP compound having the following str ucture is obtained:

N O
(2C) Me ~ ~Me Me I Me H

15 As before, the reaction is allowed to proceed overnight, after which the desired product recovered is found to have a b p of 145-6 C/0.7 mm Hg, with a yield of about 50% of theoretical.
Preparation of PIP-T:
The PSP obtained as described hereinabove is then coupled by 20 reaction with a reactive triazine compound to yield a PIP T. The triazine compound may be a monomeric triazine ring with functional groups reactive with the PSP, or the triazine compound may be an oligomer of ~ subs~ituted triazine in which the repeating unit has funetional groups which, in the oligomer are terminated with H, OH, or Cl atoms. The reaction is preferably 25 carried out at ice-bath temperatures and ambient pressure, though in many 53~2~

instances a temperature of about 20C is convenient and even higher temperatures in the range from about room temperature to about 6~)C are practical. Typically, a PIP-T may be prepared as illustrated in the following example 3.
Example 3 Preparation of 2,4-dichloro-6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5~triazine having the following structure:
lspl (3A) N o N
Cl~ Cl Me Me - CH2 ~Me wherein, PSPl represents CH - N - CH - CH - N N- H
Me I ~ Me Me In a 1 liter three-necked flask were placed 300 ml of water which was cooled to 1C. 46.1 g (0.25 mole) of cyanuric chloride was dissolved in 240 ml acetone and added to the water in the ~lask. A white slurry formed which was stirred while adding to it dropwise, 63.9 g (0.25 mole) of 1-[2-(2-butylamino)ethyl]-3,3,5,5-tetramethyl 2-piperazinone in 60 ml acetone and 15 13.3 g of sodium carbonate in 60 ml water. The addition took about 30 min.
The reaction was allowed to proceed for about 5.5 hours at about-7 to 9C, after which the slurry was filtered to isolate a white solid. After washing with 750 ml of water and drying the product obtained wieghed 77.7 g and had a melting point (m p) of 91-6C. A pure sample was prepared for 20 analysis by recrystallizing the product from he~ane-toluene (2:1 ratio) and the solid obtained had a m pt of 93-5C.
Theoretical calculation for a compound C17H28C12N6O giYes the following:
C = 50.62; H - 7.00; Cl = 17.58; N = 20.84.
The analyzed product W&S fo~md to have:
25 C = 49.84; H = 6.89; Cl = 17.94; N = 20.70.

~.. L~

In an analogous manner other PSPs may be distally linked to the triazine ring. If the reaction is allowed to proceed further, and slightly in excess of 2 moles of a PSP are provided for each mole of the triazine compound, a second PSP is distally linked to each triazine ring which in turn is already substituted with a PSP. The PIP-T so formed has the following structure:
PSP
(3B) N~ `N
1l Cl N PSPl I:t` the reaction is allowed to proceed still further, and in excess of about 3 moles of a PSP are made available for each mole of triazine ring 1~ compound in the coupling reaction9 a third PSP substituent may be distally linlced to each triazine ring which already has two distally linked PSP
substitutents. The PIP-T so formed has the following structure:
PSP
(3C) N o N
PSPl N PSPl In a manner analogous to that described in Example 3 hereinabove7 15 by reacting [2-(1,3-dimethyl-butylamino) ethyl]-3,3,5,5-tetramethyl-2-piper-`^ azinone dissolved in acetone, and sodium carbonate dissolved in water, added through separate funnels to a fine slurry of cyanuric chloride in acetone, a PIP~T compolmd having the following structure is obtained:

(3D) ~0,~ Me Me ~ Mewherein, PSP2 represents /CH - CH2- Cl H~ N - CH2~ CH2- N N - H
Me Me ¦ ¦--Me Me ~ ~53~9 The eompound, ident;fied as 2,4-dichloro-6-~1,3-dimethylbutyl[2 (3,3,5,5-tetra-methyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine is obtained in about 56% yield, and has a b p of 57-61C.
If about 2 moles of the PSP2 are added, and the reaction allowed to 5 proceed until all the PSP2 is reacted, then a second PSP2 is distally linked to each tri~zine ring; and, if more than about 3 moles of PSP2 are added and the reaction allowed to proceed, a third PSP is distally linked to the triazine ring, in a manner analogous with that described hereinabove.
Example 4 10 Preparation of 2,4-bis(l-piperidinyl~-6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-pipera~inyl)ethyl] amino]-1,3,5-triazine having the structural formula:

PSPl (4A) CN ~ N~L N3 A mixture of 4.03 g (0.01 mole) of 2,4-dichloro-6-[1-methylpropyl-[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine with 1.8715 g (0.022 mole) piperidine and 0.88 g sodium hydroxide in 150 ml toluene were reacted at 150 C for 12 hours in a 300 ml autoclave. The reaction mass was cooled and filtered to remove sodium chloride~ Concentration of the filtrate left an oil which solidified upon cooling. This off-white solid was the crude product weighing 5.03 g. An analytical sample was prepared by recrystalliza-20 tion of the crude solid from hexane. The recrystallized product had a m p of 126~128 C. The structure given above was confirmed by nmr and FD mass sepctroscope analysis.
In an analogous manner, 2,4-bis~l-piperidinyl)-6-[1,3-dimethylbutyl-[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1.3,5-triazine having25 the following structure is prepared:
PSP~2 (4B) CN_~O~N~

by re~cting 0.01 mole 2,4-dichloro~6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-5~;~9 2-oxo-1-piperazinyl)ethyl] amino] -1, 3,5-triazine with 0.022 mole piperidine.
An analytical sample of the product obtained had a m p of 141.5-142.5C.
In a manner analogous to that described immediately hereinabove, a compound identified as 2,4-bis(l-piperidinyl)-6-[cyclohexyl[2-(3,3,5,5-tetra-5 methyl-2-oxo-piperazinyl)ethyl] amino]-1,3,5-triazine having the following structure is obtained:
lp3 (4C) CN~~~O LN~ O~e wherein, PSP3 represents C} N - CH2- CH2- ~- H
¦ Me Me by reacting 2,4-dichloro-6 [cyclohexyl [2-(3,3,5,5-tetramethyl-2-oxo-1-piper-10 azinyl)ethyl] amino] -1,3,5-triazine with piperidine, in the presence of sodium hydroxide and toluene, as before. The compound recovered has a m p of 179-181C.
The compound 2,4-bis(4-morpholinyl)-6-[cyclohexyl [2-(3,3,S,5-tetra-methyl-2-oxo-1-piperazinyl)ethyl] amino]-l, 3,5-triazine having the following 1 5 structureO
P~P3 (~D) is prepared by reacting 2,4-dichloro-6-[cyclohexyl [2-(3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl] amino] -1,3,5-triazine and 0.022 mole morpholine. Re-erystallization of the product from acetone gave a white solid. The structure 20 of the solid was confirmed by nmr and FD mass spectrometer analysis.

