TW448202B - Light and thermally stable polyamide, method for producing the same and its applications - Google Patents

Abstract

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 one or more hindered piperidine compound selected from the group consisting of amino polymethylpiperidines, in the range of 0.030 to 0.800 mole percent based on the weight of the polyamide-forming monomers used, and one or more chain regulating compound comprising an aliphatic, C4-C10 alkane dicarboxylic acid and combinations thereof, in the range of 0.001 to 0.800 mole percent based on the weight of the polyamide-forming monomers used, wherein the polymerization process is carried out at a temperature range from 240 to 290 DEG C. A light and thermally stable polyamide comprising a backbone polymer chain, one or more hindered piperidine compound selected from the group consisting of amino polymethylpiperidines, in the range of 0.030 to 0.800 mole percent based on the weight of the polyamide-forming monomers used, and one or more aliphatic, C4-C10 alkane dicarboxylic acid chain regulating compound, in the range of 0.001 to 0.800 mole percent based on the weight of the polyamide-forming monomers used, wherein both the one or more hindered piperidine compound and the one or more aliphatic, C4-C10 alkane dicarboxylic acid chain regulating compound are chemically bonded to the back-bone polymer chain.

Description

^ 48202 V. Description of the invention ¢ 1) The present invention relates to a kind of polyamide which can achieve high light and thermal stability. In particular, the present invention relates to a modified nylon polymer containing a blocked hexahydrogenate compound and a chain regulator, wherein the modified nylon polymer has improved stability to light and heat. It is known that when nylon without additives is exposed to light and / or heat, nylon discolors and loses its physical properties such as strength retention and resistance to elongation. Therefore, in some cases, it is necessary to add light and / or heat stabilizers to nylon to achieve acceptable performance. The stabilizer can be added before, during, or after the polymerization. It is known that stabilizers mix polymers but are not bound to the polymer chain; therefore, stabilizers tend to migrate out of the polymer, evaporate, or be washed away during processing or use of polyamide. This means that the stability activity is reduced in an undesired manner, and impurities are released to the surrounding environment (such as air, dye bath, etc.). A variety of organic stabilizers are known for use in nylon and articles made from nylon. One problem is that organic stabilizers such as blocking phenols are expensive and have limited effectiveness. Inorganic stabilizers are generally less expensive and more effective than organic stabilizers; however, inorganic stabilizers have different disadvantages. Typical common inorganic stabilizers such as copper compounds cause processing problems. For example, during melt extrusion, copper compounds may be reduced to insoluble elemental copper. The formation of elemental copper reduces production efficiency and significantly increases equipment maintenance costs. In addition, the removal of copper deposits causes environmentally undesirable drainage water. In other methods, such as the use of copper button compounds in a dye bath to treat automotive nylon fibers, excessive copper complexes in the dye bath may also produce undesired environmentally-friendly release water. US Patent Application No. 08/8 0 4, 3 1 2 also owned by the applicant

V. Description of the invention (2) A method for preparing a dyed nylon composition with stable photochemical properties, comprising providing a dye bath in water and blocking the polymerization reaction obtained in the presence of a hexahydropyridine derivative (£ _caney) (Ammonium amine) shaped parts, dyed shaped parts using one or more metallized or non-metallized acid dyes. U.S. Patent Application No. 60/04, 269, also owned by the present applicant, relates to a method for manufacturing a stabilization solution dyed fiber, which is prepared by the presence of at least one blocked hexahydropyridine compound Melt the polyamine containing the ammonium monomer and color the molten polyamine using a colorant. PCT Application International Application No. PCT / Ep 95/01349 describes a stable poly (vinyl alcohol) amine containing at least one triacetone diamine compound having a first amine group (-NH2). Carboxyl end group reaction 'so that the polymer becomes light and thermally stable 3

A paper by Poly. Deg. And Stab. 21, 251-262 (1988) describes the modification of polyamine 6 by the addition of 2, 2, 6, 6-tetrafluorenylhexahydropyridine-4-ol ("TMP"). Light stability of / 6. Polyamide 6/6 with TMP at 275 X: Recondensed in the melt in a water vapor atmosphere. The author claims that TMP reacts with the carboxyl end groups of polyamide. Therefore, there is a need to modify polyamines, which can reduce the demand for copper-based stabilizers and prevent discoloration after exposure to light and / or heat, that is, yellowing. It is also desirable to produce polyamides that have improved resistance to yellowing when exposed to light and / or heat, especially for engineering plastics applications. An object of the present invention is to provide a modified polyamide which prevents discoloration when exposed to light and / or heat. Another object of the present invention is to reduce the need for copper-based stabilizers and polyamines.

