The B. F. Goodrich Company

Other

George Kletecka

John T Lai

Pyong-Nae Son

Victor L Ledesma

Pyong N Son

Ti Chou

Ronald M Kovach

James Stanley Dodge

Mark E Forry

A coating composition for use as an overcoat or heat resistant coating having improved heat resistance comprised of an aqueous latex polymer emulsion and a water soluble or water-dispersible resin which containing a sufficient number of either (a) carboxyl groups or (b) carboxyl and amide groups which will form at least one anhydride ring or imide, in the presence of sufficient heat, and release water molecules, with the latex polymer having a particle size of less than about 1600 Angstroms and containing an effective amount of a nitrogen containing volatile base to achieve a pH of greater than about 7.5 to keep the resin solubilized or dispersed.

Heat resistant coating composition

Only two symmetrical stabilizers in a polyolefin or copolymer thereof, provide thermooxidative ('TO') or antioxidative ('AO') stability. One is an arylphosphite or arylfluorophosphite; the other is a monomolecular tri-substituted triazine in which each of three chlorine atoms on a trihalo-s-triazine is substituted with a piperazinone in which the N atom in the 4-position is alkylated. Only a trace amount of phosphite, at least 0.01 phr but less than 0.1 phr, is used so that the ratio of the piperazinone-substituted stabilizer to ester is greater than 1; additional phosphite has no noticeable effect. The trace amount of phosphite has a surprising booster effect, giving the stabilized composition excellent TO stability. Articles thermoformed from the stabilized polyolefin or copolymer thereof may be used under the hood or the dash of a vehicle, and, in containers for packaging goods, all of which articles are subject to TO degradation even if they are not subject to ultraviolet light degradation.

Thermooxidative stabilization of polyolefins with an

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

Multi-component stabilizer system for polyolefins pigmented with azo and

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

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

Excellent stabilization to bright sunlight, is obtained in polypropylene (PP) fibers pigmented with Red 144, by combining the pigment with N-(substituted)-1-(piperazin-2-one alkyl)-.alpha.-(3,5-dialkyl-4-hydroxyphenyl)-.alpha.,.alpha.-substituted acetamide ('3,5-DHPZNA' for brevity). Stabilization of the red color is obtained for as long as the PP fibers themselves are stabilized by the 3,5-DHPZNA. 3,5-DHPZNA is a known hybrid stabilizer having a hindered amine N-(substituted)-1-(piperazin-2-one alkyl) group at one end, and a hinderd phenol (3,5-dialkyl-4-hydroxyphenyl) group at the other. This particular hybrid, containing a piperazinone group, combined through a disubstituted alpha carbon atom of the acetamide in a single molecule, affords the advantages of each group with respect to its stabilization of the fiber against degradation, but without the expected adverse interaction of each group with Red 144 pigment. With 3,5-DHPZNA and Red 144 pigment, essentially no secondary stabilizer is necessary. Red PP fibers so stabilized, exhibit an acceptably low level of discoloration (color faidng) due to degradation of the pigment, over the useful life of the PP fibers. When exposed to sunlight for 6 months in Florida at a 45.degree. South exposure, the red PP fibers suffer essentially no loss of color due to degradation of the pigment. Retention of red color in articles exposed to sunlight over their useful life, is of great practical value in clothing and household goods made from woven or non-woven fabrics of Red 144-pigmented PP fibers.