~..L~S~

In a manner analogous to that described hereinabove, a compound identified as 2,4,6-tris[cyclohexyl[2-(3,3,555-tetramethyl-2-oxo-l-piperazinyl)-ethyl] amino]-1,375-triazine which has the following structure:
,~P3 ~4E) N o N
PS~ PSP3 is prepared by reacting 0.046 mole 1-[2-(cyclohexylamino)ethyl]-3,3,5,5-tetramethyl-2-piperazinone and 0.01 mole cyanuric chloride, 1.2 g sodium hydroxide and 150 ml toluene. The reaction was carried out at 200 C for 10 hr. The resulting light straw colored solid isolated was recrystaUized from acetone and analyzed. It had a m p of 179-180C and was off-white in color.
~xample 5 Preparation of 2,4-dichloro-6-[cyclohexyl[(l-cyclohexyl-3~3,5,-trimethyl-2-oxo--l-piperazinyl)methyl] amino~-1,3,5-triazine, a PIP-T having the structural formula:

(5A) ~_ Cl N Cl To 300 ml of water cooled to 1C in a three-necked flask are added 36.9 g (0.2 mole) of cyanuric chloride in 200 ml of hot acetone, forming a white slurry. To this slurry is added dropwise, 67.1 g (0.2 mole) of 1-cyclohexyl-5-cyclohexylaminomethyl-3,3~5-trimethyl-2-piperazinone in 50 ml of acetone and 10.6 g of sodium carbonate in 70 ml of water while the 20 reaction temperature W95 maintained below 5C. After reacting for 24 hr the resulting mixture was filtered to isolate 48.6 g of crude product which after recrystallization from toluene gave a white solid having a m p 123-125C.

~.lg~3~

Example 6 Preparation of 2,4-dichloro-6-[2-propyl-[2-(3,3,5,5-tetramethyl-2-oxo-1-piper-azinyl)ethyl] amino] -1,3,5-triazine, a PIP-T having the following structural formula:
,~P4 ~, l N Cl l~e Me O~Me wherein, P~P4 represents ~ClI - N - ClI2- CH2~ H
Me I ~ Me ~qe 0.3 mole cyanuric chloride and 100 ml toluene were placed in a three-necked flask cooled in a melting ice bath, and 0.3 mole of 1-[2-(2-propylamino)ethyl] -3,3,5,5-tetramethyl-2-piperazinone in 70 ml toluene was added dropwise so as to maintain the temperature below 10C. 20% NaOH solution (0.45 mole) was lû then added again keeping the temperature below 10C and the reaction mass was stirred overnight. The product collected was a solid (70 g) which had a rn p 118-121C.
~xample 7 The Cl atoms in the PIP-T prepared in Example 6 hereinabove may 15 each be replaced by reaction with an amine such as an aliphatic secondary amine, for example, a dialkylamine; OI, a cyclic amine, for example, piperidine, morpholine and N-methylaniline, the piperidine-substituted PIP-T
giving the best results with respect to stabilization, both before and after extraction with water, as is evident from the data listed in Table I
20 hereinbelow. The minimal difference in performance before and after extraetion is evidence that the PIP-T compounds are not extracted with water.
The reaction of the PIP-T with an amine is carried out in toluene in the presence of 20% NaOH by heating in an autoclave at about 200 C for 10 ~5 hr, after which the reaction mass is cooled and separated into two layers.
The aqueous layer is dried and concentrated to yield a solid which is then recrystallized.

5~3;Z5~

The PIP~T with both Cl atoms substituted has the following structural formula:
lSP4 (7A) NoN
N'~8 N NR8 where NR8 represents the replacement amine, wherein R8 is selected from the group consisting of alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, phenyl, and aralkyl having from 7 to about 20 carbons atoms so that NR8 is represented by the structure N {~ H~

wherein R9 is alkyl, and the combined number of alkyl carbon atoms and alkylene carbon atoms p' is in the range from 1 to 14.
When HNR8 is piperidine the piperidine-substituted PIP-T has a m p 127-132C.
When HNR8 is morpholine the morpholine-substituted PIP-T has a m p 135-138C.
When HNR8 is N-methylaniline the aralkylamine substituted PIP-T has a m p 115-132C.
The Cl atoms in the PIP-T prepared in Example 6 hereinabove may also be replaced, one or preferably both, by reaction with a PSP as described in Example 3 hereinabove.
Thus, if 1 mole of cyanuric chloride in toluene is reacted with 2 moles of 1-[2-(iso-propylamino) ethyl]-3~3,5,5-tetramethyl-2-piperazinone fo-llowed by the addition of 2 moles aqueous NaOH (10%~ slowly, at a temperature below about 35C, a solid reaction product is isolated which has a m p 126-130C, and the following structure.
l4 (7B) C~
Cl J~N~PSP4 ~. L~ 3~

If an additional (~hird) mole of 1-[2-(is~propylaminc) ethyl]-3,3,5,5-tetramethyl-2-piperazinone is reacted with each mole of cyanuric chloride, a PIP-T compound with the following structure results:
pspa~
(7C) N O N
PSP ~ PSP~l The following Table I sets forth data obtained in tests conducted with 2 mil thickness samples of polypropylene. The blank and each sample includes 0.05 parts per hundred parts of resin ('phr') of Goodrite~}) 3125 antioxidant, and the amount of stabilizer used in each sample is stated. Oven aging is done at 125C in the standard test procedure, and the Weather-O--10 Meter tests give the number of hours after which a sample loses 50% of its ~; tensile strength. Chimasorb 44 is a commercially available polytriazine .~ ....
having piperidine substituents disclosed in U. S. Patent No. 4~086~20as~
TABLE I

Stabilizer used Oven aging Xenon Weather-O-Meter (hr)~*
(days)* Before H2O extr. After H2O extr.

Blanlc 25 180 180 .~4 Chimasorb 944 (0.1 phr) 25 460 400 Chimasorb~944 (0.05 phr) 25 420 420 PIP-T with PSP4 substituent & both HN R 8 is piperidine 22 1470 > 1600 Compound (8A) ~0.05 phr) 33 460 370 Compound (8A) (0.1 phr) 53 600 ~30 Compounds (8E') and (8E") mixed in ratio 2:3 (0.05 phr) 32 550 440 .oodrite is a trademark of the B.F.Goodrich Company ** hours after which tensile strength left was 50Yo of strength before exposure * days at ~25C continuously 3i~

Example 8 Other bis compounds in which two PIP-Ts are linked with a linking group by replacement of Cl atoms of the PIP-T may be prepared by reaction in a suitable solvent by the addition of aqueous NaOH, as taught in Example 5 4, inter alia, hereinabove.
A. Preparation of 1~1',1",1"'-[1,4-piperazinyH,3,5-triazine-6,2,4-triylbis[[iso-propylimino] -2,1-ethanediyl] ] ] tetrakis[3,3,5,5-tetramethylpiperazinone] hav-ing the following structure:

PSP _<PSP4 (8 A) ~N 3~No~<
PSP4 pspd~

10 0.01 mole of 2-chloro-4,6-bis[ iso-propyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piper-azinyl)ethyl] amino]-1,3,5-triazine, 0.005 mole piperazine, 40 ml mesitylene and 0.12 mole 25% NaOH solution were refluxed under ar~on for about 12 hr.
After cooling and filtration, 5 g OI a white solid are collected.

B. Preparation OI 1,1',1",1"'-[1,3-propanediylbis[4,1-piperidinyl-1,3,5-tri-15 azine-6,2,4-triylbis[[(cyclohexyl)imino] -2,1-ethanediyl] ] ] tetrakis[3,3,5,5-tetra-mathylpiperazinone] having the following structure:

PS~3 PSP3 ~ 0~ N~ (CH2)3--CN ~N
(8B) >-- ~

4.72 g (7 m mole) of 2-chloro-4,6~bis[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl3 amino] -1,3,5-triazine, 0~74 g (3.5 m mole) of 4,4'~1,3-2~ propanediyl)bis(piperidine), 0.28 g of ground sodium hydroxide, and 150 ml oftoluene were reacted at 150C for 10 hr, cooled and filteredO The white solid isolated had a m p 223-233C.

