CN110592708A - Fiber made of polyamide modified polyester - Google Patents
Fiber made of polyamide modified polyester Download PDFInfo
- Publication number
- CN110592708A CN110592708A CN201910868808.4A CN201910868808A CN110592708A CN 110592708 A CN110592708 A CN 110592708A CN 201910868808 A CN201910868808 A CN 201910868808A CN 110592708 A CN110592708 A CN 110592708A
- Authority
- CN
- China
- Prior art keywords
- fiber
- modified polyester
- polyamide
- gas
- polyester
- 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.)
- Pending
Links
Abstract
The invention relates to a polyamide modified polyester, a preparation method thereof and a fiber prepared from the polyamide modified polyester. The polyamide modified polyester is composed of structural units represented by the following structural formulas I and II: wherein x is an integer of 2 to 4, y is an integer of 4 to 6, z is an integer of 4 to 12, R1～R4Each independently selected from H. The polyamide modified polyester has high water absorption, the maximum saturated water absorption can reach 5-6%, the fiber prepared by the polyamide modified polyester has excellent dyeing performance, the addition amount of polyamide can be effectively reduced, the modification cost is reduced, and meanwhile, the problems that the spinning is influenced by residual monomers existing in amino acids such as nylon 6 or lactam type nylon and the like are solved.
Description
The application is a divisional application of Chinese patent application with the application date of 2014, 3-04, the application number of 201410077480.1, the invention name of polyamide modified polyester, a preparation method thereof and a fiber prepared from the polyamide modified polyester.
Technical Field
The invention relates to the field of high polymer materials, in particular to polyamide modified polyester, a preparation method thereof and fibers prepared from the polyamide modified polyester.
Background
Polyester fibers are widely applied due to good performance, but because the polyester fibers lack hydrophilic groups, the polyester fibers have poor affinity with rubber in the aspect of industrial yarns, and need to be subjected to gum dipping treatment for many times, and in the aspect of civil yarns, disperse dyes need to be used for dyeing at high temperature and high pressure, and because the solubility of the disperse dyes is low, azo promoters need to be added, so that serious environmental pollution is caused. In recent years, chemical fiber yield in China is rapidly developed, wherein the yield of terylene is the first world, and the productivity is still rapidly developed. At present, more and more polyester fibers are used for blending with natural protein fibers such as wool and the like and are used for preparing worsted fabrics. However, natural protein fibers such as wool, silk and the like are dyed by acid dyes which are low in price, complete in color spectrum and bright in color. If ordinary polyester fiber is blended with wool, real silk and the like, one-bath piece dyeing cannot be carried out. In order to solve this problem, many scholars and specialists at home and abroad have conducted intensive research. At present, two methods of copolymerization and blending are mainly adopted to solve the dyeability of polyester fibers.
Patent CN101942708B discloses a polyester-polyamide copolymer, which has an dye uptake of more than 80% under acid dyes, however, the added polyamide is a caprolactam prepolymer, it is known that about 10% of monomers exist in the caprolactam polymerization process, and the caprolactam prepolymer needs to be washed with water before spinning, otherwise, spinning cannot be performed.
Patent CN 103232596A discloses a method for improving dyeability of aliphatic polyamide modified copolyester, polyamide oligomer with intrinsic viscosity of 0.5-1.0 dL/g and ethylene glycol isophthalate-5-sulfonic acid alkali metal salt are added as additives in the patent, and the additives are expensive and difficult to synthesize.
In Japanese patent laid-open No. Sho 63-256716, a polyester fiber is made dyeable with a cationic dye under normal pressure conditions by copolymerizing polyethylene glycol having a molecular weight of 200 or more with a sulfonic acid isophthalic acid metal salt into a polyester molecular chain. The introduction of the flexible polyethylene glycol molecular chain segment enables the structure of the polyester fiber molecular chain to be looser, the amorphous area to be increased and the glass transition temperature to be reduced, so that the cationic dye can be dyed at relatively low temperature, namely, the cationic dye can be dyed under the condition of normal-pressure boiling dyeing. However, the introduction of polyether segment in polyester molecular chain can make the polyester fiber have poor heat resistance, unstable spinning, and affect spinnability and fabric performance.
Patent CN1291081C discloses a method for preparing acid dyeable polyester fiber by using polyamide and polyethylene-methacrylate to form a dyeing modifier and adding the dyeing modifier into polyester chips. However, because the compatibility between polyester and polyamide is poor, the spinning is still difficult in spite of the improvement of polyethylene-methacrylate, and it is difficult to realize industrial spinning. Furthermore, from the microstructure analysis, the polyamide is grafted on the side chain of the polyester only through polyethylene-methacrylate, resulting in insufficient introduction of basic groups and limited dye-uptake ability of the acid dye.
Patent CN1249141C discloses a method for preparing acid dyeable modified polyester fiber by using polymer containing one or more monomers of secondary amine or secondary amine salt as modifier and polyester to form acid dyeable composition. However, the polymer of one or more monomers containing secondary amine or secondary amine salt prepared has complex process and higher cost, and the realization of industrialization is difficult.
In patent CN101585915B, a diamide diol, a dibasic acid and an aliphatic diol are used to perform melt polycondensation to prepare a polyesteramide prepolymer having both a carboxyl-terminated structure and a hydroxyl-terminated structure, and then a diacyl bislactam and a bisoxazoline chain extender are used to perform chain extension to obtain polyesteramide. The raw material of the diamide diol disclosed by the patent is a common chemical raw material, and needs to be prepared in advance, but the method has the common defect of chain extension reaction, namely the molecular weight distribution is not easy to control, so that certain influence is caused on spinning.
The patent CN101942708B is prepared by carrying out ester exchange reaction on dimethyl terephthalate and ethylene glycol, or dimethyl terephthalate and ethylene glycol and propylene glycol, or dimethyl terephthalate and ethylene glycol and butanediol, or dimethyl terephthalate and ethylene glycol, propylene glycol and butanediol, and then carrying out copolymerization with nylon 6 polymer. Although the patent mentions that the polyester-polyamide copolymer having an approximate structure can be obtained by using nylon 66, the specific example of nylon 6 is not replaced by nylon 66 in the examples of the patent. Further, the inventors have found experimentally that a problem of uneven dispersion of nylon 6 in a polyester is likely to occur in a polyester obtained by modifying nylon 6 with nylon 6 obtained by polymerizing a monomer as a raw material during polymerization. After a lot of tests, the inventor speculates that the mechanism of the uneven dispersion problem of nylon 6 in polyester is as follows: terephthalic acid as a strong acid can basically and completely replace the connection of aliphatic carboxyl and amino, the two ends of pentamethylene diamine of a bi-monomer nylon (such as nylon 66) are connected with the same terephthalic acid and then form an ester with ethylene glycol to perform further ester exchange polymerization, namely, the two ends of a molecular chain have no difference, and for a mono-monomer nylon (such as nylon 6), after the terephthalic acid replaces fatty acid, the monomers are aliphatic carboxylic acid at one end and aromatic carboxylic acid at the other end, the asymmetry of the monomers causes the two ends to perform further esterification and the ester exchange polycondensation to generate speed difference, so that units containing amide groups cannot be uniformly distributed on the molecular chain, and the nonuniform distribution affects many performances of fibers, particularly the uniformity of mechanical properties and dyeing properties.
