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WO1999046323A1 - Polyamide photostable et thermostable - Google Patents

Polyamide photostable et thermostable Download PDF

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Publication number
WO1999046323A1
WO1999046323A1 PCT/EP1999/000889 EP9900889W WO9946323A1 WO 1999046323 A1 WO1999046323 A1 WO 1999046323A1 EP 9900889 W EP9900889 W EP 9900889W WO 9946323 A1 WO9946323 A1 WO 9946323A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
nylon
polyamide
tetramethylpiperidine
tetramethyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1999/000889
Other languages
English (en)
Inventor
Harry Y. Hu
Bobby J. Bailey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BR9908608-5A priority Critical patent/BR9908608A/pt
Priority to SK1199-2000A priority patent/SK11992000A3/sk
Priority to HU0102204A priority patent/HUP0102204A3/hu
Priority to EA200000893A priority patent/EA002974B1/ru
Priority to EP99908875A priority patent/EP1062270A1/fr
Priority to IL13764699A priority patent/IL137646A0/xx
Priority to JP2000535696A priority patent/JP2002506102A/ja
Priority to CA002323360A priority patent/CA2323360A1/fr
Priority to PL99342814A priority patent/PL342814A1/xx
Application filed by BASF Corp filed Critical BASF Corp
Publication of WO1999046323A1 publication Critical patent/WO1999046323A1/fr
Priority to BG104746A priority patent/BG104746A/bg
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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