44B2D2 V. Description of Invention (3). Yet another object of the present invention is to provide an environmentally friendly and effective method for producing light and thermally stable modified polyamide. Thus, according to a specific example of the present invention, a method for manufacturing light and heat stable polyfluorene containing an internal stabilizer is provided. The method includes one or more polyamine-forming monomers in an effective amount of at least one. The blocking hexahydropyridine compound and an effective amount of at least one aliphatic dicarboxylic acid chain regulating compound are subjected to a polymerization process. In another aspect, the present invention is directed to a light and thermally stable polyamide, comprising a polymer backbone, at least one blocking hexahydropharyngeal group, and at least one aliphatic dicarboxylic acid chain regulating compound, wherein the At least one blocking hexahydropyridine group and at least one aliphatic dicarboxylic acid chain regulating compound are chemically bonded to the polymer backbone. The polyamide of the present invention is substantially free of copper compounds. The modified polyamide containing an embedded stabilizer made according to the present invention can achieve good light and thermal stability without using other stabilizers such as copper salts. The combination of at least one aliphatic dicarboxylic acid chain regulating compound and at least one blocked hexahydropyridine compound can be used not only as a molecular weight regulator in the polymerization process, but also can impart light and thermal stability to the resulting polyamine. The modified polyamide of the present invention does not change color in the early stage of exposure to ultraviolet light. Brief Description of the Drawings The foregoing, and other objects, effects, features, and advantages of the present invention will be apparent from the detailed description of better specific examples later, especially when read in conjunction with the drawings. Figure 1 is a line graph illustrating the strength retained by a solution-dyed yarn after exposure to a weather meter.

448202 V. Description of the invention (4) Figure 2 is an example of a line diagram illustrating the yellowing of polymer thick blocks after exposure to a weather meter. DETAILED DESCRIPTION OF THE INVENTION In order to facilitate understanding of the present invention, specific examples of the present invention will be described below and will be described using specific languages. Having said that, it is obvious that the scope of the present invention is by no means limited to the use of these specific languages, and is intended to cover the variations, modifications, equivalents, and principles of the present invention discussed herein, which are generally known to those skilled in the art and related to the present invention Further application. As used herein, the term " polyamidamine " means homopolymers, copolymers, and copolymers of such long-chain polymers containing recurring amine groups (-C0-NH-) as internal components of the polymer backbone. And graft polymers. Long chain polyamide is commonly known as " nylon ". As used herein with respect to the polyamide of the present invention, the "inclusive formula π" means that these components which can make the polyamide have light and thermal stability are chemically bonded to the polymer main chain of the polyamide rather than merely physical Way to mix polyamide. -In a specific example, the present invention is a modified polyamine which is substantially free of copper compounds, and includes a polymer main bond, at least one blocking hexahydrocarbyl group, and at least one aliphatic dicarboxylic acid chain regulating compound, The at least one blocking hexahydropyridine group and the at least one aliphatic dicarboxylic acid chain regulating compound are chemically bonded to the polymer main chain. The light and thermal stability polyamide of the present invention can be nylon 6, nylon 6/6, nylon 6/9, nylon 6/1 0, nylon 6T, nylon 6/1 2, nylon 4/6, nylon 1 1, Nylon 12 or aromatic nylons are, for example, poly (m-phenylene metaphthalamide) and poly (p-phenylene terephthalamide). The light and heat stable polyamides of the present invention are nylon 6, nylon 6/6, and nylon.

