CA2323360A1 - Light and thermally stable polyamide - Google Patents
Light and thermally stable polyamide Download PDFInfo
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- CA2323360A1 CA2323360A1 CA002323360A CA2323360A CA2323360A1 CA 2323360 A1 CA2323360 A1 CA 2323360A1 CA 002323360 A CA002323360 A CA 002323360A CA 2323360 A CA2323360 A CA 2323360A CA 2323360 A1 CA2323360 A1 CA 2323360A1
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- nylon
- polyamide
- tetramethylpiperidine
- tetramethyl
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
A light and thermally stable polyamide having built-in stabilizers is prepared by polymerizing polyamide-forming monomers in the presence of an effective amount of at least one hindered piperidine compound and at least one aliphatic, dicarboxylic acid chain regulating compound.
Description
LIGHT AND THERMALLY STABLE POLYAMIDE
Description This invention relates to a polyamide that achieves high light and heat stability. More particularly, this invention relates to a modified nylon polymer containing a hindered piperidine compound and a chain regulator, wherein the modified nylon poly-mer has an improved stability to light and heat.
It is known that when unaided nylon is exposed to light and/or heat, the nylon discolors and loses its physical properties such as strength retention and resistance to elongation. Therefore, the addition of light and/or heat stabilizers to nylon is neces-sary in some cases in order for nylon to achieve acceptable per-formance. The stabilizers may be added before, during, or after polymerization. The conventional stabilizers are admixed with the polymer and are not bound to the polymer chain; therefore, during processing or use of the polyamide, the stabilizers can readily migrate out of the polymer, evaporate, or be washed out. This means that the activity of the stabilization is reduced in an un-desired manner, and impurities are released to the surroundings (e. g., air, dye bath, etc.).
Various organic stabilizers are known for use with nylon and ar-ticles manufactured therefrom. One problem, however, is that organic stabilizers such as, for example, hindered phenols, are expensive and have limited effectiveness.
Inorganic stabilizers are generally less expensive and more ef-fective than organic stabilizers; however, inorganic stabilizers suffer from a different set of problems. Typically, common inorganic stabilizers such as, for example, copper compounds, cause problems during processing. For example, in the melt extrusion process, copper compounds, may be reduced to insoluble elemental copper. Formation of elemental copper reduces produc-tion efficiency and adds significant equipment maintenance costs.
Furthermore, the removal of copper deposits generates environmen-tally-undesirable effluent. In other processes such as, for example, the treatment of automotive nylon fibers with copper complexes in a dye bath, the excess copper complexes that are in the bath also produce environmentally-undesirable effluent.
Commonly owned United States Serial No. 08/804,312 relates to a process for preparing photochemically-stable, dyed nylon composi-tions comprising providing to a dye bath a shaped article of poly(epsilon-caprolactam) hydrolytically polymerized in the pre-sence of water and a hindered piperidine derivative and, in the dye bath, dyeing the shaped article with one or more metalized or nonmetalized acid dyestuffs.
Commonly owned United States Serial No. 60/045,269 relates to a process for making stabilized solution-dyed fibers by melting a polyamide comprising amide monomers polymerized in the presence of at least one hindered piperidine compound and coloring the melted polyamide with a colorant.
A PCT application, International Application No. PCT/EP 95/01349, describes an inherently stabilized polyamide containing at least one triacetone diamine compound having a primary amino group (-NH2) that reacts with a carboxy end group of the polyamide mole-cule during polymerization, thus rendering the polymer light and heat stable.
An essay in Poly. Deg. And Stab. 21, 251-262 (1988) describes the improvement of the light stability of polyamide 6/6 by the addi-tion of 2,2,6,6-tetramethylpiperidin-4-of ("TMP"). In a reconden-sation of the TMP-containing polyamide 6/6 in the melt at 275°C
under an atmosphere of water vapor, the authors claim that TMP
reacts with the carboxyl end groups of the polyamide.
A need, therefore, exists for a modified polyamide that reduces the need for copper-based stabilizers and that avoids discolora-tion, i.e., yellowing after exposure to light and/or heat. Furt-hermore, it would be desirable to produce a polyamide having an improved resistance to yellowing upon exposure to light and/or heat, especially in engineering plastics applications.
It is an object of the present invention to provide a modified polyamide that avoids discoloration after exposure to light and/
or heat.
Another object of the present invention is to reduce the need for copper-based stabilizers in polyamides.
Yet another object of the present invention is to provide an en-vironmentally-friendly and efficient process of producing a modified polyamide that is both light and heat stable.
Thus, according to one embodiment of the present invention, there is provided a method of making a light and thermally stable poly-amide with built-in stabilizers. The method comprises subjecting one or more polyamide-forming monomers to a polymerization pro-3 PC'T/EP99/00889 cess in the presence of an effective amount of at least one hin-dered piperidine compound and an effective amount at least one aliphatic, dicarboxylic acid chain regulating compound.
In another aspect, the present invention is directed to a light and thermally stable polyamide comprising a backbone polymer chain, at least one hindered piperidine radical, and at least one aliphatic, dicarboxylic acid chain regulating compound wherein the at least one hindered piperidine radical and the at least one aliphatic, dicarboxylic acid chain regulating compound are chemically bonded to the backbone polymer chain. The polyamide of the present invention is substantially free from copper compounds.
The modified polyamide with built-in stabilizers made according to the present invention achieves good light and heat stability without the use of other stabilizers such as, for example, copper salts. The combination of at least one aliphatic, dicarboxylic acid chain regulating compound and at least one hindered piperidine compound not only functions as a molecular weight re-gulator in the polymerization process, but also endows the resul-ting polyamide with light and heat stability. The modified poly-amide of the present invention does not discolor in the early stage of ultraviolet exposure.
2s The above and other objects, effects, features, and advantages of the present invention will become more apparent from the follo-wing detailed description of the preferred embodiments thereof, particularly when viewed in conjunction with the accompanying fi-gures.
FIG. 1 is a graph illustrating the percent strength retained for solution-dyed yarns after exposure in a weatherometer.
FIG. 2 is a graph illustrating the yellowing of polymer plaques after exposure in a weatherometer.
To promote an understanding of the principles of the present in-vention, descriptions of specific embodiments of the invention follow, and specific language is used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is intended by the use of this specific language and that alterations, modifications, equivalents, and further ap-plications of the principles of the invention discussed are con-templated as would normally occur to one of ordinary skill in the art to which the invention pertains.
Description This invention relates to a polyamide that achieves high light and heat stability. More particularly, this invention relates to a modified nylon polymer containing a hindered piperidine compound and a chain regulator, wherein the modified nylon poly-mer has an improved stability to light and heat.
It is known that when unaided nylon is exposed to light and/or heat, the nylon discolors and loses its physical properties such as strength retention and resistance to elongation. Therefore, the addition of light and/or heat stabilizers to nylon is neces-sary in some cases in order for nylon to achieve acceptable per-formance. The stabilizers may be added before, during, or after polymerization. The conventional stabilizers are admixed with the polymer and are not bound to the polymer chain; therefore, during processing or use of the polyamide, the stabilizers can readily migrate out of the polymer, evaporate, or be washed out. This means that the activity of the stabilization is reduced in an un-desired manner, and impurities are released to the surroundings (e. g., air, dye bath, etc.).
Various organic stabilizers are known for use with nylon and ar-ticles manufactured therefrom. One problem, however, is that organic stabilizers such as, for example, hindered phenols, are expensive and have limited effectiveness.
Inorganic stabilizers are generally less expensive and more ef-fective than organic stabilizers; however, inorganic stabilizers suffer from a different set of problems. Typically, common inorganic stabilizers such as, for example, copper compounds, cause problems during processing. For example, in the melt extrusion process, copper compounds, may be reduced to insoluble elemental copper. Formation of elemental copper reduces produc-tion efficiency and adds significant equipment maintenance costs.
Furthermore, the removal of copper deposits generates environmen-tally-undesirable effluent. In other processes such as, for example, the treatment of automotive nylon fibers with copper complexes in a dye bath, the excess copper complexes that are in the bath also produce environmentally-undesirable effluent.
Commonly owned United States Serial No. 08/804,312 relates to a process for preparing photochemically-stable, dyed nylon composi-tions comprising providing to a dye bath a shaped article of poly(epsilon-caprolactam) hydrolytically polymerized in the pre-sence of water and a hindered piperidine derivative and, in the dye bath, dyeing the shaped article with one or more metalized or nonmetalized acid dyestuffs.