Definitions

  • 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.
  • 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.).
  • organic stabilizers are known for use with nylon and articles manufactured therefrom.
  • Inorganic stabilizers are generally less expensive and more effective than organic stabilizers; however, inorganic stabilizers suffer from a different set of problems.
  • common inorganic stabilizers such as, for example, copper compounds, cause problems during processing.
  • copper compounds may be reduced to insoluble elemental copper. Formation of elemental copper reduces production efficiency and adds significant equipment maintenance costs.
  • the removal of copper deposits generates environmen- tally-undesirable effluent.
  • 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 compositions comprising providing to a dye bath a shaped article of 2 poly (epsilon-caprolacta ) hydrolytically polymerized in the presence 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.
  • 2 poly epsilon-caprolacta
  • 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 a ino group (-NH) that reacts with a carboxy end group of the polyamide molecule during polymerization, thus rendering the polymer light and heat stable.
  • -NH primary a ino group
  • TMP 2, 2, 6, 6-tetramethylpiperidin-4-ol
  • 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 environmentally-friendly and efficient process of producing a modified polyamide that is both light and heat stable.
  • a method of making a light and thermally stable polyamide with built-in stabilizers comprises subjecting one or more polyamide-forming monomers to a polymerization pro- 3 cess in the presence of an effective amount of at least one hindered piperidine compound and an effective amount at least one aliphatic, dicarboxylic acid chain regulating compound.
  • 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 regulator in the polymerization process, but also endows the resulting polyamide with light and heat stability.
  • the modified polyamide of the present invention does not discolor in the early stage of ultraviolet exposure.
  • 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.
  • polyamide denotes homopolymers , copolymers, blends, and grafts of those long chain polymers having 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.”
  • 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 physically admixed with the polyamide.
  • 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) .
  • the light and thermally stable polyamide of this invention is nylon 6, nylon 6/6, nylon 6T, nylon 6/12, and nylon 4/6.
  • 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.
  • suitable polyamide-forming monomers are diamine compounds, dicarboxylic acids, caprolactam monomers, and combinations thereof.
  • 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 conventional 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 effective 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 5 compounds to render the resultant polyamide light and thermally stable.
  • the effective amount of the one or more hindered piperidine compounds is in the range of about 0.030 to about 0.800, and more preferably about 0.060 to about 0.400, mole 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 combination with the one or more hindered piperidine compounds to render the resultant polyamide light and thermally stable.
  • the effective amount of the one or more aliphatic, dicarboxylic 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.
  • the one or more hindered amine compounds and the one or more aliphatic, dicarboxylic acid chain regulating compounds are added to the starting monomers or to the polymerizing reaction mixture.
  • 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 reactor in which polymerization is effected.
  • the hindered piperidine compound used in the present invention is represented by the formula:
  • Ri comprises an amine- or amide-forming functional group
  • R 2 is an alkyl
  • R 3 is selected from the group consisting of hydrogen, C 1 -C 3 alkyl groups, and -0R where R 4 is selected from the group consisting of hydrogen, methyl, and C 1 -C 7 alkyl groups.
  • Ri is preferably selected from the group consisting of -NHR 5 where R 5 is hydrogen or a Ci-C ⁇ alkyl, carboxyl, carboxylic acid derivative, - (CH ) X (NH)R 5 where x is an integer of from 1 to about 6, -(CH) y COOH where y is an integer of from 1 to about 6, and -(CH ) y COOH acid derivative.
  • the hindered piperidine compound used in the present invention is preferably an amino polyalkylpiperi- 6 dine or a polyalkylpiperidine acid. Nonlimiting examples of such hindered piperidine compounds include:
  • 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 preferably, the hindered piperidine compound is 4-amino-2, 2, 6, 6-te- tramethylpiperidine.
  • Suitable chain regulating compounds for use in the present invention are aliphatic, dicarboxylic acids and combinations thereof.
  • Non-limiting examples of such aliphatic, dicarboxylic acids inc- lude the following:
  • malic acid malonic acid; methyl aIo ic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid, succinic acid; methylsuccinic acid; 2 ,2-dimethylsuccinic acid;
  • 3-methyladipic 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 C 4 -C 10 alkane dicarboxylic acids, particularly adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. Most preferably, the aliphatic, dicarboxylic acid chain regulating compound is adipic acid.
  • 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 stabilized from degradation by light and heat and that does not di- scolor, i.e., yellow, upon exposure to light and/or heat.
  • it is not necessary to use other stabilizers such as, for example, copper compounds, as additives, although 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 reduces 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 efficiency translates into hundreds of thousands of dollars in reduced annual manufacturing costs.
  • the modified polyamide of the present invention has a narrower molecular weight distribution than acetic acid- and propionic acid-regulated polyamides .
  • the molecular weight distribution of the modified polyamide of the present in- vention is about 1.65 to about 1.80
  • the molecular weight 8 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 invention and to methods of producing such articles.
  • Non-limiting examples of such articles include fibers, yarns, carpets, engineering 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 entirety of both of which are incorporated herein by reference.
  • 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 present 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 reference.
  • 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 leveling 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.
  • 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 exemplary and not intended to be limiting.
  • the polyamide of the present invention is melted and colored with a colorant selected 9 from the group consisting of pigments, dyes, any colored compound with properties between pigments and dyes, and combinations thereof.
  • 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. Patent No. 5,487,860 to Kent et al., and U.S. Patent No. 4,918,947 to Speich.
  • 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.
  • ADA refers to adipic acid
  • PPA propionic acid
  • TPA terephthalic acid
  • TAD 4-amino-2 , 2 , 6 , 6-tetramethylpiperidine
  • RV Relative Viscosity
  • the relative viscosity compares the viscosity of a solution of polymer in formic acid with the viscosity of the formic acid itself (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.
  • 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 determined 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 alcohol 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. 10
  • This test is designed to simulate extreme environmental conditions encountered inside a vehicle due to sunlight, heat, and hu- midity for the purpose of predicting the performance of automotive 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- terior Trim Components using a Controlled Irradiance Water-Cooled Xenon-Arc Apparatus. "
  • the test is designed to determine the strength retention of the controls and the experimental samples.
  • the term "strength retention” refers to the change in tenacity of the material as a result 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
  • 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) .
  • the pressure is slowly released.
  • 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 measures 37 meq/kg, and the carboxylic end group content measures 70 meq/kg.
  • 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 capacity of 340 liters, is heated by heat exchange oil.
  • 4-amino-2 , 2, 6 , 6-tetramethylpiperidine is continuously supplied 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 resulting 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. 12
  • 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.
  • 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.
  • 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.
  • Opal gray color concentrate mixed with a proper amount of nylon chip is added to the spinning machine through volumetric feeders.
  • the extruded filaments are cooled and solidified by a stream of quench air at 15°C.
  • the yarns are drawn at a 13 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.
  • 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.
  • the plaques are then exposed in an Atlas Ci65 Xenon-Arc Weatherometer ® for 1,000 hours (1,410 kJ) in 100 hour (141 kJ) increments 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 sample) 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 significantly during the exposure.