Name 48202 V. Description of the invention (ο 6T, nylon 6/1 2 and nylon 4/6. The best light and thermal stability polyamide of the present invention is nylon 6. Any suitable amine-forming monomer can be polymerized. It can be used to produce the light and thermally stable polyfluorene of the present invention. Non-limiting examples of such suitable polyamine-generating monomers are diamine compounds, dicarboxylic acids, caprolactam monomers, and combinations thereof. In a preferred embodiment of the present invention, the polyfluorene-forming single system is composed of a caprolactam monomer. The polymerization method for generating the polyfluorene of the present invention is preferably performed according to a conventional method, such as described in ^^ 1; US Patent No. 5,149,758, 1: 1 ^ 68, which is incorporated herein by reference in its entirety, but the polymerization of the present invention is based on an effective amount of one or more blocked hexahydropyridine compounds and an effective amount of one or more aliphatic dicarboxylic acids. It is carried out in the presence of an acid chain regulating compound. An effective amount of at least one blocked hexahydropyridine compound is sufficient to combine one or more aliphatic dicarboxylic acid chain regulating compounds to make the resulting polyamine into an amount having light and thermal stability. A preferred effective amount of one or more blocking hexahydropyridine compounds The polyamine-forming monomer is used in an amount of about 0.030 to about 0.80 and more preferably about 0.60 to about 0.40 mole. At least one effective amount The aliphatic dicarboxylic acid chain-modulating compound is an amount sufficient to make up one or more blocked hexahydropyridine compounds so that the resulting polyamine has light and thermal stability. An effective amount of one or more aliphatic dicarboxylic acid chain-modulating compounds The compound is preferably in the range of about 0.01 to about 0.80 and more preferably about 0.50 to about 0.50 moles / °, and is a polyamine-forming monomer. The amount is based on. In order to make the polyamide of the present invention, one or more blocking amine compounds and one or more aliphatic dicarboxylic acid chain regulating compounds are added to the starting monomer or polymerization reaction mixture. Hydropharyngeal anemia compounds, one or more

448202 V. Description of the invention (6) The aliphatic dicarboxylic acid chain regulating compound and the polyamine-forming monomer can be added to the reactor for polymerization reaction separately or in a mixture. The blocked hexahydropyridine compound used in the present invention can be expressed by the following formula:

Its center represents an amine or amidine-forming functional group, R2 is an alkyl group, and R3 is selected from the group including hydrogen, q-c3 alkyl, and -0R4. Here R4 is selected from the group including hydrogen, methyl, and d-C7 alkyl . Ri is preferably selected from the group consisting of -NHR5 where R5 is hydrogen or Q-Cs alkyl, carboxyl, carboxylic acid derivative,-(CH2) X (NH) R5 where X is an integer from 1 to about 6, _ (CH2 ) yC00H where y is an integer of 1 to about 6 and-(CH2) yC00H acid derivative ° The blocked hexahydropyridine compound used in the present invention is preferably an amino polyalkylhexahydropyridine or a polyalkylhexahydro Picolinic acid. Non-limiting examples of these blocked hexahydropyridine compounds include: 4-amino-2, 2, 6, 6-tetrafluorenylhexahydropyridine; 4- (aminoalkyl) -2, 2, 6, 6-tetrafluorenylhexahydropyridine; 4- (aminoaryl) -2, 2, 6, 6-tetrafluorenylhexahydropyridine; 4- (aminoaryl / alkyl) -2, 2, 6 , 6-tetramethylhexahydropyridine; 3-amino-2, 2, 6, 6-tetrafluorenylhexahydropyridine; 3- (aminoalkyl) -2,2,6,6-tetrafluorenyl Hexahydro specific bite; 3- (aminoaryl) -2,2,6,6_tetramethylhexahydropyridine;

# 48202 V. Description of the invention (7) 3- (Aminoaryl / alkyl) -2, 2, 6, 6-tetramethylhexahydropyridine; 2,2,6,6-tetramethyl-4- Hexahydrobarbital carboxylic acid; 2, 2, 6, 6-tetramethyl-4-hexapyridinyl carboxylic acid; 2, 2, 6, 6-tetrafluorenyl-4-hexahydropyridinyl aryl carboxylate Acid; 2, 2, 6, 6-tetramethyl-4 -hexahydropyridinyl / arylcarboxylic acid; 2, 2, 6, 6 -tetramethyl-3 -hexahydropyridinecarboxylic acid; 2, 2 , 6, 6-tetramethyl-3 -hexahydropyridinyl carboxylic acid; 2, 2, 6, 6 -tetramethyl-3-hexahydropyridinyl carboxylic acid; and 2,2, 6,6- Tetrafluorenyl-3 -hexahydropyridinyl / arylcarboxylic acid. The blocked amine compound may also be a mixture of blocked hexahydropyridine compounds. A more preferred blocking hexahydropyridine compound is 2,2,6,6-tetraalkylhexahydropyridine. The best blocking hexahydropyridine compound is 4-amino 2,2,6,6-tetramethylhexahydropyridine. Suitable chain regulating compounds for use in the present invention are aliphatic dicarboxylic acids and combinations thereof. Non-limiting examples of these aliphatic dicarboxylic acids include the following: malic acid; malonic acid; methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid; succinic acid; Methyl succinic acid; 2,2-dimethyl succinic acid; 2,3-dimethyl succinic acid;