Commonly owned United States Serial No. 60/045,269 relates to a process for making stabilized solution-dyed fibers by melting a polyamide comprising amide monomers polymerized in the presence of at least one hindered piperidine compound and coloring the melted polyamide with a colorant.
A PCT application, International Application No. PCT/EP 95/01349, describes an inherently stabilized polyamide containing at least one triacetone diamine compound having a primary amino group (-NH2) that reacts with a carboxy end group of the polyamide mole-cule during polymerization, thus rendering the polymer light and heat stable.
An essay in Poly. Deg. And Stab. 21, 251-262 (1988) describes the improvement of the light stability of polyamide 6/6 by the addi-tion of 2,2,6,6-tetramethylpiperidin-4-of ("TMP"). In a reconden-sation of the TMP-containing polyamide 6/6 in the melt at 275°C
under an atmosphere of water vapor, the authors claim that TMP
reacts with the carboxyl end groups of the polyamide.
A need, therefore, exists for a modified polyamide that reduces the need for copper-based stabilizers and that avoids discolora-tion, i.e., yellowing after exposure to light and/or heat. Furt-hermore, it would be desirable to produce a polyamide having an improved resistance to yellowing upon exposure to light and/or heat, especially in engineering plastics applications.
It is an object of the present invention to provide a modified polyamide that avoids discoloration after exposure to light and/
or heat.
Another object of the present invention is to reduce the need for copper-based stabilizers in polyamides.
Yet another object of the present invention is to provide an en-vironmentally-friendly and efficient process of producing a modified polyamide that is both light and heat stable.
Thus, according to one embodiment of the present invention, there is provided a method of making a light and thermally stable poly-amide with built-in stabilizers. The method comprises subjecting one or more polyamide-forming monomers to a polymerization pro-3 PC'T/EP99/00889 cess in the presence of an effective amount of at least one hin-dered piperidine compound and an effective amount at least one aliphatic, dicarboxylic acid chain regulating compound.
In another aspect, the present invention is directed to a light and thermally stable polyamide comprising a backbone polymer chain, at least one hindered piperidine radical, and at least one aliphatic, dicarboxylic acid chain regulating compound wherein the at least one hindered piperidine radical and the at least one aliphatic, dicarboxylic acid chain regulating compound are chemically bonded to the backbone polymer chain. The polyamide of the present invention is substantially free from copper compounds.
The modified polyamide with built-in stabilizers made according to the present invention achieves good light and heat stability without the use of other stabilizers such as, for example, copper salts. The combination of at least one aliphatic, dicarboxylic acid chain regulating compound and at least one hindered piperidine compound not only functions as a molecular weight re-gulator in the polymerization process, but also endows the resul-ting polyamide with light and heat stability. The modified poly-amide of the present invention does not discolor in the early stage of ultraviolet exposure.
2s The above and other objects, effects, features, and advantages of the present invention will become more apparent from the follo-wing detailed description of the preferred embodiments thereof, particularly when viewed in conjunction with the accompanying fi-gures.
FIG. 1 is a graph illustrating the percent strength retained for solution-dyed yarns after exposure in a weatherometer.
FIG. 2 is a graph illustrating the yellowing of polymer plaques after exposure in a weatherometer.
To promote an understanding of the principles of the present in-vention, descriptions of specific embodiments of the invention follow, and specific language is used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is intended by the use of this specific language and that alterations, modifications, equivalents, and further ap-plications of the principles of the invention discussed are con-templated as would normally occur to one of ordinary skill in the art to which the invention pertains.
As used herein, the term "polyamide" denotes homopolymers, copolymers, blends, and grafts of those long chain polymers ha-ving recurring amide groups (-CO-NH-) as an integral part of the main polymer chain. These long chain polyamides are generally re-ferred to as "nylons."
As used herein with respect to the polyamide of this invention, the term "built-in" means that the components that render the polyamide light and heat stable are chemically bonded to the backbone polymer chain of the polyamide rather than merely physi-cally admixed with the polyamide.
In one embodiment, the present invention is a modified polyamide substantially free of copper compounds comprising a backbone po-lymer chain, at least one hindered piperidine radical, and at least one aliphatic, dicarboxylic acid chain regulating compound wherein the at least one hindered piperidine radical and the at least one aliphatic, dicarboxylic acid chain regulating compound are chemically bonded to the backbone polymer chain. The light and thermally stable polyamide of the present invention may be nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6T, nylon 6/12, nylon 4/6, nylon 11, nylon 12, or aromatic nylons such as, for example, poly(meta-phenylene isophthalamide) and poly(para-pheny-lene terephthalamide). Preferably, the light and thermally stable polyamide of this invention is nylon 6, nylon 6/6, nylon 6T, ny-lon 6/12, and nylon 4/6. Most preferably, the light and thermally stable polyamide of the present invention is nylon 6.
Any suitable polyamide-forming monomers may be used to form the light and thermally stable polyamide of the present invention.
Nonlimiting examples of such suitable polyamide-forming monomers are diamine compounds, dicarboxylic.acids, caprolactam monomers, and combinations thereof. In a preferred embodiment of the pre-sent invention, the polyamide-forming monomers are composed of caprolactam monomers.
The polymerization process by which the polyamide of the present invention is formed is preferably carried out according to con-ventional processes such as, for example, those described in U.S.
Patent No. 5,149,758 to Matthies, the entirety of which is herein incorporated by reference, except that the polymerization of the present invention is carried out in the presence of an effective amount of one or more hindered piperidine compounds and an effec-tive amount of one or more aliphatic, dicarboxylic acid chain re-gulating compounds. An effective amount of at least one hindered piperidine compound is an amount sufficient in combination with the one or more aliphatic, dicarboxylic acid chain regulating compounds to render the resultant polyamide light and thermally stable. Preferably, the effective amount of the one or more hin-dered piperidine compounds is in the range of about 0.030 to ab-out 0.800, and more preferably about 0.060 to about 0.400, mole 5 percent based on the weight of the polyamide-forming monomers used. An effective amount of at least one aliphatic, dicarboxylic acid chain regulating compound is an amount sufficient in combi-nation with the one or more hindered piperidine compounds to ren-der the resultant polyamide light and thermally stable. Prefera-bly, the effective amount of the one or more aliphatic, dicarb-oxylic chain regulating compounds is in the range of about 0.001 to about 0.800, and more preferably about 0.050 to about 0.500, mole percent based on the weight of the polyamide-forming monomers used.
To make the polyamide of the present invention, the one or more hindered amine compounds and the one or more aliphatic, dicarb-oxylic acid chain regulating compounds are added to the starting monomers or to the polymerizing reaction mixture. Thus, the one or more hindered piperidine compounds, the one or more aliphatic, dicarboxylic acid chain regulating compounds, and the polyamide-forming monomers may be added separately or as a mixture to a re-actor in which polymerization is effected.
The hindered piperidine compound used in the present invention is represented by the formula:
H H Rz Rz H
Ri %
wherein R1 comprises an amine- or amide-forming functional group, Rz is an alkyl, and R3 is selected from the group consisting of hydrogen, C1-C3 alkyl groups, and -OR4 where R4 is selected from the group consisting of hydrogen, methyl, and C1-C7 alkyl groups.
R1 is preferably selected from the group consisting of -NHRS where R5 is hydrogen or a C1-Ce alkyl, carboxyl, carboxylic acid deriva-tive, -(CHz)X(NH)R5 where x is an integer of from 1 to about 6, -(CHZ)yCOOH where y is an integer of from 1 to about 6, and -(CHz)yCOOH acid derivative. The hindered piperidine compound used in the present invention is preferably an amino polyalkylpiperi-dine or a polyalkylpiperidine acid. Nonlimiting examples of such hindered piperidine compounds include:
4-amino-2,2,6,6-tetramethylpiperidine;
4-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine;
3-amino-2,2,6,6-tetramethylpiperidine;
3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine;
2,2,6,6-tetramethyl-4-piperidinecarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinealkylcarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinealkyl/arylcarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinecarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinearylcarboxylic acid; and 2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid.