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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

Un polyamide photostable et thermostable renfermant des stabilisants est préparé par polymérisation de monomères formant du polyamide en la présence d'une quantité efficace d'au moins un composé pipéridine entravé et d'au moins un composé régulateur de chaîne, l'acide aliphatique, dicarboxylique.
PCT/EP1999/000889 1998-03-09 1999-02-11 Polyamide photostable et thermostable Ceased WO1999046323A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
CA002323360A CA2323360A1 (fr) 1998-03-09 1999-02-11 Polyamide photostable et thermostable
SK1199-2000A SK11992000A3 (sk) 1998-03-09 1999-02-11 Svetelne a tepelne stabilný polyamid
HU0102204A HUP0102204A3 (en) 1998-03-09 1999-02-11 Light and thermally stable polyamide
EA200000893A EA002974B1 (ru) 1998-03-09 1999-02-11 Свето- и термостойкий полиамид на основе капролактама, способ его получения и изделие, содержащее его
EP99908875A EP1062270A1 (fr) 1998-03-09 1999-02-11 Polyamide photostable et thermostable
BR9908608-5A BR9908608A (pt) 1998-03-09 1999-02-11 Poliamida estável à luz e ao calor, processo para produção da mesma, e, artigo
JP2000535696A JP2002506102A (ja) 1998-03-09 1999-02-11 光および熱に安定なポリアミド
IL13764699A IL137646A0 (en) 1998-03-09 1999-02-11 Light and thermally stable polyamide
PL99342814A PL342814A1 (en) 1998-03-09 1999-02-11 Light and heat resistant polyamide
BG104746A BG104746A (bg) 1998-03-09 2000-09-04 Устойчив към светлина и топлина полиамид

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7726998P 1998-03-09 1998-03-09
US60/077,269 1998-03-09

Publications (1)

Publication Number Publication Date
WO1999046323A1 true WO1999046323A1 (fr) 1999-09-16

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PCT/EP1999/000889 Ceased WO1999046323A1 (fr) 1998-03-09 1999-02-11 Polyamide photostable et thermostable

Country Status (19)

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EP (1) EP1062270A1 (fr)
JP (1) JP2002506102A (fr)
KR (1) KR20010041746A (fr)
CN (1) CN1294611A (fr)
AR (1) AR014693A1 (fr)
BG (1) BG104746A (fr)
BR (1) BR9908608A (fr)
CA (2) CA2249005A1 (fr)
EA (1) EA002974B1 (fr)
HU (1) HUP0102204A3 (fr)
ID (1) ID25869A (fr)
IL (1) IL137646A0 (fr)
MX (1) MXPA00008162A (fr)
PL (1) PL342814A1 (fr)
SK (1) SK11992000A3 (fr)
TR (1) TR200002589T2 (fr)
TW (1) TW448202B (fr)
WO (1) WO1999046323A1 (fr)
ZA (1) ZA991879B (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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WO2002042357A3 (fr) * 2000-11-23 2002-08-01 Basf Ag Polyamide
WO2002079300A1 (fr) * 2001-03-30 2002-10-10 Basf Aktiengesellschaft Fibre de polyamide solide a l'humidite a haute teneur en groupes terminaux amino
WO2002092664A1 (fr) * 2001-05-15 2002-11-21 Basf Aktiengesellschaft Systeme compose d'un polyamide et d'un derive de 2,6-diamonopyridine et procede de preparation d'un systeme de ce type
WO2002098965A1 (fr) * 2001-06-06 2002-12-12 Basf Corporation Procede de fabrication d'un polymere a partir d'une composition de precurseurs polymeres
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
JP2004502005A (ja) * 2000-06-28 2004-01-22 ビーエーエスエフ　アクチェンゲゼルシャフト ポリアミド
FR2857984A1 (fr) * 2003-07-25 2005-01-28 Rhodia Performance Fibres Fils, fibres, filaments resistants a l'abrasion
WO2007079873A1 (fr) 2005-12-22 2007-07-19 Lanxess Deutschland Gmbh Matieres pour moulage a base de polyamide
WO2014017933A1 (fr) 2012-07-23 2014-01-30 Splast Sp. Z O.O. Sp. K. Composition contenant un polyamide, des nanoparticules de silice et d'argent, et des additifs de stabilisation
CN108047405A (zh) * 2017-12-14 2018-05-18 华南理工大学 一种水溶性木质素哌啶胺光稳定剂及其制备方法和应用
CN114957652A (zh) * 2022-04-12 2022-08-30 宿迁联盛亚克力有限公司 一种光热稳定型尼龙66及其制备方法
CN118834382A (zh) * 2024-07-18 2024-10-25 湘潭大学 一种基于封端策略的本征抗菌尼龙的制备方法