Stabilized polypropylene fibers pigmented with red 144

Excellent color stabilization as well as integrity is obtained in thin film and fibers exposed to bright sunlight at relatively high temperature, in polyolefin (PO) articles pigmented with blue and green phthalocyanine, and red azo and disazo pigments. The pigment is combined with two `large molecule` primary stabilizers, the first a piperidyl-based (PDYL) hindered amine light stabilizer (HALS), and the second, a 3,5-disubstituted-tert-butyl-4-hydroxybenzoate (3,5-DHBZ). The first contains at least two polysubstituted piperidyl rings in its molecule; the second is a hindered phenol with an ester group in the para- position. Stabilization of the PO's color is obtained for as long as the PO articles themselves are stabilized by the combination of primary stabilizers, typically, their useful life. With the combination, the pigmented articles are not only thermooxidatively and light-stabilized, but there is exceptionally low color fade. Because fibers may be extruded twice for better distribution of pigment, a small amount, no more than 0.1 phr of secondary melt-stabilizers, may be used. Blue-green- and red-pigmented PO articles exhibit less than a .+-.3 change in color (color fading) due to degradation of the pigment, over a period of exposure resulting in absorption of 1240 Kjoules/m.sup.2. Such exposure of pigmented articles, deemed equivalent to normal outdoor use over a period of more than 10 years, results in essentially no visible loss of color due to degradation of the pigment.

Method for imparting improved discoloration resistance to articles

The prior art solvent process for the manufacture of an oxo-piperazinyl triazine (PIP-T) compound required carrying out the reaction between an appropriately hindered cyclic amine and cyanuric chloride in the presence of caustic catalyst, in alkylbenzene solution, typically toluene. The chloride ions generated during the reaction, in presence of water present in the reaction zone, produced serious corrosion and resulted in off-color product which had a melt absorptivity greater than 3.5 mL/gm.cm. This 'color' in the product made the product generally unmarketable. Another process to make a PIP-T termed 'the solventless' process used no toluene solvent, and no caustic but required such a very large excess of amine that the catalytic function of the amine.HCl salt went unnoticed. In the novel process, referred to as the 'hybrid' process, this catalytic function allows the use of only as much toluene in the reactor as is needed to keep the product formed and the excess amine in solution, and the use of less than a two-fold molar excess over the molar amount to displace each chlorine atom of the cyanuric chloride. The result is exceptionally high purity and yield with color no greater than that which the marketplace accepts.

Hybrid process for preparing a tri-substituted triazine

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

Thermooxidative stabilization of polymers with a N4-alkylated

Excellent color stabilization as well as fiber integrity is obtained in bright sunlight and at relatively high temperature, in polyolefin (PO) articles pigmented with phthalocyanine pigments, by combining the pigment with two `large molecule` primary stabilizers, the first a hindered amine light stabilizer (HALS) and the second a metal-organic phosphonate. The first contains at least one triazine ring, and each substitutable position on each triazine ring is substituted with an oxo-piperazinyl group; the second is a 2.1 complex of an alkylated phenol phosphonate with a Group VIII or Group IIA metal, e.g. a metal bis[O-alky(3,5-di-t-butyl-4-hytdroxybenzyl)] phosphonate ('35-DHBP'). Stabilization of the PO's color is obtained for as long as the PO articles themselves are stabilized by the combination of primary stabilizers. With the combination, phthalocyanine pigmented articles are not only thermooxidatively and light-stabilized, but there is exceptionally low color fade. Because fibers are extruded twice for better distribution of pigment, a small amount, no more than 0.1 phr of a secondary melt-stabilizer, may be used. Blue- and green-pigmented PO articles in particular, so stabilized, exhibit less than a .+-.2 change in color (color fading) due to degradation of the pigment, over exposure resulting in absorption of 1240 Kjoules. Such exposure, deemed equivalent to exposure to sunlight for about 2 years in Florida at a 45.degree. South exposure, of PP fibers pigmented with the combination of primary stabilizers suffer essentially no loss of color due to degradation of the pigmented polymer.