Page 10 V. Description of the invention ¢ 8) 2-ethyl-2-methylsuccinic acid;. Glutaric acid; 2,2-difluorenylglutaric acid; 2,3-dimethylglutaric acid; 2,4-diamidylglutaric acid; adipic acid; 3-methyl adipic acid; azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid; and dodecanedioic acid. The aliphatic dicarboxylic acid chain-modulating compound used in the present invention may be the same as or different from the dicarboxylic acid used in the polyamide-generating compound. The aliphatic dicarboxylic acid chain regulating compound is preferably selected from the group consisting of C4-C1 (pentanedicarboxylic acid, particularly adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid. Optimal aliphatic dicarboxylic acid chains The adjusting compound is adipic acid. Of course, a variety of non-stabilizing additives can be used in the modified polyamide of the present invention. Examples include, but are not limited to, lubricants, coagulants, antioxidants, antistatic agents, and the like. Modified polyamidoamine which is stable when decomposed by light and heat and does not change color when exposed to light and / or heat, i.e. yellowing. The use of the present invention does not require the use of other stabilizers such as copper compounds as additives, but if required Other stabilizers may also be present. If these other stabilizers are present, their presence

Page 11 4 4 ^ 2-02-- V. Description of the invention (9) The quantity is significantly lower. Removal of productive additives reduces equipment maintenance costs and eliminates harmful release water when removing stabilizer deposits. The invention also produces a modified polyamide with improved spinning efficiency. The spinning efficiency is improved by at least about 0. This increase in spinning efficiency translates into a reduction of hundreds of thousands of dollars in annual production costs. Without wishing to be bound by theory, it is currently believed that the improvement in spinning efficiency comes from the modified polyamide of the present invention having a narrower molecular weight distribution than the polyamides adjusted by acetic acid and propionic acid. For polymers having a relative viscosity of 2, 7, the molecular weight distribution of the modified polyamide of the present invention is from about 1.65 to about 1.8, the molecular weight distribution of the polyamide adjusted by acetic acid and propionic acid. It is about 1,90 to about 2.00. The present invention is further directed to objects produced from the light and heat stable polyamides of the present invention and a process for making such objects. Non-limiting examples of such items include fibers, yarns, felts, engineering plastics such as automotive parts, and the like. The method for generating fibers, for example, allows the light and thermal stability polyamides of the present invention to undergo any of the conventional fiber forming processes, for example, as disclosed in 1 (3 『326〇1 ′ 岩 丨 〇11 No. 4,983,448 and Kent, etc. U.S. Patent No. 5,487,860, which is incorporated herein by reference in its entirety. The fiber generation process preferably involves rapid spinning light and thermal stability at a take-up speed of at least about 4,000 m / min. Polyamide. Engineering plastics are produced by subjecting the light and thermally stable polyamines of the present invention to any conventional plastic generation process, such as disclosed in US Patent No. 5,474,853 to tfatanabe et al. For reference. Fibers produced from the light and thermally stable polyamides of the present invention can be conventionally used for dyeing nylon, such as metallized and non-metallized acid dyes. Dyeing conditions for ordinary nylon dyeing can be used. The following general Sexual conditions are for steam only

Page 12 4482 02 V. Description of Invention (10) Limit its scope. The volume of dyeing is about the volume ratio to be dyed. Add processing chemicals such as chelating agents to prevent the & ions from depositing in the hard water or the leveling agent. Metallized acid dyes < h 々, · σ and f 俾 will slowly reduce the pH of the dye bath. Add dyes, adjust the dyeing, / pH. The bath is about 0,5 c to about 3. 0 in the mother minutes. Produced by Chu Ding π from 9 5 ° C to about 11 0 ac, and increase in inch rate ... ', plough about eight #, person ,, the pre-coffee degree and maintain at this temperature for about 30 minutes to% 60 knife minutes The cold part is dyed or emptied, and the objects are new. The rear objects are rolled and dried.