The hindered amine compound may be a mixture of hindered piperidine compounds as well. More preferably, the hindered piperidine compound is a 2,2,6,6-tetraalkylpiperidine. Most pre-ferably, the hindered piperidine compound is 4-amino-2,2,6,6-te-tramethylpiperidine.
Suitable chain regulating compounds for use in the present inven-tion are aliphatic, dicarboxylic acids and combinations thereof.
Non-limiting examples of such aliphatic, dicarboxylic acids inc-lude the following:
malic acid;
malonic acid;
methylmalonic acid;
ethylmalonic acid;
butylmalonic acid;
dimethylmalonic acid, succinic acid;
methylsuccinic acid;
2,2-dimethylsuccinic acid;
2,3-dimethylsuccinic acid;
2-ethyl-2-methylsuccinic acid;
glutaric acid;
2,2-dimethylglutaric acid;
2,3-dimethylglutaric acid;
2,4-dimethylglutaric acid;
adipic acid;
As used herein with respect to the polyamide of this invention, the term "built-in" means that the components that render the polyamide light and heat stable are chemically bonded to the backbone polymer chain of the polyamide rather than merely physi-cally admixed with the polyamide.
In one embodiment, the present invention is a modified polyamide substantially free of copper compounds comprising a backbone po-lymer chain, at least one hindered piperidine radical, and at least one aliphatic, dicarboxylic acid chain regulating compound wherein the at least one hindered piperidine radical and the at least one aliphatic, dicarboxylic acid chain regulating compound are chemically bonded to the backbone polymer chain. The light and thermally stable polyamide of the present invention may be nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6T, nylon 6/12, nylon 4/6, nylon 11, nylon 12, or aromatic nylons such as, for example, poly(meta-phenylene isophthalamide) and poly(para-pheny-lene terephthalamide). Preferably, the light and thermally stable polyamide of this invention is nylon 6, nylon 6/6, nylon 6T, ny-lon 6/12, and nylon 4/6. Most preferably, the light and thermally stable polyamide of the present invention is nylon 6.
Any suitable polyamide-forming monomers may be used to form the light and thermally stable polyamide of the present invention.
Nonlimiting examples of such suitable polyamide-forming monomers are diamine compounds, dicarboxylic.acids, caprolactam monomers, and combinations thereof. In a preferred embodiment of the pre-sent invention, the polyamide-forming monomers are composed of caprolactam monomers.
The polymerization process by which the polyamide of the present invention is formed is preferably carried out according to con-ventional processes such as, for example, those described in U.S.
Patent No. 5,149,758 to Matthies, the entirety of which is herein incorporated by reference, except that the polymerization of the present invention is carried out in the presence of an effective amount of one or more hindered piperidine compounds and an effec-tive amount of one or more aliphatic, dicarboxylic acid chain re-gulating compounds. An effective amount of at least one hindered piperidine compound is an amount sufficient in combination with the one or more aliphatic, dicarboxylic acid chain regulating compounds to render the resultant polyamide light and thermally stable. Preferably, the effective amount of the one or more hin-dered piperidine compounds is in the range of about 0.030 to ab-out 0.800, and more preferably about 0.060 to about 0.400, mole 5 percent based on the weight of the polyamide-forming monomers used. An effective amount of at least one aliphatic, dicarboxylic acid chain regulating compound is an amount sufficient in combi-nation with the one or more hindered piperidine compounds to ren-der the resultant polyamide light and thermally stable. Prefera-bly, the effective amount of the one or more aliphatic, dicarb-oxylic chain regulating compounds is in the range of about 0.001 to about 0.800, and more preferably about 0.050 to about 0.500, mole percent based on the weight of the polyamide-forming monomers used.
To make the polyamide of the present invention, the one or more hindered amine compounds and the one or more aliphatic, dicarb-oxylic acid chain regulating compounds are added to the starting monomers or to the polymerizing reaction mixture. Thus, the one or more hindered piperidine compounds, the one or more aliphatic, dicarboxylic acid chain regulating compounds, and the polyamide-forming monomers may be added separately or as a mixture to a re-actor in which polymerization is effected.
The hindered piperidine compound used in the present invention is represented by the formula:
H H Rz Rz H
Ri %
wherein R1 comprises an amine- or amide-forming functional group, Rz is an alkyl, and R3 is selected from the group consisting of hydrogen, C1-C3 alkyl groups, and -OR4 where R4 is selected from the group consisting of hydrogen, methyl, and C1-C7 alkyl groups.
R1 is preferably selected from the group consisting of -NHRS where R5 is hydrogen or a C1-Ce alkyl, carboxyl, carboxylic acid deriva-tive, -(CHz)X(NH)R5 where x is an integer of from 1 to about 6, -(CHZ)yCOOH where y is an integer of from 1 to about 6, and -(CHz)yCOOH acid derivative. The hindered piperidine compound used in the present invention is preferably an amino polyalkylpiperi-dine or a polyalkylpiperidine acid. Nonlimiting examples of such hindered piperidine compounds include:
4-amino-2,2,6,6-tetramethylpiperidine;
4-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine;
3-amino-2,2,6,6-tetramethylpiperidine;
3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine;
2,2,6,6-tetramethyl-4-piperidinecarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinealkylcarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-4-piperidinealkyl/arylcarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinecarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid;
2,2,6,6-tetramethyl-3-piperidinearylcarboxylic acid; and 2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid.
The hindered amine compound may be a mixture of hindered piperidine compounds as well. More preferably, the hindered piperidine compound is a 2,2,6,6-tetraalkylpiperidine. Most pre-ferably, the hindered piperidine compound is 4-amino-2,2,6,6-te-tramethylpiperidine.
Suitable chain regulating compounds for use in the present inven-tion are aliphatic, dicarboxylic acids and combinations thereof.
Non-limiting examples of such aliphatic, dicarboxylic acids inc-lude the following:
malic acid;
malonic acid;
methylmalonic acid;
ethylmalonic acid;
butylmalonic acid;
dimethylmalonic acid, succinic acid;
methylsuccinic acid;
2,2-dimethylsuccinic acid;
2,3-dimethylsuccinic acid;
2-ethyl-2-methylsuccinic acid;
glutaric acid;
2,2-dimethylglutaric acid;
2,3-dimethylglutaric acid;
2,4-dimethylglutaric acid;
adipic acid;
3-methyladipic acid;
azelaic acid;
pimelic acid;
sebacic acid;
decanedicarboxylic acid; and dodecanedioic acid.
The aliphatic, dicarboxylic acid chain regulating compound used in the present invention may be the same or different from a dicarboxylic acid that is used as a polyamide-forming compound.
The aliphatic, dicarboxylic acid chain regulating compound is preferably selected from the group consisting of C4-Clo alkane dicarboxylic acids, particularly adipic acid, azelaic acid, seba-cic acid, and decanedicarboxylic acid. Most preferably, the aliphatic, dicarboxylic acid chain regulating compound is adipic acid.
Of course, various non-stabilizing additives may be used in the modified polyamide of the present invention. These include, for example and without limitation, lubricants, nucleating agents, antioxidants, antistatic agents, etc.
The present invention produces a modified polyamide that is sta-bilized from degradation by light and heat and that does not di-scolor, i.e., yellow, upon exposure to light and/or heat. With the present invention, it is not necessary to use other stabili-zers such as, for example, copper compounds, as additives, alt-hough other stabilizers may be present, if desired. If such other stabilizers are present, they are present in significantly redu-ced amounts. The elimination of such stabilizing additives redu-ces equipment maintenance costs and eliminates harmful effluents produced in the removal of stabilizer deposits.
The present invention also produces a modified polyamide having increased spinning efficiency. Spinning efficiency is increased by at least about 0.5 percent. Such increase in spinning effi-ciency translates into hundreds of thousands of dollars in redu-ced annual manufacturing costs. While not wishing to be bound by any theory, it is currently believed that the increased spinning efficiency results from that fact that the modified polyamide of the present invention has a narrower molecular weight distribu-tion than acetic acid- and propionic acid-regulated polyamides.
For polymers having a relative viscosity of 2.7, the molecular weight distribution of the modified polyamide of the present in-vention is about 1.65 to about 1.80, and the molecular weight distribution of acetic acid- and propionic acid-regulated poly-amides is about 1.90 to about 2.00.