C. Preparation of 1,1',1",1"'-[1,4-piperazinyl-1,3,5-triazine-6,2,4-triylbis-[[(cyclohexyl~imino] -2,1-ethanediyl] ] ~ tetrakis[3,3,5,5-tetramethylpiperazinone]
having the following structure:

(8C~ >~0~ N~,~T ~ (~N

~.72 g ~7 milli mole) of 2-chloro-4,6-bis[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl]amino]-1,3,5-triazine, 0.30 g (3.5 m mole) of piper-azine, 0.28 g ground sodium hydroxide, and 150 ml of toluene are reacted at 150C for about 15 hr after which, upon cooling and filtering, 2.6 g of an of î-white solid are recovered. An analytical sample was prepared by recrystalliz-ation from ethyl acetate and methanol which sample had a m p 300-309C.
The above structure was confirmed by FD mass spectrometry.

D. Preparation of 1,1'-[[6-[4-[2-[4,6-bis[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine~2-yl] amino] ethyl] l-piperazinyl] -193,5-triazin-2,4-diyl] bis~cyclohexyl-imino-2,1-ethane-diyl] bis[3,3,5,5-tetramethyl-piperazinone] having the following structure:

(8D) I~N~NHC~I~CEI21~N ~N

.

6.07 g (9 m mole) of 2-chloro-4,6-bis [cyclohexyl [2-~3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl]amino]-1,3~5-triazine, 0.58 g (4.5 millimole~ of N-(2-aminomethyl)piperazine9 0.36 g ground sodium hydroxide, and 151) ml of 20 toluene are reacted at lS0C for about 16 hr after which, upon cooling and filtering, the filtrate was concentrated to a syrup to which 75 ml hexane was added. A light yellow solid was formed which upon recrystallization from hexane-acetone had a m p 115-118C.

aS3~

It will be appreciated that in the preparation of the foregoing bis compounds, and other analogous bis compounds, the particular conditions of the reaction will influence the ratio of reaction products formed in the 'mix' which contains bis compounds other than (8A) and (8C) u1hen each is prepared

5 as described hereinbefore. For example, in the preparation of the bis compound (8A), in addition to this eompound linked only with piperazine, a eompound of the following structure is also formed:

(8A') N O N
~--N /~N~J\N--PSP4~N~ ~

pspd~ PSP4 This PSP4 compound (8A') may be identified as 5,5',5",5"'-~[6-isopropyl[(l-10 isopropyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl] amino] -1,3,5-triazine-2,4-diyl] bis[4,1-piperazinediyl-1,3,5-triazine-6,2,4-triylbis[[~isopropyl)imino]-methyl] ] ] tetrakis~l-isopropyl-3,3,5-trimethylpiperazinone] . An analogous PSP3 bis compound (8C') is also formed along with the compound (8C), and these bis compounds which are generally forrned in a minor amount, from 15 about 5 to about 40% of the mix, relative to the (8A) and (8C) compounds are also useful stabilizers.

3~2~

E. Preparation of a mixture of 2-[(6-aminohexyl) amino]-4,6-bis~2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino]-1,3,5-triazine (identified as cornpound 8E'), and7 1,1',1",1"'-[1,6-hexanediylbis~imino-1,3,5-triazine-6,2,4-triylbis[E(2,2,6,6-tetra-methyl-4-piperidinyl)imino] -2,1-ethanediyl] ] ] tetrakis[3,3,5,5-teramethyl-piperazinone] (identified as compound 8E").
In a 100 ml three-necked flask were placed 2.37 g (3 mmole) of 2-chloro-4,6-bis [292,6,6-tetramethyl-4-piperidinyl[2-(3,3,575-tetramethyl-2-oxo-l-piperidinyl)ethyl] amino]-1,3,5-triazine and 0.174 g (1.5mmole) of 1,6-hexane-diamine, 0.132 g NaOH and 65 ml dry xylene. After refluxing overnight, the reaction mixture was filtered to remove NaCl and the filtrate concentrated to a yellow oil to which hexane was added to form a pale yellow solid. Upon recrystallization from hexane 1.15 g of pale yellow solid, m p 65-175C is obtained. A mass spectrographic (FD) analysis shows the product is a 2:3 mixture of compounds 8E' and 8E" respectively. The reaction may be represented as follows:

PSP5 PSP\5 PSP5 ~ + NH2(CH2)6NH2--~ N~o~NH(cH2)6NH ~ ~<N
Cl PSP5 PSP5 (8E") PSP5 PSP~ N

NH(CH2)6NH2 PSP5 (81~'~

~ CH--CH
wherein PSP5 represents ~
~N~O

~H~;e Me~J~ Me 20 The test results for a mixture of (8E') and (8E") is given in Table I.
.

Preparation of PIP-T oligomers:
In a typical reaction, the PIP-T oligomer is prepared from a dichloro-PIP-T compound and the appropriate compound desired as a substituent for the Cl atoms, in toluene or other suitable solvent usually in 5 the presenee of solid alkali metal, and the reaction is carried out under elevated pressure ir. an autoclave, as described in greater detail in the following examples.
Example 9 A. Preparation of poly[[6-[1-methylpropyl~2-(3,3,5,5-tetramethyl-2-oxo-1-10 piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,6-hexanediylimino~
having the following structure:

~ PSPl \
(9A) ~ N O N
~N~ NH(CH2)6NH n A mixture of 4.03 g (0.01 mole) of 2,~-dichloro-6-[1-methylpropyl [2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyll amino] -1,3,5-triazine, 1.22 g 15 (0.0105 rnole) of 1,6-hexanediamine, 0.84 g sodium hydroxide (ground solid), and lS0 ml toluene were reacted at 155C for about 16 hours in a 300 ml autoclave under autogenously developed pressure in the autoclave. The reaction mixture is cooled, filtered and con~entrated to isolate 2.4 g of light brown solid, from which 1.37 g of gray solid was collected after a water wash.
20 This was combined with 1.69 g of yellow solid obtained from the filtrate (after stripping and water wash). The combined solids are ground and sieved through a NoO 80 U.S~ standard series sieve to yield a light gray powder which has a softening point of 160C.

~PSPl has the same connotation as before (see Example 3) 53~9 B. Preparation of poly[[6-~1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(l-meth-ylethylidene)-1,4-phenyleneoxy] having the following strueture-(9B3 ~ _~ Me ~

In a manner analogous with that described hereinbefore in Example 9A, 0.01 mole of 2,4-dichloro-6-r 1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl] amino] -1,3,5-triazine, 0.0105 mole of 4,4'~1-methyl-ethylidene)bisphenol, in toluene and in the presence of finely ground NaOH
are reacted at 155C for about lfi hr in 300 ml autoclave.
After the usual workup 4.2 g of light straw colored solid was isolated from the filtrate; which solid had a softening point of 8SC.

C. Preparation of poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino~-1,3,5-triazine-2,4-diyl] imino-1,4-cyclohexanediyl~
methylene-1,4-cyclohexanediylimino] having the following structure:
P~P

--~NJ--N~}(~ 2~

In a manner analogous with that described hereinbefore in Example 9A, 0.01 mole of 2,4-dichloro-6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-l-piperazinyl)ethyl] amino]-1,3,5-triazine, 0.0105 mole of 4,4'-methylenebis-(cyclohexylamine), in toluene and in the presence of finely ground NaOH are reacted at ] 50C for about 16 hr in a 3ûQ ml autoelave.
After the usual workup, 3.2 g of pale yellow solid was isolated from the filtrate. When ground and sieved through a No. 80 mesh screen, an off white solid is obtained which softens at 105C.