On the other hand, the polyamide-modified polyester has both water-absorbing amide groups and water-repellent ester bonds, which results in a very sensitive structure, and how to spin the polyamide-modified polyester at a low processing temperature and how to obtain a polyamide-modified polyester with better flowability is a problem that has not been studied intensively in order to facilitate the practical application of the polyamide-modified polyester in spinning.
Meanwhile, whether the introduction of the pentamethylene diamine with odd carbon units can effectively destroy the crystal regularity of the traditional even carbon monomers and enable the moisture and the dye to enter the inside of the polymer more easily is unknown, so that the polyester modification effect same as that of the even carbon units is realized by using lower addition amount, and the manufacturing cost is reduced.
Accordingly, intensive and systematic studies on polyamide-modified polyesters have been conducted to develop polyamide-modified polyester fibers having a low melting point and excellent flowability, processability, moisture absorption and dye-uptake properties.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provide a polyamide modified polyester containing a bio-based structure, effectively overcome the defect of poor hydrophilicity of the polyester at low cost, and prepare fibers from the polyamide modified polyester to realize cationic dyeability and high dye uptake.
In one aspect, the present invention provides a polyamide-modified polyester comprised of structural units represented by the following structural formulae I and II:
wherein x is an integer of 2 to 18, y is an integer of 2 to 18, z is an integer of 2 to 18, R1～R4Each independently selected from H or C1～C4An alkyl group.
In one embodiment of the polyamide-modified polyester of the present invention, the molar ratio of the structural unit i to the structural unit ii is 60:40 to 99.8:0.2, preferably 70:30 to 99: 1.
In another embodiment of the polyamide-modified polyester of the present invention, the intrinsic viscosity of the polyamide-modified polyester is 0.3 to 1.8dL/g, preferably 0.5 to 1.0 dL/g.
In another embodiment of the polyamide-modified polyester of the present invention, x is an integer of 2 to 4, y is an integer of 4 to 6, and z is an integer of 4 to 12.
In another aspect, the present invention also provides a method for preparing the above polyamide-modified polyester, comprising:
(1) under the protection of nitrogen or inert gas, adding dihydric alcohol, terephthalic acid and/or derivatives thereof into a reaction vessel to enable 90-100% of terephthalic acid and/or derivatives thereof to carry out esterification reaction;
(2) and heating the reaction container to 230-320 ℃, adding aliphatic nylon, vacuumizing until the vacuum degree reaches below 30kPa, and stopping the reaction until the intrinsic viscosity of the reaction product is 0.3-1.8 dL/g to obtain the polyamide modified polyester.
In one embodiment of the method of the present invention, the diol is one or more selected from aliphatic diols having carbon chain lengths of 2 to 18 carbon atoms, the terephthalic acid and/or its derivatives are one or more selected from terephthalic acid, mono/di-esters of terephthalic acid, terephthaloyl chloride, and compounds of the above compounds in which hydrogen on the benzene ring is partially or completely substituted by an alkane having 1 to 4 carbon atoms, and the aliphatic nylon is one or more selected from nylons formed by aliphatic diacids having carbon chain lengths of 2 to 18 and aliphatic diamines having carbon chain lengths of 2 to 18.
In another embodiment of the method of the present invention, the aliphatic nylon has a relative viscosity of 1.1 to 2.7
In another embodiment of the process of the present invention, 95% to 100% of terephthalic acid and/or its derivatives are esterified in step (1).
In another embodiment of the method of the present invention, the molar ratio of nylon, glycol, terephthalic acid and/or its derivatives is (0.002-0.4): 1-3): 1, preferably (0.01-0.3): 1.2-2.5): 1. Wherein the mole number of the nylon is measured according to the mole number of the nylon structural unit.
In another embodiment of the method of the present invention, the reaction vessel is heated to 250 to 300 ℃ in step (2).
In another embodiment of the process of the present invention, the degree of vacuum in step (2) is controlled to 1kPa or less.
In another embodiment of the process of the present invention, the reaction is stopped after the intrinsic viscosity of the polyamide-modified polyester in step (2) is 0.5 to 1.0 dL/g.
In another embodiment of the process of the present invention, one or more auxiliary agents are added during the addition of the starting materials in step (1) and/or one or more auxiliary agents are added before the heating of the reaction vessel in step (2).
In another embodiment of the process of the present invention, the auxiliary agent comprises a transesterification catalyst, an esterification catalyst, an etherification inhibitor, a polymerization catalyst, a heat stabilizer, a light stabilizer, an antioxidant, a weather resistant agent, a lubricant, a crystallization nucleating agent, a conductive filler or antistatic filler, a flame retardant, a filler.
In still another aspect, the present invention also provides a fiber, wherein the raw material of the fiber comprises the polyamide modified polyester.
In one embodiment of the fiber of the present invention, the fiber is a polyamide-modified polyester nascent fiber, a polyamide-modified polyester fiber filament, a polyamide-modified polyester POY fiber, a polyamide-modified polyester plus spandex, a polyamide-modified polyester FDY, and a polyamide-modified polyester staple fiber.
In another embodiment of the fiber of the present invention, the fineness of the fiber is 0.5 to 10dtex, preferably 1.0 to 7.0 dtex.
In another embodiment of the fiber of the present invention, the fiber has a strength of 1.0 to 8.0cN/dtex, preferably 2.0 to 5.5 cN/dtex.
In another embodiment of the fiber of the present invention, the fiber has an elongation at break of 5.0 to 400.0%, preferably 15 to 130%.
In another embodiment of the fiber of the present invention, the fiber has an acid dye uptake of greater than 75% at ambient pressure.
The polyamide modified polyester has high water absorption, the maximum saturated water absorption can reach 5-6%, the fiber prepared by the polyamide modified polyester has excellent dyeing performance, the addition amount of polyamide can be effectively reduced, the modification cost is reduced, and meanwhile, the problems that the spinning is influenced by residual monomers existing in amino acids such as nylon 6 or lactam type nylon and the like are solved.
Drawings
FIG. 1 is a DSC chart of the polyamide-modified polyester of example 2.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
In one aspect, the present invention provides a polyamide-modified polyester comprised of structural units represented by the following structural formulae I and II:
wherein x is an integer of 2 to 18, preferably an integer of 2 to 4, and more preferably 2; y is an integer of 2 to 18, preferably an integer of 4 to 6, and more preferably 5; z is an integer of 2 to 18, preferably an integer of 4 to 12, and more preferably 6; wherein R is1～R4Each independently selected from H or C1～C4Alkyl, preferably H.
In the polyesteramides of the invention, a plurality of structural units I with x having different values and a plurality of structural units II with y and z having different values may be present simultaneously.
The ratio of the structural unit I to the structural unit II is 60: 40-99.8: 0.2, preferably 70: 30-99: 1, and the intrinsic viscosity of the polyamide modified polyester is 0.3-1.8 dL/g, preferably 0.5-1.0 dL/g.