The present invention is further directed to articles produced from the light and thermally stable polyamide of the present in vention and to methods of producing such articles. Non-limiting examples of such articles include fibers, yarns, carpets, engi-neering plastics such as automotive parts, and the like. Fibers may be formed by subjecting the light and thermally stable poly-amides of the present invention to any conventional fiber-forming process such as, for example, that disclosed in U.S. Patents Nos.
4,983,448 to Karageorgiou and 5,487,860 to Kent et al., the ent-irety of both of which are incorporated herein by reference. Pre-ferably, the fiber-forming process involves rapidly spinning the light and thermally stable polyamide at take-off speeds of at least about 4,000 m/min. Engineering plastics may be formed by subjecting the light and thermally stable polyamides of the pre-sent invention to any conventional plastic-forming process such as, for example, that disclosed in U.S. Patent No. 5,474,853 to Watanabe et al., the entirety of which is incorporated herein by ref erence .
Fibers formed from the light and thermally stable polyamides of the present invention may be dyed with conventional dyes used to dye nylons such as, for example, metalized and non-metalized acid dyes. Usual dyebath conditions for dyeing nylon can be employed.
The following general conditions are exemplary and not intended to be limiting. A dyebath is prepared at a volume equal to about 20 times the weight of the articles to be dyed. Processing chemicals are added including a chelating agent to prevent the deposition or complexing of metal ions in hard water, a dye leve-ling agent, and, in the case of metalized acid dyes, an acid donor to slowly lower the dyebath pH. The dyestuff is added, and the dyebath pH is adjusted. The solution is heated to the desired temperature of typically about from 95°C to about 110°C at a rate of from about 0.5°C to about 3.0°C per minute and is held at that temperature for about 30 minutes to about 60 minutes. The dyebath is cooled or emptied, and the articles are thoroughly rinsed with fresh water. The dyed articles are dried in a tumble drier or an oven such as a Tenter oven.
Alternatively, fibers made from the light and thermally stable polyamides of the present invention may be solution-dyed before being formed into articles. Usual conditions for solution-dyeing nylon can be employed. The following general conditions are exem-plary and not intended to be limiting. The polyamide of the pre-sent invention is melted and colored with a colorant selected from the group consisting of pigments, dyes, any colored compound with properties between pigments and dyes, and combinations the-reof. The colored polyamide is then spun into fibers or fabric according to conventional methods such as, for example, those disclosed in U.S. Patent No. 4,983,448 to Karageorgiou, U.S. Pa-tent No. 5,487,860 to Kent et al., and U.S. Patent No. 4,918,947 to Speich. For engineering plastics, polymer chips are mixed with colored compounds such as, for example, pigments and dyes, before charging into an extruder. The mixing before being charged into the extruder is a physical mix, not a melt mix.
The invention will be further described by reference to the fol-lowing detailed examples. The examples are set forth by way of illustration and are not intended to limit the scope of the in-vention. In the examples, "ADA" refers to adipic acid, "PPA" re-f ers to propionic acid, "TPA" refers to terephthalic acid, and "TAD" refers to 4-amino-2,2,6,6-tetramethylpiperidine. Also as used in the examples, the following terms and test conditions are defined as follows:
ao Weight Percent.
The weight percentage of that component in the charge.
Relative Viscosity (RV).
The relative viscosity compares the viscosity of a solution of polymer in formic acid with the viscosity of the formic acid it-self (ASTM D 789). The test results reported herein were obtained using 0.20 g of nylon 6 dissolved in 20 cc. of formic acid at 25°C.
End Group Content.
The amino end group content is determined by dissolving about 2.0 g of the polymer in about 60 cc. of a phenol-methanol mixture (68:32). This solution is titrated with about 0.20 normal HC1 at about 25°C by a potentiometric method, wherein the endpoint is de-termined by a steep potential increase.
The carboxy end group content is determined by dissolving about 0.30 g of the polymer in about 40 cc. of a mixture of benzyl al-cohol at 180°C. The solution is titrated with about 0.03 normal t-butyl ammonium hydroxide at about 80°C to about 100°C by a po-tentiometric method, wherein the endpoint is determined by a steep potential increase.
Exposure Test.
This test is designed to simulate extreme environmental condi-tions encountered inside a vehicle due to sunlight, heat, and hu-5 midity for the purpose of predicting the performance of auto-motive interior trim materials. This test measures the amount of yellowing (the delta b* value) of each of the exposed samples.
This test is performed in accordance with the GM SAE J1885 Test Method, which is entitled "Accelerated Exposure of Automotive In-10 terior Trim Components using a Controlled Irradiance Water-Cooled Xenon-Arc Apparatus."
Strength Retention.
This test is designed to determine the strength retention of the controls and the experimental samples. The term "strength reten-tion" ref ers to the change in tenacity of the material as a re-sult of exposure of the material to sunlight or an artificial light source. The tenacity is a measure of fiber strength. This test is performed in accordance with the AATCC Test Method 16-1993, Colorfastness to Light, Option E (Water-Cooled Xenon-Arc Lamp, Continuous Light). The materials are exposed for 2125 kJ of exposure, and the tenacity of each material is measured before exposure and after each 425 kJ increment of exposure. Percent strength retention is determined as follows:
Tenaci after ex op sure x 100%
Tenacity before exposure EXAMPLE 1 (Comparative) Polymerization of PPA/TAD-Regulated Nylon 6 A mixture of 75 kg of caprolactam, 1800 g of water, 135 g (0.18 weight percent) propionic acid, and 112.5 g (0.15 weight percent) 4-amino-2,2,6,6-tetramethylpiperidine is charged into a 250-liter autoclave. The mixture is heated to 270°C in one hour, while the pressure increases to 60 psi (3102 mm Hg). After holding the mix-ture at 60 psi for 30 minutes, the pressure is slowly released.
To accelerate the polymerization, the system is placed under a vacuum of 400 mm Hg for 75 minutes. The polymer is then extruded under a positive nitrogen pressure and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.71. The amino group content measu-res 42 meq/kg, and the carboxylic end group content measures 45 meq/kg.
azelaic acid;
pimelic acid;
sebacic acid;
decanedicarboxylic acid; and dodecanedioic acid.
The aliphatic, dicarboxylic acid chain regulating compound used in the present invention may be the same or different from a dicarboxylic acid that is used as a polyamide-forming compound.
The aliphatic, dicarboxylic acid chain regulating compound is preferably selected from the group consisting of C4-Clo alkane dicarboxylic acids, particularly adipic acid, azelaic acid, seba-cic acid, and decanedicarboxylic acid. Most preferably, the aliphatic, dicarboxylic acid chain regulating compound is adipic acid.
Of course, various non-stabilizing additives may be used in the modified polyamide of the present invention. These include, for example and without limitation, lubricants, nucleating agents, antioxidants, antistatic agents, etc.
The present invention produces a modified polyamide that is sta-bilized from degradation by light and heat and that does not di-scolor, i.e., yellow, upon exposure to light and/or heat. With the present invention, it is not necessary to use other stabili-zers such as, for example, copper compounds, as additives, alt-hough other stabilizers may be present, if desired. If such other stabilizers are present, they are present in significantly redu-ced amounts. The elimination of such stabilizing additives redu-ces equipment maintenance costs and eliminates harmful effluents produced in the removal of stabilizer deposits.
The present invention also produces a modified polyamide having increased spinning efficiency. Spinning efficiency is increased by at least about 0.5 percent. Such increase in spinning effi-ciency translates into hundreds of thousands of dollars in redu-ced annual manufacturing costs. While not wishing to be bound by any theory, it is currently believed that the increased spinning efficiency results from that fact that the modified polyamide of the present invention has a narrower molecular weight distribu-tion than acetic acid- and propionic acid-regulated polyamides.
For polymers having a relative viscosity of 2.7, the molecular weight distribution of the modified polyamide of the present in-vention is about 1.65 to about 1.80, and the molecular weight distribution of acetic acid- and propionic acid-regulated poly-amides is about 1.90 to about 2.00.
The present invention is further directed to articles produced from the light and thermally stable polyamide of the present in vention and to methods of producing such articles. Non-limiting examples of such articles include fibers, yarns, carpets, engi-neering plastics such as automotive parts, and the like. Fibers may be formed by subjecting the light and thermally stable poly-amides of the present invention to any conventional fiber-forming process such as, for example, that disclosed in U.S. Patents Nos.
4,983,448 to Karageorgiou and 5,487,860 to Kent et al., the ent-irety of both of which are incorporated herein by reference. Pre-ferably, the fiber-forming process involves rapidly spinning the light and thermally stable polyamide at take-off speeds of at least about 4,000 m/min. Engineering plastics may be formed by subjecting the light and thermally stable polyamides of the pre-sent invention to any conventional plastic-forming process such as, for example, that disclosed in U.S. Patent No. 5,474,853 to Watanabe et al., the entirety of which is incorporated herein by ref erence .
Fibers formed from the light and thermally stable polyamides of the present invention may be dyed with conventional dyes used to dye nylons such as, for example, metalized and non-metalized acid dyes. Usual dyebath conditions for dyeing nylon can be employed.
The following general conditions are exemplary and not intended to be limiting. A dyebath is prepared at a volume equal to about 20 times the weight of the articles to be dyed. Processing chemicals are added including a chelating agent to prevent the deposition or complexing of metal ions in hard water, a dye leve-ling agent, and, in the case of metalized acid dyes, an acid donor to slowly lower the dyebath pH. The dyestuff is added, and the dyebath pH is adjusted. The solution is heated to the desired temperature of typically about from 95°C to about 110°C at a rate of from about 0.5°C to about 3.0°C per minute and is held at that temperature for about 30 minutes to about 60 minutes. The dyebath is cooled or emptied, and the articles are thoroughly rinsed with fresh water. The dyed articles are dried in a tumble drier or an oven such as a Tenter oven.
Alternatively, fibers made from the light and thermally stable polyamides of the present invention may be solution-dyed before being formed into articles. Usual conditions for solution-dyeing nylon can be employed. The following general conditions are exem-plary and not intended to be limiting. The polyamide of the pre-sent invention is melted and colored with a colorant selected from the group consisting of pigments, dyes, any colored compound with properties between pigments and dyes, and combinations the-reof. The colored polyamide is then spun into fibers or fabric according to conventional methods such as, for example, those disclosed in U.S. Patent No. 4,983,448 to Karageorgiou, U.S. Pa-tent No. 5,487,860 to Kent et al., and U.S. Patent No. 4,918,947 to Speich. For engineering plastics, polymer chips are mixed with colored compounds such as, for example, pigments and dyes, before charging into an extruder. The mixing before being charged into the extruder is a physical mix, not a melt mix.
The invention will be further described by reference to the fol-lowing detailed examples. The examples are set forth by way of illustration and are not intended to limit the scope of the in-vention. In the examples, "ADA" refers to adipic acid, "PPA" re-f ers to propionic acid, "TPA" refers to terephthalic acid, and "TAD" refers to 4-amino-2,2,6,6-tetramethylpiperidine. Also as used in the examples, the following terms and test conditions are defined as follows:
ao Weight Percent.
The weight percentage of that component in the charge.
Relative Viscosity (RV).
The relative viscosity compares the viscosity of a solution of polymer in formic acid with the viscosity of the formic acid it-self (ASTM D 789). The test results reported herein were obtained using 0.20 g of nylon 6 dissolved in 20 cc. of formic acid at 25°C.
End Group Content.
The amino end group content is determined by dissolving about 2.0 g of the polymer in about 60 cc. of a phenol-methanol mixture (68:32). This solution is titrated with about 0.20 normal HC1 at about 25°C by a potentiometric method, wherein the endpoint is de-termined by a steep potential increase.
The carboxy end group content is determined by dissolving about 0.30 g of the polymer in about 40 cc. of a mixture of benzyl al-cohol at 180°C. The solution is titrated with about 0.03 normal t-butyl ammonium hydroxide at about 80°C to about 100°C by a po-tentiometric method, wherein the endpoint is determined by a steep potential increase.
Exposure Test.
This test is designed to simulate extreme environmental condi-tions encountered inside a vehicle due to sunlight, heat, and hu-5 midity for the purpose of predicting the performance of auto-motive interior trim materials. This test measures the amount of yellowing (the delta b* value) of each of the exposed samples.
This test is performed in accordance with the GM SAE J1885 Test Method, which is entitled "Accelerated Exposure of Automotive In-10 terior Trim Components using a Controlled Irradiance Water-Cooled Xenon-Arc Apparatus."
Strength Retention.
This test is designed to determine the strength retention of the controls and the experimental samples. The term "strength reten-tion" ref ers to the change in tenacity of the material as a re-sult of exposure of the material to sunlight or an artificial light source. The tenacity is a measure of fiber strength. This test is performed in accordance with the AATCC Test Method 16-1993, Colorfastness to Light, Option E (Water-Cooled Xenon-Arc Lamp, Continuous Light). The materials are exposed for 2125 kJ of exposure, and the tenacity of each material is measured before exposure and after each 425 kJ increment of exposure. Percent strength retention is determined as follows:
Tenaci after ex op sure x 100%
Tenacity before exposure EXAMPLE 1 (Comparative) Polymerization of PPA/TAD-Regulated Nylon 6 A mixture of 75 kg of caprolactam, 1800 g of water, 135 g (0.18 weight percent) propionic acid, and 112.5 g (0.15 weight percent) 4-amino-2,2,6,6-tetramethylpiperidine is charged into a 250-liter autoclave. The mixture is heated to 270°C in one hour, while the pressure increases to 60 psi (3102 mm Hg). After holding the mix-ture at 60 psi for 30 minutes, the pressure is slowly released.
To accelerate the polymerization, the system is placed under a vacuum of 400 mm Hg for 75 minutes. The polymer is then extruded under a positive nitrogen pressure and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.71. The amino group content measu-res 42 meq/kg, and the carboxylic end group content measures 45 meq/kg.
Polymerization of ADA/TAD-Regulated Nylon 6 A mixture of 75 kg of caprolactam, 1800 g of water, 240 g (0.32 weight percent) adipic acid, and 112.5 g (0.15 weight percent) 4-amino-2,2,6,6-tetramethylpiperidine is charged into a 250-liter autoclave. The mixture is heated to 270°C in one hour, while the pressure increases to 60 psi (3102 mm Hg). After holding the mix-ture at 60 psi for 30 minutes, the pressure is slowly released.
To accelerate the polymerization, the system is placed under a vacuum of 500 mm Hg for 45 minutes. The polymer is then extruded under a positive nitrogen pressure and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.67. The amino group content measu-res 37 meq/kg, and the carboxylic end group content measures 70 meq/kg.
EXAMPLE 3 (Comparative) Polymerization of PPA/0.15~5 TAD-Regulated Nylon 6 A mixture of molten caprolactam containing 0.5 by weight water and 0.19 by weight propionic acid is continuously introduced into the top of a polymerization reactor. The polymerization reactor used is a stainless steel VK column as outlined in U.S. Patent No. 4,354,020, which is incorporated herein by reference. The mixture is continuously introduced into the top of the VK column into reaction zone I at a temperature of about 265°C and at a rate of about 30-40 kg/h with stirring. The VK column, which has a ca-pacity of 340 liters, is heated by heat exchange oil. At the same time, 4-amino-2,2,6,6-tetramethylpiperidine is continuously sup-plied from a separate stream to the reaction zone I at a rate so that there is 0.15 weight percent of 4-amino-2,2,6,6-tetramethyl-piperidine in the mixture at all times. The heat of polymerization generated in further reaction zones is removed by appropriate cooling with internal heat exchangers. The temperature of the last reaction zone is about 265°C. The resul-ting polymer is extruded at the bottom of the VK column and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.68. Both the amino group content and the carboxylic end group content measure 44 meq/kg.
To accelerate the polymerization, the system is placed under a vacuum of 500 mm Hg for 45 minutes. The polymer is then extruded under a positive nitrogen pressure and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.67. The amino group content measu-res 37 meq/kg, and the carboxylic end group content measures 70 meq/kg.
EXAMPLE 3 (Comparative) Polymerization of PPA/0.15~5 TAD-Regulated Nylon 6 A mixture of molten caprolactam containing 0.5 by weight water and 0.19 by weight propionic acid is continuously introduced into the top of a polymerization reactor. The polymerization reactor used is a stainless steel VK column as outlined in U.S. Patent No. 4,354,020, which is incorporated herein by reference. The mixture is continuously introduced into the top of the VK column into reaction zone I at a temperature of about 265°C and at a rate of about 30-40 kg/h with stirring. The VK column, which has a ca-pacity of 340 liters, is heated by heat exchange oil. At the same time, 4-amino-2,2,6,6-tetramethylpiperidine is continuously sup-plied from a separate stream to the reaction zone I at a rate so that there is 0.15 weight percent of 4-amino-2,2,6,6-tetramethyl-piperidine in the mixture at all times. The heat of polymerization generated in further reaction zones is removed by appropriate cooling with internal heat exchangers. The temperature of the last reaction zone is about 265°C. The resul-ting polymer is extruded at the bottom of the VK column and cut into chips. The chips are washed with hot water (90°C) and dried in a tumble dryer. The relative viscosity measures 2.68. Both the amino group content and the carboxylic end group content measure 44 meq/kg.
Polymerization of ADA/0.15~ TAD-Regulated Nylon 6 Caprolactam is polymerized in the same VK column as in Example 3, but with the addition of 0.29 weight percent adipic acid, 0.5 weight percent water, and 0.15 weight percent 4-amino-2,2,6,6-te-tramethylpiperidine. The dried product has a relative viscosity of 2.73, an amino end group content of 43 meq/kg, and a carboxylic end group content of 59 meq/kg.
Polymerization of ADA/0.30~ TAD-Regulated Nylon 6 Caprolactam is polymerized in the same VK column as in Example 3, but with the addition of 0.29 weight percent adipic acid, 0.5 weight percent water, and 0.30 weight percent 4-amino-2,2,6,6-te-tramethylpiperidine. The dried product has a relative viscosity of 2.70, an amino end group content of 53 meq/kg, and a carboxylic end group content of 51 meq/kg.
EXAMPLE 6 (Comparative) Polymerization of TPA/0.15~ TAD-Regulated Nylon 6 Caprolactam was polymerized in the same VK column as in Example 3 with addition of 0.30 weight percent terephthalic acid, 0.5 weight percent water, and 0.15 weight percent 4-amino-2,2,6,6-te-tramethylpiperidine. The dried product had a relative viscosity of 2.68, an amino end group content of 42 meq/kg, and a carboxylic end group content of 63 meq/kg.
Spinning of 1115 Denier/58 Filament Solution-Dyed Yarn with Tri-lobal Cross-Section Nylon 6 polymer from Examples 3-6, as well as commercial nylon 6 (Ultramid B~ nylon 6 available from BASF Corporation of Mount Olive, NJ), is extruded at 260°C-265°C. Opal gray color concen-trate mixed with a proper amount of nylon chip is added to the spinning machine through volumetric feeders. The extruded fila-ments are cooled and solidified by a stream of quench air at 15°C.
After the application of spin finish, the yarns are drawn at a draw ratio of 3.3 and are textured in a texture jet at 215°C. The yarns are taken up at a draw roll speed of about 2350 m/min.
Strength Retention after Ultraviolet Exposure Opal gray solution-dyed yarns from Example 7 are exposed in an Atlas Ci65 Weather-Ometer~ for 2125 kJ exposure in increments of 425 kJ under the conditions specified by the AATCC Test Method 16-1993, Colorfastness to Light, Option E. The strength of each of the yarns is measured before exposure and after each 425 kJ
increment of exposure. The percent strength retention after each increment of exposure is shown in FIG. 1. These results show a significant improvement in retained strength for the TAD-contai-ning polymers, especially the ADA/TAD polymers. The commercial nylon 6 lost its strength dramatically during the exposure, while the TAD-containing polymers retained more than 85~ of their strength after 2125 kJ of exposure.
ao Yellowing of Plaques by GM SAE J1885 Test Method Polymer from Examples 3-6, as well as commercial nylon 6 (Ultramid B~ nylon 6 available from BASF Corporation of Mount Olive, NJ), is melted in an injection molding machine at about 265°C. The molten polymer is injected into a mold to make 110mm x 110mm x 3mm plaques. These plaques are then cut into smaller pla-ques, each measuring about 55mm x 110mm x 3mm.
The plaques are then exposed in an Atlas Ci65 Xenon-Arc Weather-Ometer~ for 1,000 hours (1,410 kJ) in 100 hour (141 kJ) incre-ments by the conditions specified in the GM SAE J1885 Test Method. The exposed plaques are measured for yellowing (or "Delta b*," where a higher Delta b* value indicates a more yellow sam-ple) at each increment of exposure using an Applied Color Systems Spectrophotometer. The results of these exposures are plotted in FIG. 2. The results show that the commercial nylon 6 polymer and the comparative TPA/0.15~ TAD-regulated polymer yellowed most si-gnificantly during the exposure. While exposure of the PPA/TAD
polymer resulted in less yellowing than the commercial nylon 6 polymer and the comparative TPA/0.15~ TAD-regulated polymer, ex-posure of the ADA/TAD polymers resulted only in minimal yello-wing.
Polymerization of ADA/0.30~ TAD-Regulated Nylon 6 Caprolactam is polymerized in the same VK column as in Example 3, but with the addition of 0.29 weight percent adipic acid, 0.5 weight percent water, and 0.30 weight percent 4-amino-2,2,6,6-te-tramethylpiperidine. The dried product has a relative viscosity of 2.70, an amino end group content of 53 meq/kg, and a carboxylic end group content of 51 meq/kg.
EXAMPLE 6 (Comparative) Polymerization of TPA/0.15~ TAD-Regulated Nylon 6 Caprolactam was polymerized in the same VK column as in Example 3 with addition of 0.30 weight percent terephthalic acid, 0.5 weight percent water, and 0.15 weight percent 4-amino-2,2,6,6-te-tramethylpiperidine. The dried product had a relative viscosity of 2.68, an amino end group content of 42 meq/kg, and a carboxylic end group content of 63 meq/kg.
Spinning of 1115 Denier/58 Filament Solution-Dyed Yarn with Tri-lobal Cross-Section Nylon 6 polymer from Examples 3-6, as well as commercial nylon 6 (Ultramid B~ nylon 6 available from BASF Corporation of Mount Olive, NJ), is extruded at 260°C-265°C. Opal gray color concen-trate mixed with a proper amount of nylon chip is added to the spinning machine through volumetric feeders. The extruded fila-ments are cooled and solidified by a stream of quench air at 15°C.
After the application of spin finish, the yarns are drawn at a draw ratio of 3.3 and are textured in a texture jet at 215°C. The yarns are taken up at a draw roll speed of about 2350 m/min.
Strength Retention after Ultraviolet Exposure Opal gray solution-dyed yarns from Example 7 are exposed in an Atlas Ci65 Weather-Ometer~ for 2125 kJ exposure in increments of 425 kJ under the conditions specified by the AATCC Test Method 16-1993, Colorfastness to Light, Option E. The strength of each of the yarns is measured before exposure and after each 425 kJ
increment of exposure. The percent strength retention after each increment of exposure is shown in FIG. 1. These results show a significant improvement in retained strength for the TAD-contai-ning polymers, especially the ADA/TAD polymers. The commercial nylon 6 lost its strength dramatically during the exposure, while the TAD-containing polymers retained more than 85~ of their strength after 2125 kJ of exposure.
ao Yellowing of Plaques by GM SAE J1885 Test Method Polymer from Examples 3-6, as well as commercial nylon 6 (Ultramid B~ nylon 6 available from BASF Corporation of Mount Olive, NJ), is melted in an injection molding machine at about 265°C. The molten polymer is injected into a mold to make 110mm x 110mm x 3mm plaques. These plaques are then cut into smaller pla-ques, each measuring about 55mm x 110mm x 3mm.
The plaques are then exposed in an Atlas Ci65 Xenon-Arc Weather-Ometer~ for 1,000 hours (1,410 kJ) in 100 hour (141 kJ) incre-ments by the conditions specified in the GM SAE J1885 Test Method. The exposed plaques are measured for yellowing (or "Delta b*," where a higher Delta b* value indicates a more yellow sam-ple) at each increment of exposure using an Applied Color Systems Spectrophotometer. The results of these exposures are plotted in FIG. 2. The results show that the commercial nylon 6 polymer and the comparative TPA/0.15~ TAD-regulated polymer yellowed most si-gnificantly during the exposure. While exposure of the PPA/TAD
polymer resulted in less yellowing than the commercial nylon 6 polymer and the comparative TPA/0.15~ TAD-regulated polymer, ex-posure of the ADA/TAD polymers resulted only in minimal yello-wing.
While the invention has been described in connection with what is presently considered to be the most practical and preferred embo-diment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is in-s tended to cover various modifications and equivalents arrange-ments included within the spirit and scope of the appended claims.
Claims (20)
1. A method for producing a light and thermally stable polyamide comprising subjecting one or more polyamide-forming monomers to a polymerization process in the presence of an effective amount of at least one hindered piperidine compound and an effective amount of at least one chain regulating compound, wherein the at least one chain regulating compound comprises an aliphatic, dicarboxylic acid and combinations thereof, wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is selected from the group consisting of malic acid; malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid, succinic acid;
methylsuccinic acid; 2,2-dimethylsuccinic acid; 2,3-dimethyl-succinic acid; 2-ethyl-2-methylsuccinic acid; glutaric acid;
2,2-dimethylglutaric acid; 2,3-dimethylglutaric acid;
2,4-di-methylglutaric acid; adipic acid; 3-methyladipic acid;
azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid; dodecanedioic acid; and combinations thereof.
methylsuccinic acid; 2,2-dimethylsuccinic acid; 2,3-dimethyl-succinic acid; 2-ethyl-2-methylsuccinic acid; glutaric acid;
2,2-dimethylglutaric acid; 2,3-dimethylglutaric acid;
2,4-di-methylglutaric acid; adipic acid; 3-methyladipic acid;
azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid; dodecanedioic acid; and combinations thereof.
2. The method according to claim 1 wherein the at least one hindered piperidine compound is selected from the group consisting of amino polyalkylpiperidines.
3. The method according to claim 1 wherein the at least one hindered piperidine compound is selected from the group consisting of 4-amino-2,2,6,6-tetramethylpiperidine;
4-(amino-alkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine; 4-(aminoaryl/
alkyl)-2,2,6,6-tetramethylpiperidine; 3-amino-2,2,6,6-tetra-methylpiperidine; 3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-4-pi-peridinealkylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidi-nearylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidinealkyl/
arylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid; 2,2,6;6-tetramethyl-3-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid;
and combinations thereof.
4-(amino-alkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine; 4-(aminoaryl/
alkyl)-2,2,6,6-tetramethylpiperidine; 3-amino-2,2,6,6-tetra-methylpiperidine; 3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-4-pi-peridinealkylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidi-nearylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidinealkyl/
arylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid; 2,2,6;6-tetramethyl-3-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid;
and combinations thereof.
4. The method according to claim 3 wherein the at least one hindered piperidine compound is 4-amino-2,2,6,6-tetramethylpipe-ridine.
5. The method according to claim 4 wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is selected from the group consisting of adipic acid, azelaic acid, decanedicarboxylic acid, sebacic acid, and combinations thereof.
6. The method according to claim 5 wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is adipic acid.
7. The method according to claim 1 wherein the light and thermally stable polyamide is selected from the group consisting of nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6T, nylon 6/12, nylon 4/6, nylon 11, nylon 12, poly(meta-phenylene isophthalamide), and poly(para-phenylene terephthalamide).
8. The method according to claim 7 wherein the light and thermally stable polyamide is nylon 6.
9. The method according to claim 1 wherein the polyamide-forming monomers comprise caprolactam monomers.
10. A light and thermally stable polyamide comprising a backbone polymer chain, at least one hindered piperidine moiety, and at least one aliphatic, dicarboxylic acid chain regulating compound, wherein both the at least one hindered piperidine moiety and the at least one aliphatic, dicarboxylic acid chain regulating compound are chemically bonded to the back-bone polymer chain, wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is selected from the group consisting of malic acid; malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid, succinic acid; methylsuccinic acid; 2,2-dimethyl-succinic acid; 2,3-dimethylsuccinic acid; 2-ethyl-2-methyl-succinic acid; glutaric acid; 2,2-dimethylglutaric acid;
2,3-dimethylglutaric acid; 2,4-dimethylglutaric acid; adipic acid; 3-methyladipic acid; azelaic acid; pimelic acid;
sebacic acid; decanedicarboxylic acid; dodecanedioic acid; and combinations thereof.
2,3-dimethylglutaric acid; 2,4-dimethylglutaric acid; adipic acid; 3-methyladipic acid; azelaic acid; pimelic acid;
sebacic acid; decanedicarboxylic acid; dodecanedioic acid; and combinations thereof.
11. The polyamide of claim 10 wherein the at least one hindered piperidine compound is selected from the group consisting of amino polyalkylpiperidines.
12. The polyamide of claim 10 wherein the at least one hindered piperidine compound is selected from the group consisting of 4-amino-2,2,6,6-tetramethylpiperidine;
4-(amino-alkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine; 4-(aminoaryl/
alkyl)-2,2,6,6-tetramethylpiperidine; 3-amino-2,2,6,6- tetra-methylpiperidine; 3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-4-pi-peridinealkylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidi-nearylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidinealkyl/
arylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid;
and combinations thereof.
4-(amino-alkyl)-2,2,6,6-tetramethylpiperidine;
4-(aminoaryl)-2,2,6,6-tetramethylpiperidine; 4-(aminoaryl/
alkyl)-2,2,6,6-tetramethylpiperidine; 3-amino-2,2,6,6- tetra-methylpiperidine; 3-(aminoalkyl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl)-2,2,6,6-tetramethylpiperidine;
3-(aminoaryl/alkyl)-2,2,6,6-tetramethylpiperidine; 2,2,6,6-tetra-methyl-4-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-4-pi-peridinealkylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidi-nearylcarboxylic acid; 2,2,6,6-tetramethyl-4-piperidinealkyl/
arylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinecarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinealkylcarboxylic acid; 2,2,6,6-tetramethyl-3-piperidinearylcarboxylic acid;
2,2,6,6-tetramethyl-3,4-piperidinealkyl/arylcarboxylic acid;
and combinations thereof.
13. The polyamide of claim 12 wherein the at least one hindered piperidine compound is 4-amino-2,2,6,6-tetramethylpiperidine.
14. The method according to claim 10 wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is selected from the group consisting of adipic acid, azelaic acid, decanedicarboxylic acid, sebacic acid, and combinations thereof.
15. The method according to claim 14 wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is adipic acid.
16. The polyamide of claim 10 wherein the polyamide is selected from the group consisting of nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6T, nylon 6/12, nylon 4/6, nylon 11, nylon 12, poly(meta-phenylene isophthalamide), and poly(para-phenylene terephthalamide).
17. The polyamide of claim 16 wherein the polyamide is nylon 6.
18. A light and thermally stable polyamide comprising a backbone polymer chain, at least one hindered piperidine moiety chemically bonded to the backbone polymer chain, and at least one aliphatic, dicarboxylic acid chain regulating compound chemically bonded to the backbone polymer chain, wherein the at least one aliphatic, dicarboxylic acid chain regulating compound is selected from the group consisting of malic acid;
malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid, succinic acid; methylsuccinic acid; 2,2-dimethylsuccinic acid; 2,3-dimethylsuccinic acid; 2-ethyl-2-methylsuccinic acid; glutaric acid;
2,2-dime-thylglutaric acid; 2,3-dimethylglutaric acid;
2,4-dimethyl-glutaric acid; adipic acid; 3-methyladipic acid; azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid;
dodecanedioic acid; and combinations thereof, wherein the spinning efficiency of the light and thermally stable polyamide is increased by at least 0.5 percent.
malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid, succinic acid; methylsuccinic acid; 2,2-dimethylsuccinic acid; 2,3-dimethylsuccinic acid; 2-ethyl-2-methylsuccinic acid; glutaric acid;
2,2-dime-thylglutaric acid; 2,3-dimethylglutaric acid;
2,4-dimethyl-glutaric acid; adipic acid; 3-methyladipic acid; azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid;
dodecanedioic acid; and combinations thereof, wherein the spinning efficiency of the light and thermally stable polyamide is increased by at least 0.5 percent.