Dry stack in an Ai oven or in a tenter oven such as a tenter oven. In addition, the light and heat stability of the present invention can be dyed with a solution before the object. , Made of fiber :: forming the following general conditions are examples and not limitative: nature: ii :: poly brewing: er ϊ i er ΐ earthen agent dyeing, * colorant is selected from the group consisting of pigments, dyes, Ϊ " F "1; Colored compounds with properties between pigments and dyes and their content. Then colored polyurethane is spun into fibers or fabrics according to conventional methods, such as disclosed in US Patent No. 4,98 3,448 to Karageorgiou , The beauty of Kent, etc.-US Patent 4, 918, 94, Speich, Lee 5, 48 7, 8 60. For engineering plastics, polymer chips are mixed with colored compounds such as pigments and dyes and then poured into the extruder. Hello The advancing section of the extruder is a physical mixing rather than a melt mixing. The present invention will be further explained with reference to the following detailed examples. The examples are for illustration only !: The use of " Means "dipic acid", "TPA" means acid donation, and "TAD" means

4-monoamine burst, 6, 6-tetrafluorenylhexahydropyridine. The following terms and test conditions are also used in the examples as defined below: lice bar I J weight percentage.

Page 13 EN 482 02 V. Description of the invention (11) The weight percentage of this ingredient in the feed. Relative viscosity (RV) «Relative viscosity compares the viscosity of a polymer in formic acid solution with the viscosity of formic acid itself (ASTM D 78 9). The test results reported here were obtained using Q · 20 Kronyl 6 solution at 25 ° C 20 cc. Formic acid. End group content. 'The amine end group content was determined via a solution of 2.0 g of polymer at about 60 ° (: phenol-formaldehyde mixture (68:32)). This solution was measured by a potential measurement method at about 2 5 t: using about 0. Titration with 20 equivalents of hydrochloric acid, the end point of which is determined by the potential suddenly rising south. The content of the terminal group is determined by the solution of about 30 grams of polymer at 80 and about 40 cc. Benzyl alcohol mixture. The solution is based on the potential The dose method is from about 80% to about 10 ° C (about 0.03 equivalents) using the third concentration of the third butyl ammonium hydroxide titration, the end point of which is determined by the sudden rise in potential. The exposure test === is intended to be inside the car due to light , Heat and humidity encounters = predict the performance of automotive interior materials. This test measures

The Jim test method was performed, and the value was:. = According to ㈣SAE. ^ Said the use of the controlled illuminance secondary A lightning arc device to accelerate exposure of automotive interior components ,. < Water-cooled alum electric strength retention. The intensity holds the value of the artificial light source. This test The test is designed to determine the strength retention of the control sample and the test sample. The term "quotation" means that the material is exposed to light or changes in the toughness of the material. Toughness is a measure of fiber strength

Root fAATCC test method 16-1993 was performed on light fastness selection condition E (water cooling, arc lamp, continuous lighting). The material is exposed to 2 1 25 kJ exposure agent 5 ′. The toughness of each material is before and after each 425 kJ incremental exposure. The percent strength retention is determined as follows: Guangqian Tangtang) X 100% Example 1 (comparative) PPA / TAD-adjusted nylon 6 polymerized 75 kg caprolactam, 180 g water, 135 g ( 〇18 weight of propionic acid and 112.5 g (0.15% by weight) of 4-amino-2, 2, 6, 6-tetramethylpyridine hexahydropyridine was fed into 250 liters of pressure steel. The mixture was mixed in 1 Heated to 270 ° C for 0 hours and raised to 60 psi (31G2 mm Hg) with 0 ^ pressure. The mixture was slowly relieved after maintaining at 60 psi for 30 minutes. In order to accelerate the polymerization reaction, the system was placed under a vacuum of 400 mm Hg 75 minutes. Then the polymer was dialed under positive nitrogen pressure and cut into chips. The chips were washed with hot water 90t and dried in a tumble dryer. The relative viscosity was 2-71. The amine content was 42 meq / kg And the content of carboxylic acid end groups is 45 meq / kg. Example 2 Polymerization of 75 kg of caprolactam in water, 240 g (0.32% by weight) of adipic acid and Π 2.5 in nylon 6 adjusted by ADA / TAD Gram (0.15 weight? 04-amino-2, 2, 6, 6-tetramethylhexahydrohexanoine bite mixture silver into a 250-liter autoclave. The mixture was heated to 27 ° C in 1 hour at the same time The force increased to 60 psi (3 102 mm Hg). The mixture was slowly relieved after maintaining at 60 ps for 30 minutes. To accelerate the polymerization reaction, the system was placed under a 500 mm Hg vacuum for 45 minutes. Then the polymer Yu ^

O: \ 5T07291.ptc Page 15 2000.10.21.016 448202 _Case No. 88103601_Year Month Day Amendment_ Five. Description of the invention (13) Extruded and cut into chips. The crumbs were washed with hot water at 90 ° C and dried in a tumble dryer. The relative viscosity is 2.67, the amine group content is 37 meq / kg, and the carboxylic acid end group content is 70 meq / kg. Example 3 (Comparative) Polymerization of nylon 6 adjusted by PPA / 0.15% TAD A molten caprolactam mixture containing 0.5% by weight water and 0.19% by weight propionic acid was continuously introduced into the top of a polymerization reactor. The polymerization reactor used was a stainless steel VK column as summarized in U.S. Patent No. 4,3,54,020, which is described herein for reference. The mixture was continuously introduced into the top of the VK column into reaction zone 1 with stirring at a temperature of about 26.5 ° C at a rate of about 30-40 kg / hr. The VK column has a capacity of 340 liters and is heated by heat exchange oil. At the same time, 4-amino-2,2,6,6-tetramethylhexahydropyridine was supplied to the reaction section 1 from a separate stream at a feed rate that could be maintained at any time. The mixture contained 0.15 wt% 4-amino-2,2,6 The ratio of 6-tetrafluorenylhexahydrofluorene is determined. The polymerization heat generated in the other reaction zones is removed by proper cooling of the internal heat exchanger. The heat of the last reaction zone is about 2 6 5 ° C. The resulting polymer was extruded at the bottom of the VK column and cut into chips. The crumbs were washed with hot water at 90 ° C and dried in a tumble dryer. The relative viscosity is 2.68. Both the amine group content and the carboxylic acid end group content were 44 meq / kg. Example 4 Polymerized caprolactam of nylon 6 adjusted by ADA / 0.15% TAD was polymerized in the same VK column as in Example 3, but 0.29 wt% adipic acid, 0.5 wt% water and 0. 1 5 weight? 4-Amino-2, 2, 6, 6-tetramethylhexahydropyridine. The dried product had a relative viscosity of 2.7 3, an amine end group content of 43 meq / kg and a carboxylic acid end group content of 59 meq / kg.

O: \ 57 \ 5729l.ptc Page 16 2000.10. 23.019 4482 0

V. Description of the invention ¢ 14) Example 5 Polymerized caprolactam of nylon 6 adjusted by ADA / 0. 30% TAD was co-polymerized in the same VK column as in Example 3, and the amount of adipic acid was 0.5% by weight. % Water and 0.30 wt. Amine-2 2 9 heavy methylhexahydropyridine. The dried product has a relative viscosity of 2, amine 6 ~ 4, 53 milliequivalents / kg, and carboxylic acid end group content of 51 milliequivalents / kg earth end group. Example 6 (comparative) TPA / 0.15% TAD adjusted nylon 6 Polymerized caprolactam was polymerized in the same VK column as in Example 3 by adding 0.30 acid, 0.5 water, and 0.15% by weight of 4-amino-2, 2, 6, 6-tetramethylhexal. % On bite. The dried product has a relative viscosity of 2 to 68, an amine end group content / kg and a carboxylic acid end group content of 63 meq / kg. House Equivalent Example 7 A solution of 1115 denier / 58 filaments with a two-lobed loading surface was dyed with rich silk, the nylon 6 polymer of Example 3-6 and the commercially available nylon 6 (Ultramid 1 (Ultramid ) Bgfe Dragon 6 was obtained from BASF Corporation, Mount Lamshan, New Jersey) at 2 ^. -26 Extruded at 5 ° C. The milky gray concentrate is mixed with an appropriate amount of nylon chips and added to the spinning machine via a volumetric feeder. The extruded filament was cooled and solidified by a chilled air flow at 15 ° C. After applying the spinning finishing agent, the yarn was drafted at a draft ratio of 3.3 and deformed by spraying at 2 15 ° C. The yarn was wound at a draft roll speed of about 2 350 m / min. Example 8 Intensity retention after UV exposure