In the present invention, the polyamide-modified polyester is a polyesteramide obtained by polymerizing a polyester as a main component with a small amount of polyamide added.
The invention also provides a method for preparing the polyamide modified polyester, which comprises the following steps:
(1) under the protection of nitrogen or inert gas, adding dihydric alcohol, terephthalic acid and/or derivatives thereof into a reaction vessel, fractionating low-boiling components (small molecular products such as water) at normal pressure or low pressure to perform esterification reaction on more than 90% of terephthalic acid and/or derivatives thereof;
(2) heating the reaction container to 230-320 ℃, adding aliphatic nylon, gradually vacuumizing until the vacuum degree reaches below 30kPa, and stopping the reaction after the inherent viscosity of the polyamide modified polyester is 0.3-1.8 dL/g to obtain the polyamide modified polyester.
The present invention has no particular requirement for the addition of aliphatic nylon. The person skilled in the art can select and determine the aliphatic nylon according to the preparation method of the invention and the requirements for the polyesteramide.
In the step (1), the dihydric alcohol is selected from one or more aliphatic dihydric alcohols with carbon chain length of 2-18 carbon atoms, including ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, pentadecadiol, hexadecanediol, heptadecanediol and octadecanediol, preferably ethylene glycol, propylene glycol and butanediol.
In the step (1), two or more than two diols can be added simultaneously to form polyesters with different structures.
In the step (1), the terephthalic acid and/or the derivatives thereof are selected from one or more of terephthalic acid, mono/di-esters of terephthalic acid, terephthaloyl chloride and compounds of the above compounds, wherein hydrogen on benzene rings of the compounds is partially or completely substituted by alkane containing 1-4 carbon atoms.
In the step (1), the aliphatic nylon is selected from one or more of nylons formed by aliphatic dibasic acid with a carbon chain length of 2-18 and aliphatic diamine with a carbon chain length of 2-18, preferably nylon 56, nylon 66, nylon 510, nylon 610, nylon 512 and nylon 612, and more preferably nylon 56 and nylon 66. The relative viscosity of the aliphatic nylon is preferably 1.1 to 2.7, more preferably 1.1 to 2.4.
In the raw materials for preparing the polyesteramide, the molar ratio of the nylon, the dihydric alcohol, the terephthalic acid and/or the derivatives thereof is (0.002-0.4): 1-3): 1, and preferably (0.01-0.3): 1.2-2.5): 1. Wherein the mole number of the nylon is measured according to the mole number of the nylon structural unit.
According to the invention, the esterification end point in the step (1) is set to be 90-100%, preferably 95-100% of the esterification reaction of the terephthalic acid and/or the derivative thereof, the esterification ratio is high, the subsequent polycondensation reaction is favorably carried out, and the side reaction is easy to control. The esterification rate can be measured based on the water discharged from the reaction system.
In the preparation method of the polyamide modified polyester, the polycondensation temperature in the step (2) is preferably 230-320 ℃, the polycondensation speed is reduced due to low temperature, and the side reaction is increased due to high temperature, so that the polycondensation temperature is more preferably 250-300 ℃. The degree of vacuum in the polycondensation in the step (2) is preferably controlled to 30kPa or less, and in order to accelerate the progress of the polycondensation reaction and obtain a polyamide-modified polyester having a higher intrinsic viscosity, the degree of vacuum in the polycondensation is more preferably controlled to 1kPa or less, and the degree of vacuum in the polycondensation can be gradually reduced to increase the degree of polymerization. In order to make the polyamide-modified polyester have practical production significance, the reaction is stopped after the inherent viscosity of the polyamide-modified polyester is 0.3-1.8 dL/g, and the inherent viscosity is more preferably 0.5-1.0 dL/g.
And (3) the polyamide modified polyester obtained in the step (2) is in a melt state, nitrogen can be introduced for pressurization, drawing and granulation, the preferable nitrogen pressure is 0.05-0.8 MPa, the slice can be spun by a single-screw spinning machine after being dried, the drying temperature is preferably 70-140 ℃, and the melt can be directly conveyed to a spinning box by a melt pump on a pilot plant continuous polymerization device to be made into fibers.
According to the present invention, the one or more auxiliary agents described in the step (1) and the step (2) include various stabilizers such as a transesterification catalyst, an esterification catalyst, an etherification inhibitor, a polymerization catalyst used in the production of a polyester amide compound, a heat stabilizer, a light stabilizer, and a polymerization regulator. The auxiliaries may also be selected from antioxidants, weathering agents, lubricants, crystallization nucleating agents, conductive or antistatic fillers, flame retardants, fillers and other polycondensation-improving materials, etc., as required for the final properties of the polyesteramide. These additives may be added as needed within a range not impairing the effects of the present invention. The addition method may be any known method.
Examples of the transesterification catalyst and the esterification catalyst include compounds such as manganese, cobalt, zinc, titanium, and calcium. Examples of the etherification inhibitor include amine compounds. Examples of the polymerization catalyst include compounds containing germanium, antimony, titanium, aluminum, and the like. For example, the germanium-containing compound includes amorphous germanium dioxide, crystalline germanium dioxide, germanium chloride, tetraethoxygermanium, tetra-n-butoxygermanium, germanium phosphite, and the like, and the amount thereof is preferably 5 to 150ppm, more preferably 10 to 100ppm, and further preferably 15 to 70ppm, in terms of the concentration of germanium atoms in the polyesteramide compound. The antimony-containing compound includes antimony trioxide, antimony acetate, antimony tartrate, potassium antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and antimony triphenyl, and the amount thereof is preferably 10 to 400ppm, more preferably 20 to 350ppm, and still more preferably 30 to 300ppm, in terms of antimony atom concentration in the polyesteramide compound. Examples of the titanium-containing compound include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, and tetra-n-butyl titanate, and partial hydrolyzates thereof, titanium oxalate compounds such as titanium oxalate, titanium ammonium oxalate, titanium sodium oxalate, titanium potassium oxalate, titanium calcium oxalate, and titanium strontium oxalate, titanium trimellitate, titanium sulfate, and titanium chloride, and the amount thereof is preferably 0.5 to 300ppm, more preferably 1 to 200ppm, and still more preferably 3 to 100ppm, in terms of the titanium atom concentration in the polyesteramide compound. Examples of the aluminum-containing compound include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate and aluminum oxalate, inorganic acid salts such as oxides, aluminum hydroxide, aluminum chloride, aluminum chlorohydroxide and aluminum carbonate, alkylaluminum such as methylaluminum and ethylaluminum ethoxide, aluminum complex compounds such as aluminum acetylacetonate and acetoacetic acid, organoaluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysates thereof, and the amount thereof is preferably 1 to 400ppm, more preferably 3 to 300ppm, and still more preferably 5 to 200ppm, in terms of the aluminum atom concentration in the polyesteramide compound. In addition, in the invention of the polyester amide compound production, can use alkali metal compounds or alkaline earth metal compounds. Examples of the alkali metal compound or alkaline earth metal compound include alkali metal or alkaline earth metal carboxylates and alkoxides. The amount of the alkali metal or alkaline earth metal is preferably 0.1 to 200ppm, more preferably 0.5 to 150ppm, and still more preferably 1 to 100ppm, in terms of the atomic concentration of the alkali metal or alkaline earth metal in the polyesteramide compound.