19. An article comprising the light and thermally stable polyamide of claim 10.
20. An article according to claim 19 wherein the article is selected from the group consisting of fibers, yarns, carpets, and engineering plastics.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US7726998P | 1998-03-09 | 1998-03-09 | |
| US60/077269 | 1998-03-09 | ||
| PCT/EP1999/000889 WO1999046323A1 (en) | 1998-03-09 | 1999-02-11 | Light and thermally stable polyamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2323360A1 true CA2323360A1 (en) | 1999-09-16 |
Family
ID=22137095
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002249005A Abandoned CA2249005A1 (en) | 1998-03-09 | 1998-10-16 | Light and thermally stable polyamide |
| CA002323360A Abandoned CA2323360A1 (en) | 1998-03-09 | 1999-02-11 | Light and thermally stable polyamide |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002249005A Abandoned CA2249005A1 (en) | 1998-03-09 | 1998-10-16 | Light and thermally stable polyamide |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP1062270A1 (en) |
| JP (1) | JP2002506102A (en) |
| KR (1) | KR20010041746A (en) |
| CN (1) | CN1294611A (en) |
| AR (1) | AR014693A1 (en) |
| BG (1) | BG104746A (en) |
| BR (1) | BR9908608A (en) |
| CA (2) | CA2249005A1 (en) |
| EA (1) | EA002974B1 (en) |
| HU (1) | HUP0102204A3 (en) |
| ID (1) | ID25869A (en) |
| IL (1) | IL137646A0 (en) |
| MX (2) | MX9808878A (en) |
| PL (1) | PL342814A1 (en) |
| SK (1) | SK11992000A3 (en) |
| TR (1) | TR200002589T2 (en) |
| TW (1) | TW448202B (en) |
| WO (1) | WO1999046323A1 (en) |
| ZA (1) | ZA991879B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001288360A (en) * | 2000-04-04 | 2001-10-16 | Unitika Ltd | Polyamide resin composition and method for producing the same |
| DE10030515A1 (en) * | 2000-06-28 | 2002-01-10 | Basf Ag | polyamides |
| DE10030512A1 (en) * | 2000-06-28 | 2002-01-17 | Basf Ag | polyamides |
| US6545156B1 (en) * | 2000-11-03 | 2003-04-08 | Cytec Technology Corp. | Oligomeric hindered amine light stabilizers based on multi-functional carbonyl compounds and methods of making same |
| DE10058292A1 (en) * | 2000-11-23 | 2002-05-29 | Basf Ag | polyamides |
| US6620208B2 (en) * | 2001-03-30 | 2003-09-16 | Honeywell International Inc. | Wetfast polyamide fiber with high amino end group content |
| HUP0303984A2 (en) * | 2001-05-15 | 2004-03-01 | Basf Ag | System made from a polyamide and a 2,6-diaminopyridine derivative and method for production of said system |
| CZ20033310A3 (en) * | 2001-06-06 | 2004-11-10 | Basf Corporation | Process for preparing a polymer from a polymer precursor composition |
| JP4189993B2 (en) * | 2002-12-02 | 2008-12-03 | ユニチカ株式会社 | Light-resistant polyamide composition and light-resistant polyamide fiber |
| FR2857984B1 (en) * | 2003-07-25 | 2008-02-08 | Rhodia Performance Fibres | THREADS, FIBERS, ABRASION RESISTANT FILAMENTS |
| KR100807040B1 (en) * | 2003-12-10 | 2008-02-25 | 주식회사 효성 | Process for the manufacture of excellent heat-resistant polyamide 6 fiber |
| DE102005062165A1 (en) | 2005-12-22 | 2007-07-05 | Lanxess Deutschland Gmbh | Use of a succinic acid ester compound as a molecular weight reducing additives for the preparation of polyamide molded mass |
| FR2924434B1 (en) * | 2007-12-04 | 2010-12-17 | Rhodia Operations | POLYAMIDE COMPOSITION STABILIZED FOR HEAT AND LIGHT |
| PL221727B1 (en) | 2012-07-23 | 2016-05-31 | Splast Spółka Z Ograniczoną Odpowiedzialnością Spółka Komandytowa | Composition comprising a polyamide |
| CN103910876B (en) * | 2012-12-31 | 2017-02-08 | 中国科学院化学研究所 | Modified nylon 66 resin, preparation method and application thereof |
| TW201506057A (en) * | 2013-05-01 | 2015-02-16 | Invista Tech Sarl | Addition of copper to transfer line in nylon synthesis |
| CN106905517A (en) * | 2017-04-20 | 2017-06-30 | 福建中锦新材料有限公司 | A kind of polyamide 6 and its manufacture method for spinning |
| CN108047405B (en) * | 2017-12-14 | 2019-11-15 | 华南理工大学 | A kind of water-soluble lignin piperidines amine light stabilizer and its preparation method and application |
| CN110982063A (en) * | 2019-12-05 | 2020-04-10 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
| CN114957652A (en) * | 2022-04-12 | 2022-08-30 | 宿迁联盛亚克力有限公司 | Photo-thermal stable nylon 66 and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618909A (en) * | 1995-07-27 | 1997-04-08 | Alliedsignal Inc. | Light stabilized polyamide substrate and process for making |
| US5851238A (en) * | 1996-07-31 | 1998-12-22 | Basf Corporation | Photochemically stabilized polyamide compositions |
| US6136433A (en) * | 1997-05-01 | 2000-10-24 | Basf Corporation | Spinning and stability of solution-dyed nylon fibers |
-
1998
- 1998-10-16 CA CA002249005A patent/CA2249005A1/en not_active Abandoned
- 1998-10-26 MX MX9808878A patent/MX9808878A/en not_active Application Discontinuation
-
1999
- 1999-02-11 WO PCT/EP1999/000889 patent/WO1999046323A1/en not_active Application Discontinuation
- 1999-02-11 EA EA200000893A patent/EA002974B1/en not_active IP Right Cessation
- 1999-02-11 IL IL13764699A patent/IL137646A0/en unknown
- 1999-02-11 ID IDW20001719A patent/ID25869A/en unknown
- 1999-02-11 KR KR1020007009982A patent/KR20010041746A/en not_active Application Discontinuation
- 1999-02-11 JP JP2000535696A patent/JP2002506102A/en active Pending
- 1999-02-11 PL PL99342814A patent/PL342814A1/en not_active Application Discontinuation
- 1999-02-11 EP EP99908875A patent/EP1062270A1/en not_active Withdrawn
- 1999-02-11 CA CA002323360A patent/CA2323360A1/en not_active Abandoned
- 1999-02-11 TR TR2000/02589T patent/TR200002589T2/en unknown
- 1999-02-11 CN CN99803797A patent/CN1294611A/en active Pending
- 1999-02-11 BR BR9908608-5A patent/BR9908608A/en not_active IP Right Cessation
- 1999-02-11 SK SK1199-2000A patent/SK11992000A3/en unknown
- 1999-02-11 HU HU0102204A patent/HUP0102204A3/en unknown
- 1999-03-08 ZA ZA9901879A patent/ZA991879B/en unknown
- 1999-03-09 AR ARP990100998A patent/AR014693A1/en not_active Application Discontinuation
- 1999-05-18 TW TW088103601A patent/TW448202B/en not_active IP Right Cessation
-
2000
- 2000-08-21 MX MXPA00008162 patent/MXPA00008162A/en not_active Application Discontinuation
- 2000-09-04 BG BG104746A patent/BG104746A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002506102A (en) | 2002-02-26 |
| HUP0102204A3 (en) | 2002-10-28 |
| CN1294611A (en) | 2001-05-09 |
| WO1999046323A1 (en) | 1999-09-16 |
| SK11992000A3 (en) | 2001-04-09 |
| CA2249005A1 (en) | 1999-09-09 |
| TW448202B (en) | 2001-08-01 |
| EA002974B1 (en) | 2002-12-26 |
| MX9808878A (en) | 1999-09-01 |
| HUP0102204A2 (en) | 2001-10-28 |
| EA200000893A1 (en) | 2001-04-23 |
| PL342814A1 (en) | 2001-07-02 |
| TR200002589T2 (en) | 2001-07-23 |
| BG104746A (en) | 2001-04-30 |
| ID25869A (en) | 2000-11-09 |
| BR9908608A (en) | 2000-11-14 |
| ZA991879B (en) | 2000-10-11 |
| AR014693A1 (en) | 2001-03-28 |
| KR20010041746A (en) | 2001-05-25 |
| MXPA00008162A (en) | 2001-03-01 |
| IL137646A0 (en) | 2001-10-31 |
| EP1062270A1 (en) | 2000-12-27 |
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