Page 17 4 48 V. Description of the invention (15) The milky gray solution-dyed yarn obtained from Example 7 was exposed to A11 under AAtcc test method 1 6- 1 99 3 according to the selected conditions for color fastness to light. as C i 6 5 weather meter, exposure 2 1 2 5 kJ, increment 4'2 5 kJ. The strength of each yarn was measured before each exposure and after each 42 5 kJ incremental exposure. Percent intensity retention after each incremental exposure is shown in Figure i. The results show that TAD-containing polymers, particularly ADA / TAD polymers, can retain a significant improvement in strength. Market 隹 Nylon 6 lost much strength during exposure, while the polymer containing tad retained its strength over 85% after 2125 kJ exposure. Example 9 Using the GM SAE J1 885 test method to test the yellowing of thick blocks. The polymer obtained from Example 3-6 and the commercially available nylon 6 (Altermide b nylon 6 obtained from BASF Company, Lanlan Mountain, New Jersey) were used for injection molding. The machine dissolves at about 265 t. The molten polymer was injected into the mold to make a 110 mm x 110 mm millimeter-thick block. Then cut this thick piece into smaller thick pieces of about 55 mm x 100 mm x 3 mm. 〃 The thick block was exposed to 8: 1 in increments of 100,000 hours and 411,000 joules under the conditions specified in the GM SAE J 1 88 5 measurement method; 1 ^ (^ 65 xenon-arc weather resistance for 1,000 hours ( 1 4 1 0 kJ). Thickness after exposure is measured using the application color system ^ Division's spectrophotometer at each exposure increment to measure yellowing (or " here 3 high means the sample is yellower). Exposure results are made as The graph is shown in Figure 2. The results show that the commercial nylon 6 polymer and the comparative Q polymer adjusted by TPA / 0.15% TAD have the most significant yellowing after b exposure. The yellowing ratio caused by TPA / TAD polymer exposure is more significant.隹 Nylon 6 polymer and comparatively polymerized by TPA / 0.15% TAD: less ADA / TAD polymer exposure results in only minimal yellowing.

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Claims (1)

-Left case in this case No. 88103601 丨 Beta Month Amendment _ Yixue, Zhongshen_Li Liwei 1. A method for producing light and thermal stability polyamides, including the production of one or more polyamine-forming monomers The usage range is one or more kinds of blocked hexahydropyridine compounds selected from amino polymethyl hexahydropyridines from 0.030 to 0.800 based on the weight of the polyamine-forming monomer used, and the usage range is The polymerization process is performed using one or more chain-adjusting compounds containing aliphatic c4-c1 () alkanedicarboxylic acid and combinations thereof from 0,001 to 0.800 by weight of polyamine-forming monomers, wherein the polymerization process is It is carried out at a temperature from 240 to 290 ° C. 2. The method of claim 1, wherein the one or more blocked hexahydropyridine compounds are selected from the group consisting of 4-amino-2,2,6,6-tetramethylhexamidine; 4- (Amine base) -2,2,6,6-tetramethylhexahydropyridine; 3-amino-2, 2, 6, 6-tetramethylhexahydropyridine; 3- (amine Alkyl) -2,2,6,6-tetramethylhexahydropyridine; 2,2,6,6-tetramethyl-4-hexahydropyridinecarboxylic acid; 2,2,6,6-tetramethyl 4-Hexahydropyridinylcarboxylic acid; 2, 2, 6, 6-tetramethyl-3-hexahydropyridinecarboxylic acid; 2, 2, 6, 6-tetramethyl-3-hexahydropyridine Carboxylic acids and combinations thereof. 3. The method according to item 2 of the scope of patent application, wherein the one or more blocked hexaargine alpha-determining compounds are 4-amino2,2,6,6-tetramethylhexazine-alpha-determine. 4. The method of claim 1, wherein the one or more aliphatic c4-clflane dicarboxylic acid chain regulating compounds are selected from the group consisting of malic acid; malonic acid; fluorenylmalonic acid; ethylmalonic acid Acid; butyl malonic acid; dimethyl malonic acid; succinic acid: methyl succinic acid; 2, 2-diamidyl succinic acid; 2, 3- dimethyl succinic acid; 2- ethyl 2-methylsuccinic acid; adipic acid; 2,2-dimethylglutaric acid; 2,3-difluorenylglutaric acid; 2,4-dimethylglutaric acid; adipic acid O: \ 57 \ 57291.ptc Page 1 2000.10.23. 024 _Case No. 88103601_Year_Month__ VI. Patent application scope acid; 3-T-based adipic acid; azelaic acid; pimelic acid; dec Diacids; decanedicarboxylic acids and combinations thereof. 5. The method according to item 4 of the patent application, wherein the one or more aliphatic dicarboxylic acid chain regulating compounds are selected from the group consisting of adipic acid, azelaic acid, decanedicarboxylic acid, sebacic acid, and combinations thereof . 6. The method according to claim 5 in which the one or more aliphatic dicarboxylic acid chain regulating compounds are adipic acid. 7. If the method of the scope of application for item 1 of the patent is applied, it makes the light and thermal stability polyamide 6 be nylon 6. 8. The method of claim 1, wherein the polyamidine-forming monomer comprises caprolactam monomer. 9. A light and thermally stable poly (vinyl alcohol) amine, comprising a polymer main bond, in an amount ranging from 0.030 to 0.800 based on the weight of the polyamine-forming monomer used, or more than one selected from aminopolymethylhexahydro Pyridine-blocking hexahydropyridine compounds, and one or more aliphatic C4-C10 alkyldicarboxylic acid chain adjusting compounds in an amount ranging from 0.001 to 0.800 based on the weight of the polyamine-forming monomer used, wherein the One or more blocked hexahydro roars. Chemical compounds and one or more aliphatic C4-C10 alkyl dicarboxylic acid chain regulating compounds are chemically bonded to the polymer backbone. 1 0. The polyamide according to item 9 of the application, wherein the one or more blocked hexahydropyridine compounds are selected from the group consisting of 4-amino-2,2,6,6-tetramethylhexahydropyridine ; 4- (aminoalkyl) -2, 2,6,6-tetramethylhexahydropyridine; 3-amino-2,2,6,6-tetramethylhexahydropyridine; 3- (amino Alkyl) -2,2,6,6-tetrafluorenylhexahydropyridine; 2,2,6,6-tetrafluorenyl-4-hexahydropyridinecarboxylic acid; O: \ 57 \ 5729l.ptc Page 2 2000.10. 23.025 4482 02 _Case No. 88103601_Year Month and Revise Potassium complex acid; 2, 2, 6, 6-tetramethyl-3-hexahydropyridinecarboxylic acid: 2, 2, 6,6-tetramethyl-3-hexahydropyridinyl carboxylic acid and combinations thereof. 11. The polyamidoamine according to item 10 of the application, wherein the one or more blocked hexahydropyridine compounds are 4-amino 2,2,6,6-tetramethylpyridine. 1 2. The polyamidamine according to item 11 of the application, wherein the one or more aliphatic (: 4-(: 1 () alkanedicarboxylic acid chain regulating compounds are selected from the group consisting of malic acid; malonic acid; Methylmalonic acid; ethylmalonic acid; butylmalonic acid; dimethylmalonic acid; succinic acid; fluorenyl succinic acid; 2, 2-dimethyl succinic acid; 2, 3- Dimethyl succinic acid; 2-ethyl-2-methylsuccinic acid; glutaric acid; 2, 2-dimethylglutaric acid; 2,3-dimethylglutaric acid; 2,4- Difyl glutaric acid; adipic acid; 3-methyl adipic acid; azelaic acid; pimelic acid; sebacic acid; decanedicarboxylic acid; dodecanedioic acid; and combinations thereof. 1 3. For example, the polyamine of the scope of application for the patent No. 12 makes the one or more aliphatic c4-c1D alkanedicarboxylic acid chain adjusting compounds selected from the group consisting of adipic acid, azelaic acid, decanedicarboxylic acid, and Diacids, and combinations thereof. 1 4. Polyamines as claimed in item 13 of the scope of the application, wherein the one or more aliphatic C4-C, alkylene dicarboxylic acid chains are regulated. The compound is adipic acid. 1 5 . For example, the polyamide of item 9 of the patent scope, wherein the polyamide is nylon 6. 1 6. According to the application The light and heat-stabilizing polyamide of item 9 of the patent scope, wherein the spinning effect of the light and heat-stabilizing polyamide is increased by at least 0.5%. 1 7. If the light and heat of item 9 of the patent scope is applied Stable Polyamines O: \ 57 \ 57291.ptc Page 3 2000.10. 23.026 448202 O: \ 57 \ 57291.ptc Page 4 2000.10.23.027