In addition, in the production of the polyester amide compound of the present invention, as the heat stabilizer, 1 or more kinds of phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, and derivatives thereof can be used. Examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monobutyl phosphate, dibutyl phosphate, phosphorous acid, sodium hypophosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, methylphosphonic acid, dimethyl methylphosphonate, dimethyl ethylphosphonate, diethyl phenylphosphonate, and diphenyl phenylphosphonate. The amount of the phosphorus-containing compound is preferably 1 to 200ppm, more preferably 2 to 150ppm, and still more preferably 3 to 100ppm, based on the concentration of phosphorus atoms in the polyesteramide compound.
In addition, in the production of the polyester amide compound of the present invention, a higher alcohol such as lauryl alcohol may be added in order to adjust the weight average molecular weight. In addition, a polyol such as glycerin may be added to improve physical properties.
The antioxidant includes copper-based antioxidants, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like, and among them, hindered phenol-based antioxidants and phosphorus-based antioxidants are preferable.
The weather resistant agent includes a diphenol compound, a salicylate compound, a benzotriazole compound, a benzophenone compound, a hindered amine compound, and the like.
The anti-sticking agent or lubricant includes aliphatic alcohol, aliphatic amide, aliphatic bisamide, diurea, polyethylene wax, etc.
The crystallization nucleating agent comprises inorganic particles such as talc, silicon dioxide, kaolin, clay, boron nitride and the like, or metal oxides, high-melting point nylon and the like.
The plasticizer comprises octyl p-hydroxybenzoate, N-butylbenzenesulfonamide and the like.
The antistatic agent includes alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine type amphoteric antistatic agents, and the like.
The flame retardant includes melamine cyanurate, hydroxides (e.g., magnesium hydroxide, aluminum hydroxide, etc.), ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or a combination of these brominated flame retardants with antimony trioxide, and the like.
The filler includes a granular, needle-like or plate-like filler such as glass fiber, carbon black, black ink, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium dioxide, alumina, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, stainless steel, bentonite, montmorillonite, mica, etc.
The other polycondensates include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, AS resin, polystyrene, and the like.
The invention also provides a fiber, and the raw material of the fiber comprises the polyamide modified polyester. If necessary, other necessary raw materials may be added during the process of preparing the fiber, for example, preparing the sea-island fiber.
Further, the fiber may be polyamide-modified polyester nascent fiber, polyamide-modified polyester filament, polyamide-modified polyester POY fiber, polyamide-modified polyester plus spandex, polyamide-modified polyester FDY, and polyamide-modified polyester staple fiber.
The fiber fineness of the fiber provided by the invention is preferably 0.5-10 dtex, and the single fiber fineness can be adjusted by the device and the process provided by the invention according to different application fields. Due to the fact that the filament number is too low, abnormal phenomena such as end breakage and the like easily occur, and meanwhile, due to the fact that the filament number is too high, bending strength of the fabric is too high, and hand feeling is hard. Therefore, the fineness of the fiber of the present invention is more preferably in the range of 1.0 to 7.0 dtex. Meanwhile, if the monofilament fineness is kept within the range required by the invention, the appropriate number of filaments can be selected according to the application to meet the application requirement.
The strength of the fiber of the present invention is preferably 1.0 to 8.0 cN/dtex. The strength is too low, fluff is easy to appear in the weaving process, a finished product is easy to damage, the strength is too high, the spinnability is poor in spinning, the yarn breakage phenomenon is easy to appear, and the fiber is more preferably in the strength range of 2.0-5.5 cN/dtex through polymerization and spinning process adjustment according to different application fields.
The fiber of the present invention has an elongation at break of 5.0 to 400.0%, preferably 15 to 130%. The dye-uptake of the fiber dyed by the acid dye under normal pressure is more than 75 percent.
The method of preparing the above-mentioned fibers is not particularly limited in the present invention, and any suitable technique can be used, and those skilled in the art can know and determine suitable process parameters.
In one embodiment, the polyamide modified polyester chip or melt is introduced into a spinning machine by a melt pump or a single screw to be spun at 210-285 ℃, preferably 220-275 ℃, and the spinning speed is 200-1500 m/min, preferably 400-1200 m/min, more preferably 500-1100 m/min, so as to obtain the polyamide modified polyester nascent fiber.
And spinning the polyamide modified polyester at 210-285 ℃ at a spinning speed of 1500-3500 m/min, more preferably 1800-3200 m/min to obtain the polyamide modified polyester POY fiber.
Spinning polyamide modified polyester at 210-285 ℃, directly feeding the fiber from a spinneret plate into a first hot plate, wherein the temperature of the hot plate is 75-100 ℃, the speed is 800-2000 m/min, then feeding the fiber into a second hot plate, the temperature of the hot plate is 120-180 ℃, the speed is 3200-5200 m/min, and the fiber is drawn between the first hot plate and the second hot plate by 2-5 times; and (3) feeding the fiber bundle coming out of the second guide disc into a winding machine for winding at the winding speed of 3100-5200 m/min, and winding to obtain the polyamide modified polyester FDY fiber.
Performing primary drafting on the polyamide modified polyester nascent fiber at 40-90 ℃, wherein the drafting multiple is 1.5-6 times, performing secondary drafting at 80-120 ℃, the drafting multiple is 1.1-1.6 times, and performing heat setting at 120-160 ℃ to obtain a fiber filament.
Performing primary drafting on polyamide modified polyester nascent fibers at 40-90 ℃, wherein the drafting multiple is 1.5-4 times, performing secondary drafting at 80-120 ℃, and the drafting multiple is 1.1-2 times, then crimping the fibers, the number of crimps is 10-20/25 cm, then performing heat setting at 120-180 ℃ for 15 minutes, cutting the fibers after setting on a cutting machine, and packaging to obtain the polyester amide staple fibers.
The polyamide modified polyester POY fiber is drawn on a texturing machine at the speed of 300-1200 m/min by 1.3-3 times, the temperature of a preheating box is 120-220 ℃, the D/Y is 1.4-2.6, the temperature of a shaping box is 140-200 ℃, and the winding speed is 800-2200 m/min, so that the polyamide modified polyester textured yarn is obtained.
The polyamide modified polyester has higher water absorption which can reach 5-6% at most, and the fiber prepared by the polyamide modified polyester has more excellent dyeing property, so that the addition of the polyamide can be effectively reduced, and the modification cost is reduced. Meanwhile, the problems that the spinning is influenced by residual monomers existing in amino acid or lactam type nylon such as nylon 6 and the like are solved.