Multi-component stabilizer system for polyolefins pigmented with

Excellent stabilization to bright sunlight, is obtained in polypropylene (PP) fibers pigmented with Red 144, by combining the pigment with N-(substituted)-1-(piperazin-2-one alkyl)-.alpha.-(3,5-dialkyl-4-hydroxyphenyl)-.alpha.,.alpha.-substituted acetamide ('3,5-DHPZNA' for brevity). Stabilization of the red color is obtained for as long as the PP fibers themselves are stabilized by the 3,5-DHPZNA. 3,5-DHPZNA is a known hybrid stabilizer having a hindered amine N-(substituted)-1-(piperazin-2-one alkyl) group at one end, and a hindered phenol (3,5-dialkyl-4-hydroxyphenyl) group at the other. This particular hybrid, containing a piperazinone group, combined through a disubstituted alpha carbon atom of the acetamide in a single molecule, affords the advantages of each group with respect to its stabilization of the fiber against degradation, but without the expected adverse interaction of each group with Red 144 pigment. With 3,5-DHPZNA and Red 144 pigment, essentially no secondary stabilizer is necessary. Red PP fibers so stabilized, exhibit an acceptably low level of discoloration (color fading) due to degradation of the pigment, over the useful life of the PP fibers. When exposed to sunlight for 6 months in Florida at a 45.degree. South exposure, the red PP fibers suffer essentially no loss of color due to degradation of the pigment. Retention of red color in articles exposed to sunlight over their useful life, is of great practical value in clothing and household goods made from woven or non-woven fabrics of Red 144-pigmented PP fibers.

Stabilized polypropylene fibers pigmented with Red 144

A process is taught for recovering a white reaction product of a cyanuric halide with an amine reactant (white being indicative of the product's high purity), in high yield. In the absence of a solvent for either reactant, the first step comprises reacting the cyanuric halide, as a finely divided solid, with a liquid amine which is to provide a saturated heterocyclic amine group, such as a polysubstituted piperazinone, piperazine, or piperidine as the substituent for each of the three halogen atoms of the cyanuric halide used. This solventless process carried out under essentially anhydrous conditions, with a large molar excess of the amine reactant chosen, not only shortens the long time required to make the desired tri-substitution in a conventional solvent process, but also obviates using a pressurized reactor. Since (i) the reaction temperature is relatively low, (ii) there is no solvent, and (iii) the amine reactants are relatively high-boiling, and the reaction occurs in the liquid phase, there is no build-up of pressure. Fortuitously, the appropriate amount of alkanol and concentrated aqueous alkali provides a partition coefficient such that salt formed by neutralization of the excess amine hydrohalide is effectively precipitated nearly quantitatively. In addition to providing 'easy' processing conditions, the solventless reaction in our process provides higher yields than can be obtained, under comparable conditions, with the `solvent process`; a lower by-product `make` because of the low temperature and substantially atmospheric pressure used; and, the batch reaction is completed in less than 12 hr.

Solventless process for preparing a tri-substituted triazine

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

Stabilized pigmented polypropylene fiber resistant to gas fade

Excellent stabilization of polypropylene (PP) is obtained with a hindered amine containing a polysubstituted piperazin-2-one (PSP) moiety, for example, a C.sub.2 -C.sub.12 alkylene connecting two PSP moieties, or a polyalkylene polyamine having pendant substituted oxo-piperazinyltriazine moieties (PIP-T), that is, having pendant triazine rings substituted with PSP substituents. The stabilizers are particularly effective for PP irradiated with high energy gamma-radiation. Irradiated articles made from PP stabilized with such a hindered amine have improved strength and discoloration resistance, compared to articles made from polymer stabilized with several other hindered amines tested, particularly the 2,2,6,6-tetramethyl-4-piperidyl sebacate.

Stabilized gamma-irradiated polypropylene and sterilizable articles

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

Oligomeric phenylphosphonites

An improved method for the reaction of .beta.-naphthol with p-phenylenediamine to produce N,N'-di-2-naphthyl-p-phenylenediamine at lower temperatures and with decreased formation of undesirable by-products is accomplished by reacting with said materials in the presence of boric anhydride or boric acid.

Growing community of inventors

Fairview Park, OH, United States of America

George Kletecka