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KR100807040B1 (ko) * 2003-12-10 2008-02-25 주식회사 효성 내열 안정성이 우수한 개질 폴리아미드6 섬유의 제조방법
FR2924434B1 (fr) * 2007-12-04 2010-12-17 Rhodia Operations Composition polyamide stabilisee vis-a-vis de la chaleur et de la lumiere
CN103910876B (zh) * 2012-12-31 2017-02-08 中国科学院化学研究所 一种改性尼龙66树脂及其制备方法和应用
TW201506057A (zh) * 2013-05-01 2015-02-16 Invista Tech Sarl 尼龍合成中傳送管線之銅的添加
CN106905517A (zh) * 2017-04-20 2017-06-30 福建中锦新材料有限公司 一种用于纺丝的聚酰胺6及其制造方法
CN110982063A (zh) * 2019-12-05 2020-04-10 中仑塑业（福建）有限公司 一种半芳香族聚酰胺树脂及其制备方法
CN115991934B (zh) * 2023-02-15 2024-08-16 万华化学集团股份有限公司 一种具有抗长期热氧老化性能的尼龙组合物

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Cited By (22)

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JP2001288360A (ja) * 2000-04-04 2001-10-16 Unitika Ltd ポリアミド樹脂組成物及びその製造法
JP2004502005A (ja) * 2000-06-28 2004-01-22 ビーエーエスエフ　アクチェンゲゼルシャフト ポリアミド
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
CZ298974B6 (cs) * 2000-11-23 2008-03-26 Basf Aktiengesellschaft Polyamidy
US6958381B2 (en) 2000-11-23 2005-10-25 Basf Aktiengesellschaft Polyamide
WO2002042357A3 (fr) * 2000-11-23 2002-08-01 Basf Ag Polyamide
KR100760766B1 (ko) * 2000-11-23 2007-10-04 바스프 악티엔게젤샤프트 폴리아미드
US6783560B2 (en) 2001-03-30 2004-08-31 Honeywell International, Inc. Process for preparing wetfast polyamide fibers
US6620208B2 (en) 2001-03-30 2003-09-16 Honeywell International Inc. Wetfast polyamide fiber with high amino end group content
WO2002079300A1 (fr) * 2001-03-30 2002-10-10 Basf Aktiengesellschaft Fibre de polyamide solide a l'humidite a haute teneur en groupes terminaux amino
WO2002092664A1 (fr) * 2001-05-15 2002-11-21 Basf Aktiengesellschaft Systeme compose d'un polyamide et d'un derive de 2,6-diamonopyridine et procede de preparation d'un systeme de ce type
US6828377B2 (en) 2001-06-06 2004-12-07 Basf Corporation Method of making a polymer from a polymer precursor composition
WO2002098965A1 (fr) * 2001-06-06 2002-12-12 Basf Corporation Procede de fabrication d'un polymere a partir d'une composition de precurseurs polymeres
WO2005019510A3 (fr) * 2003-07-25 2005-05-06 Rhodia Performances Fibres Fils, fibres, filaments resistants a l'abrasion.
FR2857984A1 (fr) * 2003-07-25 2005-01-28 Rhodia Performance Fibres Fils, fibres, filaments resistants a l'abrasion
AU2004266274B2 (en) * 2003-07-25 2008-05-29 Rhodia Performances Fibres Abrasion-resistant wires, fibres and filaments
WO2007079873A1 (fr) 2005-12-22 2007-07-19 Lanxess Deutschland Gmbh Matieres pour moulage a base de polyamide
WO2014017933A1 (fr) 2012-07-23 2014-01-30 Splast Sp. Z O.O. Sp. K. Composition contenant un polyamide, des nanoparticules de silice et d'argent, et des additifs de stabilisation
CN108047405A (zh) * 2017-12-14 2018-05-18 华南理工大学 一种水溶性木质素哌啶胺光稳定剂及其制备方法和应用
CN108047405B (zh) * 2017-12-14 2019-11-15 华南理工大学 一种水溶性木质素哌啶胺光稳定剂及其制备方法和应用
CN114957652A (zh) * 2022-04-12 2022-08-30 宿迁联盛亚克力有限公司 一种光热稳定型尼龙66及其制备方法
CN118834382A (zh) * 2024-07-18 2024-10-25 湘潭大学 一种基于封端策略的本征抗菌尼龙的制备方法

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MX9808878A (es) 1999-09-01
JP2002506102A (ja) 2002-02-26
CN1294611A (zh) 2001-05-09
EP1062270A1 (fr) 2000-12-27
EA200000893A1 (ru) 2001-04-23
TW448202B (en) 2001-08-01
PL342814A1 (en) 2001-07-02
HUP0102204A3 (en) 2002-10-28
EA002974B1 (ru) 2002-12-26
ZA991879B (en) 2000-10-11
SK11992000A3 (sk) 2001-04-09
MXPA00008162A (es) 2001-03-01
CA2249005A1 (fr) 1999-09-09
KR20010041746A (ko) 2001-05-25
BR9908608A (pt) 2000-11-14
HUP0102204A2 (hu) 2001-10-28
BG104746A (bg) 2001-04-30

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