The polyester amide of the invention has simple process and high production efficiency, and can be directly produced by simply modifying the prior polyester device. The cotton type or wool type fiber prepared by the invention can be blended with cotton or wool in any proportion, and the fabric woven by the blended yarn can be dyed in one bath, has no color difference in dyeing, high dye uptake and deep dyeing. This greatly simplifies the dyeing process of the fabric and effectively reduces the cost. The acid amide groups contained in the polyester amide fiber fully react with the acid groups in the acid dye, so that the dye uptake of the acid dye at the temperature of 80-110 ℃ under normal pressure can reach more than 75 percent, the deep dyeing degree can be completely reached, the dyeing is uniform, the color difference is avoided, and the acid dyeability of the polyester is greatly improved. The fiber has simple preparation process, can be smoothly spun in a common polyester spinning device, has good performance, the breaking strength of the fiber is more than 1.0cN/dtex, the elongation at break is more than 5 percent, all indexes can meet the requirements of subsequent weaving, and the fiber has simple production operation and lower cost and is suitable for industrial production. Meanwhile, compared with the mixture of polyester and polyamide, the polyesteramide of the invention overcomes the problems of poor compatibility and difficult spinning of the mixture.
Unless otherwise defined, all terms used herein have the meanings that are commonly understood by those skilled in the art.
The present invention will be described in further detail with reference to examples.
Examples
The properties of the examples and comparative examples were measured by the following methods and methods known in the industry:
intrinsic viscosity η (dL/g), test method: reference is made to ASTM D4603-2003;
melting point Tm (° c), test method: reference GB/T19466.3-2004;
saturated water absorption (%), test method: reference is made to GB/T1034-2008;
breaking strength (CN/dtex), test method: reference GB/T3916-1997;
elongation at break (%), test method: reference GB/T3916-1997;
dye uptake (%), test method: refer to FZ/T54037-2011.
EXAMPLE 1 preparation of Polyamide-modified polyester
Adding 19.4kg of dimethyl terephthalate and 11.6kg of ethylene glycol into a 200L reaction kettle, heating to 202 ℃, reacting, fractionating low-boiling components, reacting for 90 minutes, and ending the ester exchange reaction when the fraction reaches 98% of the theoretical amount. Heating the system to 226 ℃, adding 10g of tetrabutyl titanate polycondensation catalyst and 0.12kg of nylon 66 with the relative viscosity of 2.0, vacuumizing to 40Pa, gradually heating to 280 ℃, reacting for 4 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.80dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 258 ℃, and the saturated water absorption is 0.32%.
EXAMPLE 2 preparation of Polyamide-modified polyester
Adding 19.4kg of dimethyl terephthalate, 12.4kg of ethylene glycol and 3.8g of tetrabutyl titanate into a 200L reaction kettle, heating to 198 ℃, reacting, fractionating low-boiling components, reacting for 80 minutes, and finishing the ester exchange reaction when the fraction reaches 98% of the theoretical amount. Heating the system to 260 ℃, adding 10g of tetrabutyl titanate polycondensation catalyst and 0.58kg of nylon 56 with the relative viscosity of 1.8, vacuumizing to 50Pa, gradually heating to 275 ℃, reacting for 4 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.86dL/g, and drawing and granulating. The melting point of the obtained polyamide modified polyester is 244 ℃, and the saturated water absorption is 0.68%.
EXAMPLE 3 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 11.1kg of ethylene glycol, 0.9kg of butanediol and 2.2g of tetrabutyl titanate into a 200L reaction kettle, heating to 205 ℃, reacting, fractionating low-boiling components, reacting for 80 minutes, and finishing the esterification reaction when the fraction reaches 99% of the theoretical amount. Heating the system to 260 ℃, adding 8.2g of tetrabutyl titanate polycondensation catalyst and 1.16kg of nylon 56 with the relative viscosity of 2.2, vacuumizing to 60Pa, gradually heating to 275 ℃, reacting for 4 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.82dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 235 ℃, and the saturated water absorption is 1.1%.
EXAMPLE 4 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 11.1kg of ethylene glycol, 0.5kg of propylene glycol, 0.6kg of butanediol and 2g of sodium hypophosphite into a 200L reaction kettle, heating to 200 ℃, reacting, fractionating low-boiling-point components, reacting for 100 minutes, and finishing the esterification reaction when the fraction reaches 98% of the theoretical amount. Heating the system to 262 ℃, adding 8.2g of tetrabutyl titanate polycondensation catalyst and 2.33kg of nylon 56 with the relative viscosity of 1.4, vacuumizing to 30Pa, gradually heating to 278 ℃, reacting for 4 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.78dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 224 ℃, and the saturated water absorption is 2.2%.
EXAMPLE 5 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 10.3kg of ethylene glycol, 0.7kg of propylene glycol, 0.9kg of butanediol, 2g of sodium hypophosphite and 18g of antimony trioxide into a 200L reaction kettle, heating to 205 ℃, reacting, fractionating low-boiling-point components, reacting for 120 minutes, and finishing the esterification reaction when the fraction reaches 99% of the theoretical amount. Heating the system to 265 ℃, adding 6.2g of tetrabutyl titanate polycondensation catalyst, 5.8kg of nylon 56 with relative viscosity of 2.0 and 1.2kg of nylon 66 with relative viscosity of 1.8, vacuumizing to 60Pa, gradually heating to 282 ℃, reacting for 4 hours, filling 0.4MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.76dL/g, and carrying out wire drawing and granulation. The obtained polyamide modified polyester has no melting point and the saturated water absorption rate is 5.3 percent.
EXAMPLE 6 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 0.6kg of ethylene glycol, 16.2kg of butanediol and 2.4g of tetrabutyl titanate into a 200L reaction kettle, heating to 210 ℃, reacting, fractionating low-boiling-point components, reacting for 120 minutes, and finishing the esterification reaction when the fraction reaches 99% of the theoretical amount. Heating the system to 270 ℃, adding 8.0g of tetrabutyl titanate polycondensation catalyst and 1.16kg of nylon 66 with the relative viscosity of 2.4, vacuumizing to 50Pa, gradually heating to 285 ℃, reacting for 4 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.84dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 220 ℃, and the saturated water absorption is 0.71%.
EXAMPLE 7 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 10.3kg of ethylene glycol, 0.7kg of propylene glycol, 0.9kg of butanediol, 2g of sodium hypophosphite and 60g of titanium dioxide into a 200L reaction kettle, heating to 220 ℃, reacting, fractionating low boiling point components, reacting for 120 minutes, and finishing the esterification reaction when the fraction reaches 99% of the theoretical amount. Heating the system to 272 ℃, adding 6.2g of tetrabutyl titanate polycondensation catalyst and 6.8kg of nylon 66 with the relative viscosity of 1.7, vacuumizing to 60Pa, gradually heating to 285 ℃, reacting for 4 hours, filling 0.4MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.82dL/g, and carrying out wire drawing and granulation. The obtained polyamide modified polyester has no melting point and the saturated water absorption rate is 3.1 percent.