3~

D. Preparation of poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine-2,4-diyl] imino-1,2-etharlediylimino]
having the following structure- PSPl ,1~ ~
(9D3 _ ~O~NH(CH2)2NH~

In a manner analogous with that described hereinbef'ore in Example 9A, but substituting 0.0105 mole of 1,2-ethanediamine for the 1,6-hexanedi-amine9 the reaction carried out at 1605 yields 3.41 g of light gray solid whichsoftens at 8UC.

E. Preparation of poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-10 piperazinyl)ethyll amino]-1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl] having the following structure: PSPl (9E) ~O~,~N/~\N)~

In a manner analogous with that described hereinbefore in Example 9A, but substituting 0.0105 mole of piperazine for the 1,6-hexanediamine, the 15 reaction carried out at 150 C for about 16 hr directly yields 0.87 g of a grayish solid upon filtration, and an additional 2.49 g of a pale yellow solid from the filtrateafter it is stripped and washed with water. The solids are combined, ground and sieved as above to yield a very light gray powder which softens at 192C.

20 F. Preparation of poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5 triazine-2,4-diyl] imino-1,2-cyclohexanediyl-imino] having the following structure:
~9F~ ~N Q ~
~LNH NH

In a manner analogous with that described hereinbefore in Example 25 9A, but substituting 0.0105 mole of 1,2-cyclohexanediamine for the 1~6--3~5~

hexanediamine, the reaction carried out at 150C for about 1~ hr directly yields 3.5 g of yellow (brown tinted) solid which when ground and sieved softened at 105C.
As will be evident from the foregoing examples, the oligomerization is best carried out at elevated temperature in the range from about 30C to about 300C, and more preferably in the range from about 100C to about 250C. Since the reactions are carried out in solvent, the pressure must be sufficient to avoid undue vaporization of solvent and will generally be above atmospheric, most preferably in the range from about 15 to about 100 psig, the higher pressures generally assisting the speed of the reactionO
Example 10 In a manner analogous to that described hereinbefore in Example 9, PIP-T oligomers are prepared with other PSPs such as PSP2, PSP3, and PSP4.
For example, with P~P2 the following oligomers are prepared in a manner analogous with the PSPl oligomers:
10~. Corresponding to (9A) the compound (lOA) may be identified as follows:
poly[[6-[1,3- dimethyl-butyl[2-(3,3,5,5-tetramethyl-~-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-triazi~e-2~4-diyl3 imino-1,6-hexanediylimine] . The compound is recovered as a straw colored solid which, when ground to a powder, softens at 70C.
lOB. Corresponding to (9B) the compound (lOB) may be identified as follows:
poly[[6-[1,3-dimethyl-butyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] ~
amino]-1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(l-mlethylethylidene)-1,4-phenyleneoxy] .
It is prepared in a manner analogous to the preparation of compound lOA, and specifically as follows: A mixture o~ 4.31 g (0.01 mole) of 2,~}-di-chloro-6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl]
amino]-1,3,5-triazine, 2.4 g (0.0105 mole) of 4,~1-(l-methylethylidene)-bisphenol, 0.84 g sodium hydroxide (ground solid)3 and 150 ml toluene were reacted at 155C for a~out 16 hours in a 300 ml autoclave under autogenously developed pressure in ~he autoclave. The reaction mixture is cooled9 filtered and eoncentrated to recover 5.16 g of a light strawcolored solid. When the solid is ground it is an off-white color and softens at 95C.

3~

lOC. Corresponding to (9C) the compound (lOC) may be identified as follows:
poly[[6-[1,3-dimethyl-butyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-tria~ine-2,4-diyl] imino-1,4-cyclohexanediylmethylene 1,4-cyclo-hexanediylimino] . The cyclohexanediylimino susbstituent linking the triazine 5 nuclei in the oligomer is introduced by reacting 4,4'-methylenebis(cyclohexyl-amine) and recovering the rea(!tion product with the usual workup, namely cooling, filtering and concentrating the reaction mixture. A light straw colored solid is recovered which, when ground, softens at 95C.

lOD. Corresponding to (9D), the compound (lOD) may be identified as follows:
10 poly[[6-[l~3-dimethyl-butyl[2-~3~3~s~s-tetramethyl-2-oxo-l-piperazinyl)ethyl]amino] 1,3,5-triazine-2,4-diyl] imino-1,2-ethanediamino] . The linking subst-ituent is introduced by reacting 1,2-ethanediamine and recovering a light yellow solid after the usual workup. The solid softens at 125C.

lOE. Corresponding to (9E), the compound (lOE) may be identified as follows:
15 poly[[6-[1,3-dimethyl-butyl[2 (3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino]-1,3,5-triazine-2,4-diyl]-1,4-piperazinediyll . The linking substituent is introduced by adding piperazine. A pale yellow solid is recovered whieh when ground, softens at 170C.

lOF. Corresponding to (9F) the compound (lOF) may be identified as ~ollows:
20 poly[[6-[1,3 dimethyl-butyl[2-(3,395,5-tetramethyl-2-oxo-l-piperazinyl~ethyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1l2-cyclohexanediylimino] . The linking substituent is introduced by the addition of 1,2-cyclohexanediamine and the product reco~,~ered is a brown solid which, when ground7 sGftens at 100C.

In each of the foregoing examples lOA-lOF, PSP2 has the same 25 connotation as hereinbefore (see Example 3D).

3 ~953~5~

Example 11 Ir a manner analogous to that described hereinbefore in Example 9 PIP-T oligomers are prepared with PSP3 substituents, as illustrated below:
llA. Corresponding to (9A) the compound (UA) may be identified as follows:
poly[[6-[cyelohexyl[(l-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,6-hexanediylimino] which is obtained as light yellow straw colored solid which was washed with water and dried.
It has a softening point of 80 C.

llB. Corresponding to (9B) the compound (llB~ may be identified as follows:
poly[[6-[cyclohexyl[2-(3,3,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(l-methylethylidene)-1,4-phenylene-oxy~ which is obtained as a straw colored solid softening at 100C.

llC. Corresponding to (9C) the compound (llG) may be identified as follows:
poly[~6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,4-cyclohexanediylmethylene-1,4-cyclohexane-diylimino] which is obtained as a light straw colored solid which softens a 115C
llE. Corresponding to (9E) the compound (llE) may be identified as follows:
poly[[6-[cyclohexyl[(l-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl] -amino]-1,3,5-triazine-2,4-diyll-1,4-piperazinediyl] which is obtained as a light yellow solid so~tening at 115C.

llF. Corresponding to (9F) the compound (lIF) may be identified as foUows.
poly[~6-[cyclohexyl[(l-cyclohexyl 3,3,5-trimethyl-2-oxo-S-pipera~inyl)methyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexanediylimino] whieh is obtained as a yellow (brown tint) solid which sof~ens at 12ûC.