EXAMPLE 8 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 13.2kg of ethylene glycol, 0.7kg of propylene glycol, 2g of sodium hypophosphite, 2.4g of tetrabutyl titanate and 1.6g of sodium hypophosphite into a 200L reaction kettle, heating to 202 ℃, reacting, fractionating low-boiling-point components, reacting for 90 minutes, and finishing the esterification reaction when the fraction reaches 99% of the theoretical amount. Heating the system to 245 ℃, adding 8.0g of tetrabutyl titanate polycondensation catalyst and 1.6kg of nylon 512 with the relative viscosity of 1.8, vacuumizing to 60Pa, gradually heating to 270 ℃, reacting for 5 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.91dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 228 ℃, and the saturated water absorption is 0.51%.
EXAMPLE 9 preparation of Polyamide-modified polyester
Adding 16.6kg of terephthalic acid, 14.4kg of propylene glycol, 0.5kg of butanediol, 2g of sodium hypophosphite, 3.2g of tetraisopropyl titanate and 32g of sodium pyrophosphate solution containing titanium dioxide into a 200L reaction kettle, heating to 220 ℃, reacting, fractionating low-boiling-point components, reacting for 120 minutes, and finishing the esterification reaction when the fraction reaches 98% of the theoretical amount. Heating the system to 248 ℃, adding 6.5g of tetraisopropyl titanate polycondensation catalyst and 1.8kg of nylon 610 with the relative viscosity of 1.4, vacuumizing to 80Pa, gradually heating to 270 ℃, reacting for 5 hours, filling 0.5MPa of nitrogen into a polymerization kettle when the intrinsic viscosity of the polyesteramide in the kettle is 0.72dL/g, and carrying out wire drawing and granulation. The melting point of the obtained polyamide modified polyester is 206 ℃, and the saturated water absorption is 0.47%.
EXAMPLE 10 preparation of Polyamide-modified polyester filament
The polyamide-modified polyester chips obtained in example 2 were vacuum-dried at 120 ℃ for 10 hours, spun at 265 ℃ and wound at a speed of 600m/min to obtain polyesteramide nascent fibers, and the nascent fibers were subjected to primary drawing at 75 ℃ at a draw ratio of 3, secondary drawing at 115 ℃ at a draw ratio of 1.4 and heat-setting at 150 ℃ to obtain filaments. The breaking strength of the fiber is 4.1cN/dtex, the elongation at break is 29 percent, and the fiber modulus is 36 cN/dtex; the obtained fiber is dyed for 90 minutes at 93 ℃ and normal pressure in red acid dye with the bath ratio of 1: 20, washed and dried, and the dye uptake of the polyester amide filament yarn can reach 75 percent through detection. Dyeing is uniform and has no color difference.
Example 11 preparation of Polyamide-modified polyester FDY fiber
After the polyamide modified polyester chip obtained in the embodiment 3 is dried in vacuum at 120 ℃ for 12 hours, spinning is carried out at 255 ℃, the temperature of a first hot plate is 80 ℃, the speed is 1500m/min, then the polyamide modified polyester chip enters a second hot plate, the temperature of the hot plate is 160 ℃, the speed is 3750m/min, fiber drawing is carried out between the first hot plate and the second hot plate, and the drawing multiple is 2.5 times; and (4) feeding the fiber bundle coming out of the second guide disc into a winding machine for winding at the winding speed of 3700m/min to obtain the polyamide modified polyester FDY fiber after winding. The breaking strength of the fiber is 3.77cN/dtex, and the elongation at break is 26%; dyeing the obtained fiber in a red acid dye with a bath ratio of 1: 20 at 93 ℃ for 30 minutes under normal pressure, washing with water, drying, and detecting that the dye uptake of the polyamide modified polyester copolymer FDY fiber can reach 81%. Dyeing is uniform, and no color difference or broken filament exists.
Example 12 preparation of Polyamide-modified polyester plus Elastic yarn
The polyamide-modified polyester chip obtained in example 4 was vacuum-dried at 120 ℃ for 12 hours, spun at 248 ℃ at a winding speed of 2800m/min to obtain a polyester amide copolymer POY fiber, and this fiber was drawn on a draw texturing machine at a speed of 900m/min by 1.6 times, the preheating oven temperature was 200 ℃, the D/Y was 1.7, and the winding speed was 1400m/min to obtain a polyamide-modified polyester textured yarn. The breaking strength of the fiber is 2.77cN/dtex, and the elongation at break is 30%; dyeing the obtained fiber in a blue acid dye with a bath ratio of 1: 20 at 95 ℃ for 60 minutes under normal pressure, washing with water, drying, and detecting that the dye uptake of the polyamide modified polyester plus spandex can reach 86%. Dyeing is uniform, and no color difference or broken filament exists.
EXAMPLE 13 preparation of Polyamide-modified polyester staple fiber
The polyamide modified polyester chip obtained in example 6 was vacuum-dried at 120 ℃ for 10 hours, and then the pretreated polyester amide copolymer was spun at 243 ℃ at a winding speed of 800m/min to obtain a polyester amide nascent fiber, which was then subjected to primary drawing at 55 ℃ at a draw ratio of 3.2, secondary drawing at 120 ℃ at a draw ratio of 1.3, and then the fiber was crimped, and then heat-set at 160 ℃ for 15 minutes, and the shaped fiber was cut and packaged on a cutter to obtain cotton type polyamide modified polyester staple fiber having a fineness of 1.8dtex and a length of 38 mm. The breaking strength of the fiber is 2.09cN/dtex, the elongation at break is 41 percent, and the number of crimps is 13/25 cm; dyeing the obtained fiber in a blue acid dye with a bath ratio of 1: 20 at 90 ℃ under normal pressure for 35 minutes, washing with water, drying, and detecting that the dye uptake of the cotton type polyamide modified polyester copolymer short fiber can reach 80%. Dyeing is uniform and has no color difference.
EXAMPLE 14 preparation of Polyamide-modified polyester as-spun fiber
The polyamide modified polyester chip obtained in the example 9 is dried in vacuum at 120 ℃ for 10 hours, then is added into a single screw extruder, and is subjected to melt extrusion at 240 ℃ to prepare polyamide modified polyester melt, the obtained melt enters a spinning manifold after being metered by a metering pump, and is sprayed out from a spinneret plate hole after being subjected to melt distribution and homogenization in a spinning assembly of the spinning manifold to form melt stream; and cooling and oiling the melt trickle, and winding at the spinning speed of 1100m/min to obtain the polyamide modified polyester copolymer nascent fiber. The as-spun fiber had a breaking strength of 1.0cN/dtex and an elongation at break of 360%.
Comparative example 1 preparation of Polyamide-modified polyester
Adding 19.4kg of dimethyl terephthalate, 12.4kg of ethylene glycol and 3.8g of tetrabutyl titanate into a 200L reaction kettle, heating to 198 ℃, reacting for 80 minutes, and ending the ester exchange reaction when the fraction reaches 98% of the theoretical amount. Then 10g of tetrabutyl titanate polycondensation catalyst is added, 0.58kg of polycaprolactam oligomer with the relative viscosity of 2.0 is added after the temperature is raised to 240 ℃, the vacuum pumping is carried out until the pressure reaches 50Pa, the temperature is continuously raised to 270 ℃, the reaction is carried out for 4 hours, when the intrinsic viscosity of the polyesteramide in the polymerization kettle is 0.82dL/g, 0.5MPa nitrogen is filled into the polymerization kettle, and the wire drawing and the granulation are carried out. The melting point of the obtained polyesteramide was 246 ℃ and the saturated water absorption was 0.42%.
Comparative example 2 production of Polyamide-modified polyester filament
The polyester amide chip obtained in comparative example 1 was vacuum dried at 120 ℃ for 10 hours, spun at 265 ℃ and wound at a speed of 600m/min to obtain a polyester amide nascent fiber, and the nascent fiber was subjected to primary drawing at 75 ℃ at a draw ratio of 3 times, secondary drawing at 115 ℃ at a draw ratio of 1.4 times, and heat-setting at 150 ℃ to obtain a polyester amide fiber filament. The breaking strength of the fiber is 3.9cN/dtex, the elongation at break is 30 percent, and the fiber modulus is 35 cN/dtex; the obtained fiber is dyed for 90 minutes at 93 ℃ and normal pressure in red acid dye with the bath ratio of 1: 20, and the dye uptake of the polyester amide filament yarn can reach 70 percent through detection after the fiber is washed and dried. Dyeing is uniform, no color difference exists, and broken filaments exist.
The above embodiments are merely illustrative of the technical solutions and do not limit the technical solutions of the present invention. According to the knowledge of the existing polyamide modified polyester preparation method, the polyamide modified polyester with different viscosity numbers can be realized by adjusting the raw material ratio in the preparation process, the temperature and the pressure in the preparation process and the like by the technical personnel in the field.
The polyamide-modified polyester of example 2 was subjected to differential scanning calorimetry to obtain a DSC spectrum, as shown in FIG. 1, having only one glass transition temperature (Tg) and one melting peak (Tm), which indicates that the polyamide was completely incorporated into the main chain of the polyester and no phase separation occurred, and also indicates that the obtained polyamide-modified polyester is a homogeneous copolymer and does not contain homopolymers or blends.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.
Claims (7)
1. A fiber characterized in that a raw material of the fiber comprises a polyamide-modified polyester composed of structural units represented by the following structural formulae I and II:
wherein x is an integer of 2 to 4, y is an integer of 4 to 6, z is an integer of 4 to 12, R1～R4Each independently selected from H;
wherein the molar ratio of the structural unit I to the structural unit II is 60: 40-99.8: 0.2, preferably 70: 30-99: 1;
the preparation method of the polyamide modified polyester comprises the following steps:
(1) under the protection of nitrogen or inert gas, adding dihydric alcohol, terephthalic acid and/or derivatives thereof into a reaction vessel to enable 95-100% of terephthalic acid and/or derivatives thereof to carry out esterification reaction;
(2) and heating the reaction container to 250-300 ℃, adding aliphatic nylon, vacuumizing until the vacuum degree reaches below 1kPa, and stopping the reaction when the intrinsic viscosity of the reaction product is 0.5-1.0 dL/g to obtain the polyamide modified polyester.
2. The fiber according to claim 1, wherein the diol is one or more selected from the group consisting of aliphatic diols having carbon chain lengths of 2 to 4 carbon atoms,
the terephthalic acid and/or the derivatives thereof are selected from one or more of terephthalic acid, terephthalic acid mono/diester and terephthalic acid dichloride,
the aliphatic nylon is selected from one or more of nylons formed by aliphatic dibasic acid with a carbon chain length of 6-12 and aliphatic diamine with a carbon chain length of 4-6; and/or the presence of a gas in the gas,
the molar ratio of the nylon, the dihydric alcohol, the terephthalic acid and/or the derivatives thereof is (0.002-0.4): 1-3): 1, preferably (0.01-0.3): 1.2-2.5): 1; and/or the presence of a gas in the gas,
the relative viscosity of the aliphatic nylon is 1.1-2.7.
3. The fiber of claim 1, wherein one or more auxiliary agents are added during the addition of the starting material in step (1) and/or prior to the heating of the reaction vessel in step (2).
4. The fiber of claim 3, wherein the auxiliary agent comprises a transesterification catalyst, an esterification catalyst, an etherification inhibitor, a polymerization catalyst, a heat stabilizer, a light stabilizer, an antioxidant, a weather resistant agent, a lubricant, a crystallization nucleating agent, a conductive filler or an antistatic filler, a flame retardant, a filler.
5. The fiber of claim 1, wherein the fiber is a polyamide-modified polyester nascent fiber, a polyamide-modified polyester filament, a polyamide-modified polyester POY fiber, a polyamide-modified polyester plus spandex, a polyamide-modified polyester FDY, and a polyamide-modified polyester staple fiber;
preferably, the preparation method of the fiber comprises the following steps:
introducing the polyamide modified polyester chips or melts into a spinning machine by using a melt pump or a single screw, spinning at 210-285 ℃, preferably at 220-275 ℃, at 200-1500 m/min, preferably at 400-1200 m/min, more preferably at 500-1100 m/min, and thus obtaining polyamide modified polyester nascent fibers; and/or the presence of a gas in the gas,
spinning the polyamide modified polyester at 210-285 ℃, wherein the spinning speed is 1500-3500 m/min, more preferably 1800-3200 m/min, and obtaining polyamide modified polyester POY fiber; and/or the presence of a gas in the gas,
spinning the polyamide modified polyester at 210-285 ℃, directly feeding the fiber from a spinneret plate into a first hot plate, wherein the temperature of the hot plate is 75-100 ℃, the speed is 800-2000 m/min, then feeding the fiber into a second hot plate, the temperature of the hot plate is 120-180 ℃, the speed is 3200-5200 m/min, and the fiber is drawn between the first hot plate and the second hot plate by 2-5 times; feeding the fiber bundle coming out of the second guide disc into a winding machine for winding at the winding speed of 3100-5200 m/min to obtain the polyamide modified polyester FDY fiber after winding; and/or the presence of a gas in the gas,
carrying out primary drafting on the polyamide modified polyester nascent fiber at 40-90 ℃, wherein the drafting multiple is 1.5-6 times, carrying out secondary drafting at 80-120 ℃, the drafting multiple is 1.1-1.6 times, and carrying out heat setting at 120-160 ℃ to obtain a fiber filament; and/or the presence of a gas in the gas,
performing primary drafting on the polyamide modified polyester nascent fiber at 40-90 ℃, wherein the drafting multiple is 1.5-4 times, performing secondary drafting at 80-120 ℃, the drafting multiple is 1.1-2 times, then crimping the fiber, the number of crimps is 10-20/25 cm, then performing heat setting at 120-180 ℃ for 15 minutes, cutting the shaped fiber on a cutting machine, and packaging to obtain polyester amide staple fiber; and/or the presence of a gas in the gas,
drawing the polyamide modified polyester POY fiber on a texturing machine at a speed of 300-1200 m/min by 1.3-3 times, wherein the temperature of a preheating box is 120-220 ℃, the D/Y is 1.4-2.6, the temperature of a shaping box is 140-200 ℃, and the winding speed is 800-2200 m/min, so as to obtain the polyamide modified polyester textured yarn.