~ 33 -In addition to the foregoing~ the following PSP3-substituted oligomers are prepared in a manner analogous to that described hereinabove:
~xample 12 12A. A compound identified aS poly[[6-[cyclohexyl[2-(3~3,5~5-tetramethyl-2-oxo-piperazinyl)ethyl~ amino] -1,3~5-triazille-2,4-diyl] oxy~l~4-[2-(1~1-dimethyl-ethyl)J phenylene(l methylethylidene)-1,4-[3-(1,1-dimethylethyl)] phenyleneoxy]
having the following StrUctUre iS obtained as a solid WhiCh softens at 90C:

Mé~ Me_~_ Me n 12B. A compound identiried as poly[[6-[cyclohexyl[2-(3,3,5,5~tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1~3~5-triazine-2~4-diyl] iminO-l~2-ethailediy,4-piperaZi71ediyl] haVillg the following structure iS Obtaitled as a yellow to light brown solid lNhiCh softens at 128C.
PSP

~~ (12B) ~NHCH2CE~2--N/~

12G. A compound identified as poly[[6-[cyclohexyl[2-(3,3,5~5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1~3-propanediyl-1~4~piperazinediyl-1~3-propanediylimino] iS obtained as a light yellow solid having a softening point 0~ 82C, and has the following structUre:
PSP

(12C) +~' NH(C~2)3~N/~ (CH2)3 3~

12D. A compound identified as poly[[6-[cyclohexyl[l-cyclohexyl-3,3,5-tri-methyl-2-oxo-5-piperazinyl)methyl] amino]-1,3,5-triazine-2,4-diyl] imino-1,2-ethanediyl-1,4-piperazinediyl] having the following structure is obtained as a yellow-brown solid which softens at 125C:

1 O~ /CM2 CH2~ _ As will readily be ascertained, the molecular weights of the monomeric PIP-T compounds with a single triazine nucleus may be calculated from their structural formulae. For example the compound (3A) prepared in Example 3 will have a molecular weight of 96. The molecular weight oî such 10 a PIP-T may be increased by changing the substituents on the pipera~inone, aswell as well as those on the N atom linlced to the triazine nucleus. Similarly, the molecular weight of a monomeric PIP-T with more than one triazine nucleus, such as the bis compounds illustrated in Example 8, may also be readily calculated.
The molecular weights of the oligomers will generally range from about 500 to about 5000, though higher molecular weights up to al~out 10,000 may be prepared with appropriate substituents. The molecular weights of oligomers are most preferably determined with a vapor pressure osmometer which provides a number average molecular weight ( Mn ). The molecular 20 weight may also be obtained by mass spectrographie analysis, and if the molecular weight is above about 4000, gel permeation chromatography may be used.

~ ~53~

Example 13 Still other oligomers such as PSP4-substituted oligomers illustratively listed herebelow in this example 13, were prepared in a manner analogous to that described hereinabove for the other oligomers. Thus, by reaction of N -5 (2-N-isoproylaminoethyl)-2-methyl-1,2-propanediamine with acetone and chlo-roform, both the latter in excess, and dripping in NaOH (the ketoform reaction), the PSP formed is 1-(2-N-isopropylaminoethyl)-3,3,5,5-tetramethyl-2-pieprazinone. This PSP is reacted with cyanuric chloride on a 1:3 molar basis so that the major portion of the substituted product, if no~ essen~ia~ly 10 all of it, is a PIP-T which is mono-substituted with the PSP4. The 2,4-dichloro-6-N-(N-isopropyl-N-(2-(1-3,3,5,5-tetramethyl-2-piperazinone) ethyl-amino)-1,3,5-triazine (the PIP-T) is a solid (m p 118-121C) which is reacted with an equimolar amount of a primary or secondary diamine chosen to provide a desired linking substituent in the oligomer, in the presence of 15 aqueous alkali and toluene solvent, in an autoclave at about 200C for about 10 hr. When the reaction product is cooled, solids are filtered and the organic layer of the filtrate is concentrated to provide additional solid.
The reaction producing the oligomers may be written as follows:

~ + Rll HNRIoNHR12 ~I~N~LNR ON

20 wherein, Rlo represents alkyl having from 2 to about 24 carbon atoms, or cycloalkyl having from 5 to about 7 carbon atoms, and Rll and R12 independently represent H or alkyl having from 1 to about 24 carbon RtomS with reactive functional groups.

3~

The following diamines are conveniently used to provide a linking group for the oligomers which generally constitute from 3 to about 10 linked molecules depending upon the linking group.
Oligomer's Diamine melting point9 C
piperazine > 250 1,6-hexanediamine 125-145 ethylenediamine 205-285 1,3-propanediamine 165-200 methylamino-~,N-bis-(3-aminopropane) 65-100 p-phenylenediamine > 250 The number average molecular weights determined by vapor pressure osmometer for some of the oligomers prepared are listed hereinbelow:
Oligomer Mn lOC 1350 lS lOD 1350 lOE 2430 lOF 1190 llA. 864 ~lB 1440 llC 790 llE 1180 llF 965 53~

~ t will now be more readily appreciated that the preparation of the PIP-T compounds of this invention depends upon the ability to prepare the precursor piperazinone with the serially linked N and C atoms of the substituent bridge (to the triazine ring) at the Nl position of the piperazinone.
5 The preparation of the substituted piperazinone, in turn, depends upon the ability to preferentially selectively reductively alkylate a suitable PAPA.
Having made the substituted piperazinone which itself has good uY-light stabiliz~tion properties, there was no reason to expect that connecting the piperazinone to a triazine nucleus9 as illustrated in Example 6, would provide 10 superior uv-stabilization compared with that provided by the substituted piperazinone alone~ It does not. This result is consistent with the knowledge that trizaine by itself has no significant uv-stabilization properties. Yet, by introducing the additional substituted piperazinone substituents in the remaining two positions of the triazine ring, unexpectedly results in excellent 15 uv-stabilization properties of the PIPT-T compounds. Alternatively, the rem-aining two positions on the triazine ring may be substituted with an amine as illustrated in Example 7A which also yields compounds with excellent u-v light stabilization properties.
I~ is most preferred, for practical reasons, to use a cyanuric halide, 20 for example cyanuric chloride or bromide, as the reactant to form a PIP-T
compound9 though it wi31 be appreciated that any triazine compound with a reactive functional group will serve the purpose. Compositions containing an effective amount of a PIP-1` stablizer in which two PSPs are linked to a triaæine ring (as sho~rn in the structural formula IV) exhibit satisfactory u-v 25 light stability even when the third position is occupied by Cl or Br. The u-v light stability of sueh compounds is enhanced by substituting any othel zubstitIIent (Z) for the remaining Cl, which is effected without difficulty.
Illustrative of compounds so formed are:
2-[(6-aminohe~yl)amino] -4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5 30 tetramethyl-2-oxo-1-piperazinyl)ethyl3 amino]-1,3,5-triazine;
2-piperidinyl-4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine;
2-morpholinyl-4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2 ~3,3~5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] 1,3,5-triazine; and, 35 2 cyclohexylamino-496-bis[2,2,6,6-tetramethyl-4-piperidinyl~2-(3,3,5,5-tetra- methyl-2-oxo-1-piperazinyl)ethyl~ amino~-1,3,5-triazine.

?S329 Illustrative of PIP-T compounds in which the triazine ring has two PSP susbtituents and a remaining Cl in the third position, and which are effective u-v light stabilizers are the following:
2-chloro-4,6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-5 ethyl] amino]-1,3,5-triazine;
2-chloro-4,6-[1,3-dimethylbutyl [2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] aminol-1,3~5-triaziIle;
2-chloro-4,6-[cyclohexyl [(1-cy~lohexyl-3,3,5,-trimethyl-2-oxo-1-piperazinyl)-methyl] amino]-1,3,5-triaæine; and, 10 2-ehloro-4~6-bis-~isopropyl-[2-(3~3~3~5~-tetramethyl-2-oxo-l-piperazin ethyl] amino] -1,3,5-triazine.
The foregoing reactions of a triazine compound with reactive functional groups and PSPs take place readily at the lower portion of the temperature range ~rom about -10C to about 250 C. If a third PSP is to be 15 introduced on to the triazine nucleus (as shown in structural formula III) the higher portion of the indicated temperature range will generally be ~ound more suitable. Illustrative of PIP-T compounds in which three PSPs are distally linked to a triazine nucleus are the following:
2,4,6-tris[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -20 amino] 1,395-triazine;
2,4,6-tris[N~N-isopropyl-N-(2-(1,3,3,5,-tetramethyl-2-piperazinone)-ethylam ino)] -1, 3, 5-triazine;
2,4,6-tris~l-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine;
25 2,4,6-tris[1,3--dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine; and, 2,4,6-tris[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2~oxo-l-piperidinyl~ethyl] amino]-1,3,5-triazine.

53~9 Though it will also now be apparent that the pri mary purpose of preparing a 2AAD is to provide the necessary PSP substituent for the triazine ring and thus form the PIP-T compounds of this invention, it will be realized that numerous 2AAD compounds may be prepared with substituents which 5 may have no especial importance relative to the efficacy of the u-v light stability of the eventual PIP-T stabilizer compound, but which may have significance in other applications, and none of these 2AAD compounds could be prepared except by the selective reductive alkylation reaction described herein. These alkylated polyalkyleneamines are more particularly N-(alkyl)-10 N'-(aminoalkyl, or aminoaryl, or aminoaralkyl, or aminocyeloalkyl)-l,p-alkanediamines, wherein "p" refers to the number of methylene C atoms, which compounds have the structural formula Ra ~ Rc Rb_ C CH2 - NH - (CH2)p- NH - CH
NH2 Rd wherein, 5 Ra and Rb independently represent alkyl having from 1 to about 24 carbon atoms, aralkyl having from 7 to about 20 carbon atoms;
Ra or Rbmay be cycloalkyl; or, Ra and Rb together, when cyclized, may be cycloalkyl having from 5 to about 7 carbon atoms; U Rc and Rd independently represent alkyl having from 1 to about 24 carbon atoms, aralkyl having ~rom 7 to about 20 carbon atoms;
Rc or Rd may be cycloalkyl; or, Rc and Rd together, when cyclized, may be cycloalkyl having from 5 to about 7 carbon atoms; and, 25 p represents an integer in the range from 2 to about 10.
Illustrative of 2AAD compounds which may be prepared by the reductive alkylation process of this invention are the following:
N-(2-propyl) N'~2-amino-2-ethylbutyl)1,2-ethanediamine;
N-cyclohexyl)-N'~ 2-am ino-2-ethylbutyl)l, 3-propanediam ine;
30 N-(2-octyl)-N'-(2~amino-2-ethylbutyl)196-hexanediamine;
N (2-propyl)-N'-(2-amino-2-2-diphenylethyl)-1,2-ethanediamine;
N-cyclohexyl-N'~2-amino-2-2-diphenylethyl)-1,6-hexanediamine~
N-(2-propyl)-N'~l-aminocyclohexylmethyl)-1,2-ethanediamine; and, N-cyclohexyl-NI~l-aminocyclohexylmethyl)-1,6-hexanediamine.

Claims (34)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A class of compounds comprising polysubstituted piperazinones distally linked to a triazine nucleus ("PIP-T"), and bis compounds and oligomers of said PIP-T compounds represented by the structural formula (I) wherein, n is an integer in the range from 1 to about 10, said compound having functional end groups selected from H, OH and Cl when n is greater than 1; X is a substituent having the following formula (II):

(II) wherein, R1 represents alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, azaalkyl having from 1 to about 24 carbon atoms, and azacycloalkyl having from 6 to about 20 carbon atoms; R2, R3, R4 and R5 independently represent alkyl having from 1 to about 24 carbon atoms; p represents an integer in the range from 2 to about 10;

Y may be the same as X or M; M may be Z or Z', wherein Z
represents a radical selected from the group consisting of Cl, R6, R7 represent alkyl having from 2 to about 24 carbon atoms;
Ar represents aryl; aralkyl or phenyl; Me is methyl, R16 represents alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms; or NR16 represents an amine wherein R16 is selected from phenyl and aralkyl having from 7 to about 20 carbon atoms so that NR16 is represented by the structure wherein R9 is alkyl, and the combined number of alkyl carbon atoms and alkylene carbon atoms p' is in the range of from 1 to 14; Z' represents a radical selected from the group consisting of wherein, Me is methyl, x represents an integer in the range from 1 to about 50; and, when n = 1, Y and M may be the same as X, and, Z and Z' each includes a terminal functional group selected from H, lower alkyl having from 1 to about 5 carbon atoms, and hydroxyalkyl having from 1 to about 5 carbon atoms.

2. The compounds of claim 1 having the structural formula (III)

3. The compounds of claim 1 having the structural formula (IV)

4. The compounds of claim 1 having the structural formula (V)

5. The compounds of claim 1 having the structural formula (VI)

6. The compounds of claim 1, selected from the group con-sisting of 2,4-bis(1-piperidinyl)-6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]amino]-1,3,5-triazine;
2,4-bis(1-piperidinyl)-6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1piperazinyl)ethyl]amino]-1,3,5-triazine;
2,4-bis(1-piperidinyl)-6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-1,3,5-triazine; and 2,4-bis(4-morpholinyl)-6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]amino]-1,3,5-triazine.

7. The compounds of claim 1, having the structure:

wherein NR8 represents an amine, wherein R8 is selected from the group consisting of alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, and PSP4 represents wherein Me is methyl.

8. The compounds of claim 1 selected from the group consisting of:
2-chloro-4,6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine;
2-chloro-4,6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl]amino] -1,3,5-triazine;
2-chloro-4,6-[cyclohexyl[(1-cyclohexyl-3,3,5,-trimethyl-2-oxo-1-piperazinyl)-methyl] amino]-1,3,5-triazine; and, 2-chloro-4,6-bis-(isopropyl-[2-(3,3,3,5,-tetramethyl-2-oxo-1-piperazinyl]-ethyl] amino]-1,3,5-triazine.

9. The compounds of claim 2 selected from the group consisting of:
2,4,6-tris[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] 1,3,5-triazine;
2,4,6-tris[N-(N-isopropyl-N-(2-(1,3,3,5,-tetramethyl-2-piperazinone)-ethylamino)] -1,3,5-triazine;
2,4,6-tris[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine;
2,4,6-tris[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl) ethyl] amino] -1,3,5-triazine; and, 2,4,6-tris[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperidinyl)ethyl] amino] -1,3,5-triazine.

10. The compounds of claim 3 selected from the group consisting of:
2-[(6-aminohexyl)amino] -4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine;
2-piperidinyl-4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine;
2-morpholinyl-4,8-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine; and, 2-cyclohexylamino-4,6-bis[2,2,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetra-methyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine.

11. The compounds of claim 4 selected from the group consisting of:
1,1',1",1?-[1,4-piperazinyl-1,3,5-triazine-6,2,4-triylbis[[ iso-propylamino]-2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethylpiperazinone];
1,1',1",1?-[1,3-propanediylbis[4,1-piperidinyl--1,3,5-triazine-6,2,4-triylbis-[[(cyclohexyl)imino] 2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethylpiperazinone];
1,1',1",1?-[1,4-piperazinyl-1,3,5-triazine-6,2,4-triylbis[[(cyclohexyl)imino] -2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethylpiperazinone];
1,1'-[[6-[4-[2-[4,6-bis [cyclohexyl [2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino] -1,3,5-triazine-2-yl] amino]ethyl] 1-piperazinyl]-1,3,5-triazin-2,4-diyl] bis [cyclohexyl-imino-2,1-ethane-diyl] bis[3,3,5,5-tetramethylpiper-azinone]; and, 1,1',1",1?-[1,6-hexanediylbis[imino-1,3,5-triazine-6,2,4-triylbis[[(2,2,6,6-tetra-methyl-4-piperidinyl)imino]-2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethyl-piperazinone].

12. The compounds of claim 5 selected from the group consisting of:
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,6-hexanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] -amino]-1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(1-methylethylidene)-1,4-phenyleneoxy];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine-2,4-diyl] imino-1,4-cyclohexanediylmethylene-1,4-cyclohexanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,2-ethanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexanediyl imino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino]-1,3 5-triazine-2,4-diyl]imino-1,6-hexanediylimino];

poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(1-methylethylidene)-1,4-phenyleneoxy];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino]-1,3,5-triazine-2,4-diyl] imino-1,4-cyclohexanediylmethylene-1,4-cyclo-hexanediylimino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino] -1,3,5-triazine-2,4-diyl] imino-1,2-ethanediylimino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl]-1,4-piperazinediyl];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] -amino]-1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexanediylimino];
poly[[6-[cyclohexyl[(1-cyclohexyl-(3,3,5,5-tetramethyl-2-oxo-5-piperazinyl)-methyl] amino]-1,3,5-triazine-2,4-diyl] imino-1,6-hexanediylimino];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(1-methylidene)-1,4-phenyleneoxy];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,4-cyclohexanediylmethylene-1,4-cyclohexane-diylimino];
poly[[6-[cyclohexyl[(1-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl] -amino] -1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl];
poly[[6-[cyclohexyl[(1-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl] -amino]-1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexanediylimino];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine-2,4-diyl] oxy-1,4-[2-(1,1-dimethylethyl)] phenylene(1-methylethyl-idene)-1,4-[3-(1,1-dimethylethyl)] phenyleneoxy];
poly[[6-[cyclohexyl[2-(3,3,5,5 tetramethyl-2-oxo-5-piperazinyl)ethyl]amino]-1,3,5-triazine-2,4-diyl] imino-1,2-ethanediyl-1,4-piperazinediyl];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine-2,4-diyl] imino-1,3-propanediyl-1,4-pipeazinediyl-1,3-propanediyl-imino]; and, poly[[6-[cyelohexyl[1-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,2-ethanediyl-1,4-piperazinediyl].

13. The compounds of claim 1, having the structure wherein NR18 is selected from the group consisting of piperidyl, morpholinyl and N-methylanilino, and, wherein PSP4 represents:

wherein Me is methyl.

14. A composition of matter resistant to degradation by ultraviolet light comprising an organic material subject to ultraviolet light degradation having dispersed therein from about 0.01 part to about 5 parts by weight of a stabilizer compound consisting of a polysubstituted piperazinone distally linked to a triazine nucleus, per 100 parts of said organic material, said stabilizer compound being represented by the structural formula (I) wherein, n is an integer in the range from 1 to about 10, said compound having functional end groups selected from H, OH and Cl when n is greater than 1;
X is a substituent having the following formula (II):

(II) wherein, R1 represents alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, azaalkyl having from 1 to about 24 carbon atoms, and azacycloalkyl having from 6 to about 20 carbon atoms;
R2, R3, R4 and R5 independently represent alkyl having from 1 to about 24 carbon atoms;
P represents an integer in the range from 2 to about 10;
Y may be the same as X or M;
M may be Z or Z', wherein Z represents a radical selected from the group consisting of Cl, R6, R7 represent alkyl having from 2 to about 24 carbon atoms;
Ar represents aryl;
Z' represents a radical selected from the group consisting of x represents an integer in the range from 1 to about 50; and, when n = 1, Y and M may be the same as X, and, Z and Z' each includes a terminal functional group selected from H, lower aL'cyl having from 1 to about 5 carbon atoms, and hydroxyalkyl having from 1 to about 5 carbon atoms.

15. The composition of claim 14 wherein said stabilizer compound has the structural formula (III)

16. The composition of claim 14 wherein said stabilizer compound has the structural formula (IV)

17. The composition of claim 14 wherein said stabilizer compound has the structural formula (V)

18. The composition of claim 14 wherein said stabilizer compound has the structural formula (VI)

19. The composition of claim 14 wherein said stabilizer compound is selected from the group consisting of:
2,4-bis(1-piperidinyl)-6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]amino] -1,3,5- triazine;
2,4-bis(1-piperidinyl)-6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine;
2,4-bis(l-piperidinyl)-6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine; and, 2,4-bis(4-morpholinyl)-6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine.

20. The composition of claim 14 wherein NR8 represents an amine, wherein R8 is selected from the group consisting of alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, phenyl, and aralkyl having from 7 to about 20 carbons atoms so that NR8 is represented by the structure or wherein R9 is alkyl, and the combined number of alkyl carbon atoms and alkylene carbon atoms p' is in the range from 1 to 14.

21. The composition of claim 15 wherein said stabilizer compound is selected from the group consisting of:
2,4,6-tris[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] 1,3,5-triazine;
2,4,6-tris[N-(N-isopropyl-N-(2-(1-3,3,5,-tetramethyl-2-piperazinone)-ethylamino)] -1,3,5-triazine;
2,4,6-tris[l-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino] -1,3,5-triazine;
2,4,6-tris[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine; and, 2,4,6-tris[292,6,6-tetramethyl-4-piperidinyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperidinyl)ethyl] amino]-1,3,5-triazine.

22. The composition of claim 16 wherein said stabilizer compound is selected from the group consisting of:
2-chloro-4,6-[1-methylpropyl[2-(3,3,5,5 tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine;
2-chloro-4,6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino]-1,3,5-triazine;
2-chloro-4,6-[cyclohexyl[(1-cyclohexyl-3,3,5,-trimethyl-2-oxo-1-piperazinyl)-methyl] amino]-1,3,5-triazine;
2-chloro-4,6-bis-(isopropyl-[2-(3,3,3,5,-tetramethyl-2-oxo-1-piperazinyl]-ethyl] amino] -1,3,5-triazine;
2-[(6-aminohexyl) amino]-4,6-bis [2,2,6,6-tetramethyl-4-piperidinyl [2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine.

23. The composition of claim 17 wherein said stabilizer compound is selected from the group consisting of:
1,1',1",1"'-[1,4-piperazinyl-1,3,5-triazine-6,2,4-triylbis[[iso-propylamino]-2,1-ethanediyl]]]tetrakis[3,3,5,5-tetramethylpiperazinone];
1,1',1",1"'-[1,3-propanediylbis[4,1-piperidinyl--1,3,5-triazine-6,2,4-triylbis-[[(cyclohexyl)imino]2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethylpiperazinone];1,1',1",1"'-[1,4-piperazinyl-1,3,5-triazine-6,2,4-triylbis[[(cyclohexyl)imino]-2,1-ethanediyl]]] tetrakis[3,3,5,5-tetramethylpiperazinone];
1,1'-[[6-[4-[2-[4,6-bis[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl]amino]-1,3,5-triazine 2-yl] amino] ethyl]1-piperazinyl]-1,3,5-triazin-2,4-diyl] bis[cyclohexyl-imino-2,1-ethane-diyl] bis[3,3,5,5-tetramethylpiper-azinone]; and, 1,1',1",1"'-[1,6-hexanediylbis[imino-1,3,5-triazine-6,2,4-triylbis[[(2,2,6,6-tetra-methyl-4-piperidinyl)imino] -2,1 ethanediyl]]] tetrakis[3,3,5,5-tetramethyl-piperazinone].

24. The composition of claim 18 wherein said stabilizer compound is selected from the group consisting of:
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] amino] -1,3,5-triazine-2,4-diyl]imino-1,6-hexanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl] -amino]-1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(1-methylethylidene) 1,4-phenyleneoxy];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)-ethyl]amino] -1,3,5-triazine-2,4-diyl]imino-1,4-cyclohexanediylmethylene-1,4-cyclohexanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl-amino]-1,3,5-triazine-2,4-diyl]imino-1,2-ethanediylimino];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino]-1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl];
poly[[6-[1-methylpropyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4 diyl]imino-1,2-cyclohexanediyl imino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl]imino-1,6-hexanediylimine];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino]-1,3,5-triazine-2,4-diyl]oxy-1,4-phenylene(1-methylethylidene)-1,4-phenyleneoxy];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl]imino-1,4-cyclohexanediylmethylene-1,4-cyclo-hexanediylimino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino]-1,3,5-triazine-2,4-diyl]imino-1,2-ethanediylimino];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl];
poly[[6-[1,3-dimethylbutyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexarlediylimino];
poly[[6-[cyclohexyl[(1-cyclohexyl-(3,3,5,5-tetramethyl-2-oxo-5-piperazinyl)-methyl] amino] -1,3,5-triazine 2,4-diyl] imino-1,6-hexanediylimino];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]amino] -1,3,5-triazine-2,4-diyl] oxy-1,4-phenylene(1-methylidene)-1,4-phenyleneoxy];

poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino]-1,3,5-triazine-2,4-diyl]imino-1,4 cyclohexanediylmethylene-1,4-cyclohexane-diylimino];
poly[[6-[cyclohexyl[(1-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl]-amino] -1,3,5-triazine-2,4-diyl] -1,4-piperazinediyl];
poly[[6-[cyclohexyl[(1-cyclohexyl-3,3,5-trimethyl-2-oxo-5-piperazinyl)methyl] -amino]-1,3,5-triazine-2,4-diyl] imino-1,2-cyclohexanediylimino];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl]amino] -1,3,5-triazine-2,4-diyl] oxy-1,4-[2-(1,1-dimethylethyl)] phenylene(1-methylethyl-idene)-1,4-[3(1,1-dimethylethyl)] phenyleneoxy];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-5-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,2-ethanediyl-1,4-piperazinediyl];
poly[[6-[cyclohexyl[2-(3,3,5,5-tetramethyl-2-oxo-1-piperazinyl)ethyl] amino] -1,3,5-triazine-2,4-diyl] imino-1,3-propanediyl-1,4-pipeazinediyl-1,3-propanediyl-imino]; and, poly[[6-[cyclohexyl[1-cyclohexyl-3,3,5-trimethyl-2 oxo-5-piperazinyl)methyl]-amino] -1,3,5-triazine-2,4-diyl] imino-1,2-ethanediyl-1,4-piperazinediyl].

25. A process comprising reductively alkylating a polyalkyleneamine having one sterically hindered terminal amino group, one unhindered terminal amino group and one secondary amino group therebetween, represented by the structural formula:
wherein, Ra and Rb independently represent alkyl having from 1 to about 24 carbon atoms, aralkyl having from 7 to about 20 carbon atoms;
Ra or Rb may be cycloalkyl; or, Ra and Rb together, when cyclized, may be cycloalkyl having from 5 to about 7 carbon atoms; and, p represents an integer in the range from 2 to about 10; including contacting said polyalkyleneamine with hydrogen and a ketone in the presence of a catalytically effective amount of a Group VIII metal on a catalyst support at a pressure in the range of from about 100 psi to about 1000 psi and a temperature in the range of from about 50°C to about 200°C for a period of time sufficient to preferentially alkylate said unhindered terminal amino group essentially without alkylating either said sterically hindered terminal amino group or the intermediate secondary amino group, so as to yield a N-(alkyl)-N'-(aminoalkyl/aryl/aralkyl/cycloalkyl)-1,N-alkanediamine("2AAD").

26. The process of claim 25 wherein said Group VIII metal is selected from the group consisting of nickel, platinum and palladium.

27. The process of claim 26 wherein p = 2.

28. The process of claim 27 wherein Ra and Rb are each lower alkyl having from 1 to about 6 carbon atoms.

29. The process of claim 25 including, in addition, reacting said 2AAD with sufficient amounts of chloroform and a ketone, optionally in the presence of a phase transfer catalyst, at a temperature in the range from about -10°C to about 30°C, to yield a polysubstituted piperazinone ("PSP").

30. The process of claim 29 including in addition, reacting said PSP with a triazine compound having reactive functional groups at a temperature in the range from about -10°C to about 250°C, so as to yield a distally linked 2-oxo-piperazinyl-triazine ("PIP-T") having the structure wherein, X is a substituent having the structure wherein, R1 represents alkyl having from 1 to about 24 carbon atoms, cycloalkyl having from 5 to about 7 carbon atoms, aralkyl having from 7 to about 20 carbon atoms, azaalkyl having from 1 to about 24 carbon atoms, and azacycloalkyl having from 6 to about 20 carbon atoms;
R2, R3, R4 and R5 independently represent alkyl having from 1 to about 24 carbon atoms;
p represents an integer in the range from 2 to about 10; and, Q and Q' each represents a reactive functional moiety or X.

31. An alkylated polyalkyleneamine having the structure wherein, Ra and Rb independently represent alkyl having from 1 to about 24 carbon atoms, aralkyl having from 7 to about 20 carbon atoms;
Ra or Rb may be cycloalkyl; or, Ra and Rb together, when cyclized, may be cycloalkyl having from 5 to about 7 carbon atoms;
Rc and Rd independently represent alkyl having from 1 to about 24 carbon atoms, aralkyl having from 7 to about 21) carbon atoms;
Rc or Rd may be cycloalkyl; or, Rc and Rd together, when cyclized, may be cycloalkyl having from 5 to about 7 carbon atoms; and, p represents an integer in the range from 2 to about 10.

32. The compounds of claim 31, including:
N-(2-propyl)-N'-(2-amino-2-ethylbutyl)1,2-ethanediamine;
N-cyclohexyl)-N'-(2-amino-2-ethylbutyl)1,3-propanediamine;
N-(2-octyl)-N'-(2-amino-2-ethylbutyl)1,6-hexanediamine;
N-(2-propyl)-N'-(2-amino-2-2 diphenylethyl)-1,2-ethanediamine;
N-cyclohexyl-N'-(2-amino-2-2-diphenylethyl)-1,6-hexanediamine;
N-(2-propyl)-N'-(1-aminocyclohexylmethyl)-1,2-ethanediamine; and, N-cyclohexyl-N'-(1-aminocyclohexylmethyl)-1,6-hexanediamine.

33. The compounds of claim 1, having the structure wherein NR28 represents an amine wherein R28 is selected from phenyl and aralkyl having from 7 to about 20 carbon atoms so that NR28 is represented by the structure wherein R9 is alkyl, and the combined number of alkyl carbon atoms and alkylene carbon atoms p' is in the range of from 1 to 14; and wherein PSP4 represents:

wherein Me is methyl.

34. A process according to claim 25, wherein said pressure is from about 500 psi to about 1000 psi.