6. The fiber according to claim 1, wherein the fiber has a fineness of 0.5 to 10dtex, preferably 1.0 to 7.0 dtex; and/or the presence of a gas in the gas,
the strength of the fiber is 1.0-8.0 cN/dtex, preferably 2.0-5.5 cN/dtex; and/or the presence of a gas in the gas,
the elongation at break of the fiber is 5.0-400.0%, preferably 15-130%.
7. The fiber of any one of claims 1 to 6, wherein the fiber has an acid dye uptake of greater than 75% at ambient pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910868808.4A CN110592708A (en) | 2014-03-04 | 2014-03-04 | Fiber made of polyamide modified polyester |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410077480.1A CN104892933A (en) | 2014-03-04 | 2014-03-04 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
| CN201910868808.4A CN110592708A (en) | 2014-03-04 | 2014-03-04 | Fiber made of polyamide modified polyester |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410077480.1A Division CN104892933A (en) | 2014-03-04 | 2014-03-04 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110592708A true CN110592708A (en) | 2019-12-20 |
Family
ID=54025930
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910868849.3A Pending CN110563942A (en) | 2014-03-04 | 2014-03-04 | preparation method of polyamide modified polyester |
| CN201410077480.1A Pending CN104892933A (en) | 2014-03-04 | 2014-03-04 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
| CN201910868808.4A Pending CN110592708A (en) | 2014-03-04 | 2014-03-04 | Fiber made of polyamide modified polyester |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910868849.3A Pending CN110563942A (en) | 2014-03-04 | 2014-03-04 | preparation method of polyamide modified polyester |
| CN201410077480.1A Pending CN104892933A (en) | 2014-03-04 | 2014-03-04 | Polyamide-modified polyester and preparation method thereof, and fibers prepared from polyamide-modified polyester |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN110563942A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107011516B (en) * | 2017-04-07 | 2020-05-12 | 东华大学 | Polyester-polypentamethylenediamine diacid block copolymer, preparation method thereof and fiber |
| CN109867779B (en) * | 2017-12-05 | 2021-12-07 | 上海凯赛生物技术股份有限公司 | Preparation method of polyesteramide and product thereof |
| CN109930229A (en) * | 2017-12-19 | 2019-06-25 | 上海凯赛生物技术研发中心有限公司 | A kind of copolyamide Blulked continuous Filament and its preparation method and application |
| CN109023566A (en) * | 2018-07-30 | 2018-12-18 | 江苏百利达股份有限公司 | A kind of preparation method of high intensity 66 long filament of high-shrinkage polyamide |
| CN110528108B (en) * | 2019-08-20 | 2021-09-28 | 浙江恒澜科技有限公司 | Preparation method of multicomponent copolyester elastic fiber |
| CN112899879B (en) * | 2021-01-18 | 2022-07-26 | 万华新材料有限公司 | Preparation method of environment-friendly base fabric |
| CN113956472B (en) * | 2021-10-22 | 2023-09-19 | 擎天材料科技有限公司 | Polyester resin and preparation method and application thereof |
| CN116695272A (en) * | 2023-08-08 | 2023-09-05 | 江苏恒科新材料有限公司 | Breathable cationic dyeable polyester fiber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2851443A (en) * | 1955-04-26 | 1958-09-09 | Eastman Kodak Co | Quenchable copolyesters of a glycol, terephthalic acid and an alkylene diamine dicarboxylate and their preparation |
| US4116943A (en) * | 1976-03-22 | 1978-09-26 | Rhone-Poulenc-Textile | Polyester-amides |
| CN101942708A (en) * | 2010-08-19 | 2011-01-12 | 中国纺织科学研究院 | Polyester-polyamide copolymer fiber and manufacturing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5650469A (en) * | 1995-10-25 | 1997-07-22 | Eastman Chemical Company | Polyester/polyamide blend having improved flavor retaining property and clarity |
| DE19643143C2 (en) * | 1996-10-18 | 2002-06-20 | Inventa Ag | Adhesion promoter for polyamide composites, process for their production and their use |
| DE19806930A1 (en) * | 1998-02-19 | 1999-08-26 | Bayer Ag | Biodegradable aliphatic-aromatic polyester-amide with good mechanical properties |
| CN100567600C (en) * | 2007-05-11 | 2009-12-09 | 东华大学 | A kind of copolyester section of modification or fiber and preparation method thereof |
| CN101906211B (en) * | 2010-08-19 | 2012-06-27 | 中国纺织科学研究院 | Polyester-polyamide copolymer and synthetic preparation method thereof |
-
2014
- 2014-03-04 CN CN201910868849.3A patent/CN110563942A/en active Pending
- 2014-03-04 CN CN201410077480.1A patent/CN104892933A/en active Pending
- 2014-03-04 CN CN201910868808.4A patent/CN110592708A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2851443A (en) * | 1955-04-26 | 1958-09-09 | Eastman Kodak Co | Quenchable copolyesters of a glycol, terephthalic acid and an alkylene diamine dicarboxylate and their preparation |
| US4116943A (en) * | 1976-03-22 | 1978-09-26 | Rhone-Poulenc-Textile | Polyester-amides |
| CN101942708A (en) * | 2010-08-19 | 2011-01-12 | 中国纺织科学研究院 | Polyester-polyamide copolymer fiber and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104892933A (en) | 2015-09-09 |
| CN110563942A (en) | 2019-12-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892932B (en) | Polyester amide, preparation method thereof and product fiber thereof | |
| CN110592708A (en) | Fiber made of polyamide modified polyester | |
| CN107177903B (en) | Blended fiber, preparation method thereof and fabric containing blended fiber | |
| CN109134850B (en) | Polyester amide, preparation method thereof and fiber prepared from polyester amide | |
| CA2887654C (en) | Polyamide apparel textile yarns and fabrics and garments made therefrom | |
| US6537475B1 (en) | Melt extrusion spinning polyamide fibers with sulfonated reagent | |
| US20080268736A1 (en) | Dope Dyed Flame Retardant Polyester Fibers, Textile Products Therefrom and the Method of Manufacturing Thereof | |
| CN109957856B (en) | Parallel composite fiber and preparation method thereof | |
| US6635346B2 (en) | Stain-resistant polyamide composition and fibers and method of production thereof | |
| CN104892934A (en) | Polyester amide and preparation method thereof, and fibers prepared from polyester amide | |
| JP5912669B2 (en) | Cationic dye-dyeable flame retardant polyester fiber and its fiber products | |
| CN111748092B (en) | Polyester amide, preparation method thereof and product fiber thereof | |
| EP0590365B1 (en) | A method for producing polyamide with reduced flammability | |
| EP3400254A1 (en) | Process for suppressing foam formation in the manufacture of hydrophilic polyamides | |
| CN115536838B (en) | Copolyamide resin, fiber, and preparation method and application thereof | |
| CN103467930B (en) | Polyester composition and manufacture method thereof and purposes | |
| KR102276231B1 (en) | Polyester composition for manufacturing one-component fiber with excellent deep coloration, one-component fiber manufactured thereby and manufacturing method thereof | |
| CN116234853A (en) | Polyester resin for preparing CD-PET and CD-PET composite resin containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |