WO2011076085A1 - Yellowing-proof polyamide fiber and producing method thereof - Google Patents

Yellowing-proof polyamide fiber and producing method thereof Download PDF

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Publication number
WO2011076085A1
WO2011076085A1 PCT/CN2010/079930 CN2010079930W WO2011076085A1 WO 2011076085 A1 WO2011076085 A1 WO 2011076085A1 CN 2010079930 W CN2010079930 W CN 2010079930W WO 2011076085 A1 WO2011076085 A1 WO 2011076085A1
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WIPO (PCT)
Prior art keywords
polyamide
fiber
yellowing
anhydride
polymer
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PCT/CN2010/079930
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French (fr)
Chinese (zh)
Inventor
赵锁林
单伯军
藤森稔
佐藤雅伸
Original Assignee
东丽纤维研究所（中国）有限公司
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Publication date
Priority claimed from CN2009102662890A external-priority patent/CN102108564A/en
Priority claimed from CN2010102366616A external-priority patent/CN102337607A/en
Application filed by 东丽纤维研究所（中国）有限公司 filed Critical 东丽纤维研究所（中国）有限公司
Priority to CN201080059395.2A priority Critical patent/CN102666949B/en
Priority to KR1020127019172A priority patent/KR101803802B1/en
Priority to JP2012545067A priority patent/JP5839290B2/en
Publication of WO2011076085A1 publication Critical patent/WO2011076085A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00—Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02—Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16—Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/23—Inflatable members
    • B60R21/235—Inflatable members characterised by their material
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/446—Yarns or threads for use in automotive applications
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D1/00—Woven fabrics designed to make specified articles
    • D03D1/02—Inflatable articles
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/061—Load-responsive characteristics elastic
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/062—Load-responsive characteristics stiff, shape retention
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/12—Vehicles
    • D10B2505/124—Air bags

Definitions

  • the present invention relates to an anti-yellowing polyamide fiber and a method of producing the same.
  • Polyamide fiber is one of the strongest chemical fibers. It has the properties of resistance to friction, bending and deformation, wrinkles, water absorption, and quick drying after moisture absorption. At the same time, polyamide fiber has excellent elasticity. Elastic recovery rate is comparable to wool), and light weight (polyamide fiber specific gravity 1.14, in commercial synthetic fiber, second only to polyethylene and polypropylene with specific gravity less than 1), corrosion resistance It is not afraid of insects and is not afraid of mold. It is widely used in various fields such as clothing, carpets, towels, artificial leather, fishing nets and fishing lines.
  • polyamide fibers have the above advantages, they still have some disadvantages.
  • the main disadvantage of polyamide fiber is its resistance to yellowing. Poor, such as when exposed to sunlight for a long time outdoors, or during transportation, the fiber itself is prone to yellowing, which affects the scope of use and the field of use.
  • polyester fiber Compared with its poor shape retention, the fabric is not quite straight and straight, and its fiber surface is smooth and waxy.
  • various improvement measures have been developed in recent years, such as adding a light stabilizer to improve the light resistance. Or made into a profiled section to improve the appearance and luster, DTY or ATY is processed or blended or interwoven with other fibers to improve hand feel.
  • the phenol series BHT used as an antioxidant contained in the amino terminal group in the fiber and the packaging material used in the circulation process Di-tert-butyl p-cresol
  • the sublimate produced by sublimation generates a series of inducers under the catalysis of NOx (nitrogen oxide), and one of the inducers in this series is a colored substance, causing the fiber to yellow.
  • Another one is the amino terminal group in the fiber and vanillin (3-methoxy-4-hydroxybenzaldehyde) contained in the packaging material used in the circulation process.
  • the dehydration reaction takes place, and the resulting material is then subjected to the action of oxygen to finally produce a colored ⁇ -type structure, thereby causing yellowing of the fiber.
  • the service life of the polyamide nylon fibers is affected, and some fields that can be used.
  • the yellowing problem of polyamide nylon fiber affects its use in the outer casing, and has to be used more in underwear and the like.
  • the amino terminal group is reacted at the polymerization stage, thereby reducing the content of the amino terminal group in the polymer, thereby suppressing yellowing of the fiber.
  • the reaction mode of the amino terminal group is inhibited, so that the content of the amino terminal group in the polymer is not easily controlled, and the excessive reduction of the amino terminal group content causes the dyeing stage to be difficult to color and affect color development. Affect the use of fiber.
  • the excessive amount of unreacted small molecular substances added will affect the fiber material in the fiber stage; the control mode in the polymerization stage will greatly increase the polymerization cost, thereby affecting the fiber's own competitiveness in the market. .
  • the post-treatment processing method is used to suppress the yellowing problem.
  • the polyamide nylon fabric is subjected to an organic acid treatment to suppress a part of the amino terminal group to ensure that the fiber does not yellow, and a part of the amino terminal group is retained to ensure The dyeing properties of the fabric.
  • the post-processing processing method is not a good treatment method.
  • the packaging material used is treated to ensure that the polyamide nylon fiber does not cause yellowing problems by not using vanillin or the phenol series antioxidant BHT.
  • this method is costly and has a huge impact and cannot be implemented.
  • An object of the present invention is to provide a polyamide fiber which has a terminal amino group content to prevent yellowing and which has good dyeing properties and a method for producing the same.
  • Anti-yellowing A polyamide fiber characterized in that the end of the molecular chain of the fiber-forming polymer polyamide contains a terminal amino group and a nitrogen-containing terminal structure as shown below:
  • R 1 is a saturated or unsaturated aliphatic hydrocarbon group having a carbon atom of 2 to 20; the nitrogen-containing terminal structure is formed by a C 2 - C 10 carboxylic acid or a derivative thereof and a terminal amino group of the polyamide molecular chain Formed by a chemical reaction.
  • the derivative of the C 2 -C 10 carboxylic acid is oxalic anhydride, malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, sebacic anhydride, alkalic anhydride or maleic anhydride.
  • the polyamide is copolymerized with terephthalic acid before being reacted with the dibasic acid, and the viscosity of the polyamide during the spinning process can be controlled, and the increase in viscosity is not required by the control of the sliced water during the spinning process.
  • the acid anhydride of the dibasic acid is added in an amount of 50% to 150% by mole of the terminal amino group of the polyamide.
  • the polyamide is polycaprolactam or polyhexamethylene adipate.
  • the fiber-forming polymer polyamide has a terminal amino group content of 1.0 ⁇ 10 -5 to 3.0 ⁇ 10 -5 mol/g.
  • an acid anhydride of a metered dibasic acid is continuously added to the polyamide polymer, and is mixed and melted, spun, and wound up in a screw extruder.
  • An acid anhydride of a metered dibasic acid is continuously added to the polyamide polymer by a volumetric powder micro-addition device.
  • the polyamide is copolymerized with terephthalic acid prior to reaction with the dibasic acid.
  • Polyamide 6 obtained by copolymerization with terephthalic acid The slice is introduced into the silo disposed directly above the feed port of the screw extruder, and the carboxylic acid or its derivative is continuously added to the silo through the open pipe;
  • the opening pipe is disposed from a position below the slice stacking portion in the silo up to a position vertically upward from 10% to 50% of the stacking height.
  • the polyamide fiber is produced by continuously adding a metered acid anhydride of a dibasic acid to a conventional polyamide polymer at an inlet in a screw extruder, and mixing, melting, spinning, and coiling into a screw extruder. .
  • the anhydride of the metered dibasic acid is preferably continuously added to the conventional polyamide polymer by a volumetric powder micro-addition device.
  • a method of reducing the molecular chain terminal amino group content of a fiber-forming polymer polyamide in a polyamide fiber comprising a method of treating a conventional polyamide with an acid anhydride.
  • the addition of trace anhydride solids to the conventional polyamide is carried out, and the acid anhydride is melt-reacted with the conventional polyamide to control the terminal amino group content of the molecular chain of the fiber-forming polymer polyamide.
  • the purpose is to ensure that the polyamide fiber does not yellow during transportation and use, has excellent yellowing inhibition performance, and at the same time ensures the fiber life and the field of use is not limited; at the same time, it is added through the powder device during the spinning stage.
  • the blocking agent further causes the terminal amino group content of the molecular chain of the fiber-forming polymer polyamide in the polyamide fiber to not be excessively reduced to the extent that the dyeing is affected.
  • the invention can ensure the fiber to inhibit the yellowing effect, and can ensure the fiber does not receive the amino terminal group blockage, and still has good dyeing performance.
  • polyamides suitable for use in the present invention are those generally referred to as the term 'nylon' and long-chain synthetic polymers containing the amide (-CO-NH-) along the main polymer chain.
  • polyamides include homopolyamides and copolyamides obtained by polymerization of lactams or aminocaproic acid, and copolymerization products obtained from a mixture of diamines and dicarboxylic acids or lactams.
  • Typical polyamines include nylon 6 [poly( ⁇ caprolactam)], nylon 6/6 (polyhexamethylene hexamethylene diamine).
  • Polyamide can also be nylon 6 Or a copolymer of nylon 6/6 with a nylon salt that passes a dicarboxylic acid component, such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid, with a diamine, such as hexamethylene Diamine, m-xylenediamine Diamine) or l,4-bisaminomethylcyclohexane) is obtained by reaction.
  • a preferred conventional polyamide is nylon 6 or nylon 6/6, i.e., polycaprolactam or polyhexamethylene adipate, most preferably nylon 6, i.e., polycaprolactam.
  • the knitted fabric formed by the polyamide fiber obtained by the above materials and methods has good yellowing resistance and at the same time ensures the dyeing property of the polyamide fiber itself.
  • the content of the amino terminal group was determined by dissolving about 2.0 g of the polymer in about 60 ml of a mixture of phenol-methanol (68:32). The solution was titrated with about 0.2 N of HCI by potentiometric titration at about 25 °C, where the endpoint was determined by a sharp increase in potential.
  • the anti-yellowing property of polyamide fiber is divided into anti-vanillin yellowing property, NOx yellowing property, anti-phenol yellowing property, good yellowing inhibition effect, and ensuring whiteness of fiber;
  • the resulting fibers have excellent heat resistance compared to non-terminal amino-blocked nylon fibers.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine.
  • 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T polyamide nylon. 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.22 ⁇ 10 -5 mol/g and contained a nitrogen-containing terminal structure as shown below.
  • R 1 is a saturated aliphatic hydrocarbon group having 2 carbon atoms.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine.
  • 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 33T nylon 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 1.96 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine.
  • 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 84T nylon 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 1.86 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder.
  • the device added 0.6wt% of a sebacic acid anhydride additive to the N6 slice, and the two melt-mixed and reacted in a screw extruder.
  • the spinning box of 255° C. was sprayed through a spinneret, cooled and wound to obtain 56T nylon 6 . fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.58 ⁇ 10 -5 mol/g and contained a nitrogen-containing terminal structure as shown below.
  • R 1 is a saturated aliphatic hydrocarbon group having 8 carbon atoms.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder.
  • the device added 0.5 wt% of succinic anhydride additive to the N6 section, and the two were melt-mixed and reacted in a screw extruder.
  • the spinning box was sprayed through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.18 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder.
  • the device added 0.21% by weight of succinic anhydride additive to the N6 slice, and the two were melt mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.65 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.63 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun, spun, and wound through a spinneret at 255 ° C to obtain 56T nylon 6 fiber. .
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.11 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (Toray T100) having a terminal amino group content of 5.4 ⁇ 10 -5 mol/g was fed by using a small amount of powder before being fed to the screw extruder inlet of the spinning machine.
  • the material device added 0.3wt% of succinic anhydride additive to the N6 slice, and the two melt-mixed and reacted in a screw extruder.
  • the spinning box was sprayed through a spinneret at 275 ° C, cooled, and wound to obtain 56T nylon. 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 2.65 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 66 (polyhexamethylene adipamide) having a terminal amino group content of 3.5 ⁇ 10 -5 mol/g was sliced before being fed into the extruder screw extruder inlet by using a micro powder feeding device.
  • the N66 section was added with 0.3 wt% of succinic anhydride additive, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 285 ° C, cooled, and wound to obtain 56T nylon 66 fiber.
  • the obtained polyamide nylon 66 had a terminal amino group content of 2.31 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber.
  • the obtained polyamide nylon 6 had a terminal amino group content of 3.97 ⁇ 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
  • a polyamide nylon 6 (poly( ⁇ -caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2 ⁇ 10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine.
  • 0.7 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret through a spinning box of 255 ° C, and the spinning pressure was seriously reduced from the spinning
  • the hole in the plate hole is smeared and cannot be taken up.
  • the polyamide 6 slice copolymerized with terephthalic acid is put into a slicing silo directly above the inlet of the extruder of the melt spinning machine, and then placed in the silo through the panel rotary powder micro-adding device.
  • the vertically downwardly open opening pipe adds 0.3% by weight of succinic anhydride to the sliced silo, and the two are fed together into the screw extruder, and The mixture was melted and reacted in a screw extruder, passed through a spinning box at 255 ° C, and then spouted through a spinneret, cooled, and wound to obtain 52Den polyamide 6 fibers.
  • the resulting polyamide 6 fiber had a terminal amino group content of 2.22 ⁇ 10 -5 mol/g.
  • the polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the feed inlet of the extruder of the melt spinning machine, and then passed through the open tube to the opposite section through a panel rotary powder micro-adding device.
  • the silo is added with 0.3% by weight of succinic anhydride, and the two are fed together into a screw extruder, and are mixed and melted in a screw extruder and reacted. After passing through a spinning box at 255 ° C, the spinneret is sprayed and cooled. Winding to obtain 31Den polyamide 6 fiber.
  • the resulting polyamide 6 fiber had a terminal amino group content of 1.96 ⁇ 10 -5 mol/g.
  • Example 2 In the same manner as in Example 1, 74Den polyamide 6 fiber was obtained.
  • the resulting polyamide 6 fiber had a terminal amino group content of 1.86 ⁇ 10 -5 mol/g.
  • the polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and then added to the polyamide 6 slice via a panel rotary powder micro-addition device.
  • the resulting polyamide 6 fiber had a terminal amino group content of 2.18 ⁇ 10 -5 mol/g.
  • the polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and then added to the polyamide 6 slice via a panel rotary powder micro-addition device. 0.7 wt% of sebacic acid, the remainder of the same as in Example 1, to obtain 52Den polyamide 6 fibers.
  • the obtained polyamide 6 fiber had a terminal amino group content of 2.31 ⁇ 10 -5 mol/g.
  • the polyamide 6 chips copolymerized with terephthalic acid were placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and directly spun without adding any additives to obtain 52Den polyamide 6 fibers.
  • the obtained polyamide 6 fiber had a terminal amino group content of 3.97 ⁇ 10 -5 mol/g.

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Abstract

A yellowing-proof polyamide fiber and the producing method thereof are disclosed. The molecular chain's terminal of the fiber-forming polymer of the polyamide fiber includes terminal amino groups and terminal groups with nitrogen, said terminal groups with nitrogen are obtained by reacting binary acid anhydrides with terminal amino groups of general polyamide molecular chains. The method for producing the yellowing-proof polyamide fiber includes adding continuously the binary anhydrides metered to the general polyamide polymer at the entrance of a screw extruder, mixing and melting them in the screw extruder, then spinning, and then winding. The polyamide fiber can be effectively prevented from yellowing and has good dyeing performances.

Description

一种防黄变聚酰胺纤维及其制造方法  Anti-yellowing polyamide fiber and manufacturing method thereof
技术 领域 　 Technology field
本发明涉及一 种防黄变聚酰胺 纤维 及其生产方法 。 The present invention relates to an anti-yellowing polyamide fiber and a method of producing the same.
背景 技术 Background technique
聚酰胺纤维是强度较大的化学纤维中的一种，具有耐摩擦、耐弯曲变形、不易产生皱纹、不易吸水、吸湿后能够较快干燥等性能，同时 聚酰胺纤维 具有优良的 弹性 ( 弹性回复率 可与 羊毛媲美 ) ，还有 质轻 ( 聚酰胺纤维 比重为 1.14 ，在商业化合成纤维中，仅次于比重小于 1 的聚乙烯、 聚丙烯 ) 、 耐腐性 、 不怕虫蛀 、 不怕发霉 等特点，因而在衣料、地毯、毛巾、人工皮革、渔网、钓鱼线等各种各样的领域里被广泛使用。 Polyamide fiber is one of the strongest chemical fibers. It has the properties of resistance to friction, bending and deformation, wrinkles, water absorption, and quick drying after moisture absorption. At the same time, polyamide fiber has excellent elasticity. Elastic recovery rate is comparable to wool), and light weight (polyamide fiber specific gravity 1.14, in commercial synthetic fiber, second only to polyethylene and polypropylene with specific gravity less than 1), corrosion resistance It is not afraid of insects and is not afraid of mold. It is widely used in various fields such as clothing, carpets, towels, artificial leather, fishing nets and fishing lines.
在聚酰胺纤维具有以上优点的同时，它还是具有一些缺点。 聚酰胺纤维 的主要 缺点为耐 黄变性能 差，如在室外长时间受日 光 照 射 时， 或者运输过程中，纤维本身 易 发 生黄 变 ， 影响到纤维的使用范围、使用领域。同时，在发生黄变时， 与聚酯 纤维 相比其保型性较差，因此织物较不够挺拔，还有其纤维表面光滑，较有蜡状感，关于这些缺点近年来已研究出各种改善措施，如加入耐光剂以改善耐旋光性，或制成异型断面以改善外观及光泽，以 DTY 或 ATY 加工或与其它纤维混纺或交织，以改善手感。 While polyamide fibers have the above advantages, they still have some disadvantages. The main disadvantage of polyamide fiber is its resistance to yellowing. Poor, such as when exposed to sunlight for a long time outdoors, or during transportation, the fiber itself is prone to yellowing, which affects the scope of use and the field of use. At the same time, in the case of yellowing, with polyester fiber Compared with its poor shape retention, the fabric is not quite straight and straight, and its fiber surface is smooth and waxy. With regard to these shortcomings, various improvement measures have been developed in recent years, such as adding a light stabilizer to improve the light resistance. Or made into a profiled section to improve the appearance and luster, DTY or ATY is processed or blended or interwoven with other fibers to improve hand feel.
针对上述的黄变问题，进行了各种各样的研究，发现左右聚酰胺尼龙纤维黄变现象的为聚酰胺纤维中的氨基末端基的含量。 In view of the above-mentioned yellowing problem, various studies have been conducted, and it has been found that the yellowing phenomenon of the polyamide polyamide fiber is the content of the amino terminal group in the polyamide fiber.
纤维中的氨基末端基与流通过程中所使用的包装材料中所含有的作为抗氧化剂来使用的苯酚系列的BHT( 二特丁基化对甲酚 ) 升华所产生的升华物在NOx(氧化氮气)的催化作用下，生成一系列的诱导体，其中的这系列中某一种诱导体为有色物质，使得纤维发生黄变现象。 The phenol series BHT used as an antioxidant contained in the amino terminal group in the fiber and the packaging material used in the circulation process ( Di-tert-butyl p-cresol The sublimate produced by sublimation generates a series of inducers under the catalysis of NOx (nitrogen oxide), and one of the inducers in this series is a colored substance, causing the fiber to yellow.
再一个就是，纤维中氨基末端基与流通过程中所使用包装材料中所含有的香兰素( 3- 甲氧基 -4- 羟基苯甲醛 ) 发生脱水反应，所得物质接下来在氧气的作用下，最后产生有色的醌式构造，从而使得纤维发生黄变现象。 Another one is the amino terminal group in the fiber and vanillin (3-methoxy-4-hydroxybenzaldehyde) contained in the packaging material used in the circulation process. The dehydration reaction takes place, and the resulting material is then subjected to the action of oxygen to finally produce a colored 醌-type structure, thereby causing yellowing of the fiber.
以上两种在流通过程中与所使用的包装材料中的某些物质反应所发生的黄变现象，使得纤维发黄，影响了聚酰胺尼龙纤维的使用范围及领域。 The above-mentioned yellowing phenomenon caused by the reaction between some of the materials in the packaging material used in the circulation process causes the fiber to yellow, which affects the scope and field of use of the polyamide nylon fiber.
另外，在消费者所用阶段，尼龙制品上附着的一些附着物，如洗涤用剂、脏污等一些物质，在外界的NOx(氧化氮气)的催化作用下，与聚酰胺尼龙纤维所含有的氨基末端基相结合，生成有色物质，纤维发生黄变现象。 In addition, at the stage used by consumers, some attachments attached to nylon products, such as detergents, dirt and other substances, under the catalysis of external NOx (nitrogen oxide), and the amino groups contained in polyamide nylon fibers The terminal groups are combined to form a colored substance, and the fiber undergoes yellowing.
由于以上的聚酰胺尼龙纤维的发黄问题，影响了聚酰胺尼龙纤维的使用寿命，以及可以使用的一些领域。比如，在衣料领域，聚酰胺尼龙纤维的黄变问题就影响其在外套的方面的使用，而不得不较多的局限使用在内衣等方面。 Due to the yellowing problem of the above polyamide nylon fibers, the service life of the polyamide nylon fibers is affected, and some fields that can be used. For example, in the field of clothing, the yellowing problem of polyamide nylon fiber affects its use in the outer casing, and has to be used more in underwear and the like.
针对上述的由聚酰胺尼龙纤维中氨基末端基所引起的黄变问题，以往进行了以下的处理方式。 In view of the yellowing problem caused by the amino terminal group in the polyamide nylon fiber described above, the following treatment methods have been conventionally performed.
在聚酰胺尼龙聚合物聚合的阶段，通过添加酸性物质，让氨基末端基在聚合阶段被反应掉，从而减少聚合物中氨基末端基的含量，从而达到抑制纤维发黄。但是，在聚合阶段来抑制氨基末端基的反应方式，使得聚合物中的氨基末端基的含量不易控制，氨基末端基含量过量减少会导致在织物染色阶段，不易上色，影响发色性，从而影响纤维的使用。还有就是，添加进去的过量的未反应小分子物质会在纤维阶段影响纤维物质；在聚合阶段的控制方式，会比较大幅度的增加聚合成本，从而影响了纤维的本身在市场上的竞争力。 At the stage of polymerization of the polyamide nylon polymer, by adding an acidic substance, the amino terminal group is reacted at the polymerization stage, thereby reducing the content of the amino terminal group in the polymer, thereby suppressing yellowing of the fiber. However, in the polymerization stage, the reaction mode of the amino terminal group is inhibited, so that the content of the amino terminal group in the polymer is not easily controlled, and the excessive reduction of the amino terminal group content causes the dyeing stage to be difficult to color and affect color development. Affect the use of fiber. In addition, the excessive amount of unreacted small molecular substances added will affect the fiber material in the fiber stage; the control mode in the polymerization stage will greatly increase the polymerization cost, thereby affecting the fiber's own competitiveness in the market. .
在织物阶段通过后处理加工方式来抑制黄变问题的话，通过在后处理工序，对聚酰胺尼龙织物进行有机酸处理，抑制一部分氨基末端基来保证纤维不发黄，保留一部分氨基末端基来保证织物的染色性能。在实际对氨基末端基的处理上，存在误差较大，制品性能不能很好控制的问题，后处理加工方式也不是一个良好的处理方式。 In the fabric stage, the post-treatment processing method is used to suppress the yellowing problem. In the post-treatment process, the polyamide nylon fabric is subjected to an organic acid treatment to suppress a part of the amino terminal group to ensure that the fiber does not yellow, and a part of the amino terminal group is retained to ensure The dyeing properties of the fabric. In the actual treatment of the amino terminal group, there is a problem that the error is large and the product performance cannot be well controlled, and the post-processing processing method is not a good treatment method.
再有就是，对所使用的包装材料进行处理，通过不使用香兰素、苯酚系列抗氧化剂BHT，来保证聚酰胺尼龙纤维不发生发黄问题。但是，此种方式费用巨大、影响巨大，无法实施。 Furthermore, the packaging material used is treated to ensure that the polyamide nylon fiber does not cause yellowing problems by not using vanillin or the phenol series antioxidant BHT. However, this method is costly and has a huge impact and cannot be implemented.
以往，针对 聚酰胺 黄变问题也进行过一些防黄变处理，例如，在 聚酰胺 的聚合阶段，通过添加酸性物质与末端氨基反应以减少 聚酰胺 中末端氨基的含量，从而达到抑制 聚酰胺纤维 发黄。不过，此处理方式会降低 聚酰胺 的聚合能力，并且聚合成本也会大幅增加。另外，也有在织物阶段通过对 聚酰胺 织物进行有机酸或有机酸酐（例如，醋酸或醋酸酐）处理来减少一部分末端氨基以抑制纤维发黄。不过，这种后期的处理方式也存在工序复杂且不易控制等缺点。还有的处理方式就是对所使用的包装材料进行筛选或改进以保证 聚酰胺纤维 不发生黄变，不过，此种方式费用巨大、可行性差，而且不能根本上解决 聚酰胺纤维 黄变问题。 In the past, some anti-yellowing treatments have been carried out on the problem of polyamide yellowing, for example, in polyamides. The polymerization stage inhibits the yellowing of the polyamide fiber by adding an acidic substance to react with the terminal amino group to reduce the content of the terminal amino group in the polyamide. However, this treatment will reduce the polyamide The ability to aggregate, and the cost of polymerization will also increase significantly. In addition, there are also polyamides in the fabric stage. The fabric is treated with an organic acid or an organic anhydride (eg, acetic acid or acetic anhydride) to reduce a portion of the terminal amino groups to inhibit yellowing of the fibers. However, such post-processing methods also have disadvantages such as complicated processes and difficulty in control. Another way to deal with is to filter or improve the packaging materials used to ensure Polyamide fibers do not yellow, but this method is costly and unfeasible, and does not fundamentally solve the problem of yellowing of polyamide fibers.
就上述处理方式所出现的问题，研究开发一种低成本，工艺简单且既不影响 聚酰胺纤维 性能又能很好的解决黄变问题的技术变得十分必要。现今随着纤维纺丝阶段的微量添加技术的成熟，在纺丝阶段进行微量酸性添加剂的添加，来达到控制 聚酰胺纤维 中末端氨基的含量，从而确保纤维不发生黄变成为可能。 In view of the problems arising from the above treatment methods, research and development of a low cost, simple process and neither affecting the polyamide fiber The technology that can solve the yellowing problem well is very necessary. Nowadays, with the maturity of the micro-addition technology in the fiber spinning stage, a small amount of acidic additives are added during the spinning stage to control the polyamide fiber. The content of the terminal amino group in the middle, thereby ensuring that the fiber does not yellow.
发明内容 Summary of the invention
本发明的目的是提供一种控制末端氨基含量达到防止黄变且具有良好染色性能的聚酰胺纤维及其制造方法。 SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide fiber which has a terminal amino group content to prevent yellowing and which has good dyeing properties and a method for producing the same.
本发明的技术解决方案是： The technical solution of the present invention is:
一种 防黄变 聚酰胺纤维，其特征在于：成纤聚合物聚酰胺分子链的末端含有末端氨基以及如下所示含氮末端结构： Anti-yellowing A polyamide fiber characterized in that the end of the molecular chain of the fiber-forming polymer polyamide contains a terminal amino group and a nitrogen-containing terminal structure as shown below:
Figure PCTCN2010079930-appb-I000001
Figure PCTCN2010079930-appb-I000001
且R 1 为碳原子为 2 ~2 0 的饱和或不饱和的脂肪族烃基；所述含氮末端结构由 C2 ～ C10 的羧酸或者其衍生物 与聚酰胺分子链的末端氨基通过发生化学反应而形成。And R 1 is a saturated or unsaturated aliphatic hydrocarbon group having a carbon atom of 2 to 20; the nitrogen-containing terminal structure is formed by a C 2 - C 10 carboxylic acid or a derivative thereof and a terminal amino group of the polyamide molecular chain Formed by a chemical reaction.
所 述 C2 ～ C10 的羧酸 的 衍生物 为乙二酸酐、丙二酸酐、丁二酸酐、戊二酸酐、己二酸酐、庚二酸酐、辛二酸酐、壬二酸酐、葵二酸酐或马来酸酐。The derivative of the C 2 -C 10 carboxylic acid is oxalic anhydride, malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, suberic anhydride, sebacic anhydride, alkalic anhydride or maleic anhydride.
聚酰胺在与二元酸反应前先经过与对苯二甲酸共聚合，能够控制聚酰胺在纺丝过程中的粘度上升，纺丝过程中无需通过切片水分的控制来抑制粘度的上升。 The polyamide is copolymerized with terephthalic acid before being reacted with the dibasic acid, and the viscosity of the polyamide during the spinning process can be controlled, and the increase in viscosity is not required by the control of the sliced water during the spinning process.
二元酸的酸酐的添加量为聚酰胺末端氨基摩尔含量的50% ~ 150% 。 The acid anhydride of the dibasic acid is added in an amount of 50% to 150% by mole of the terminal amino group of the polyamide.
聚酰胺为聚己内酰胺或聚己二酸己二胺。 The polyamide is polycaprolactam or polyhexamethylene adipate.
该纤维的成纤聚合物聚酰胺的末端氨基含量为1.0×10-5 ~ 3.0 ×10-5mol/g。The fiber-forming polymer polyamide has a terminal amino group content of 1.0 × 10 -5 to 3.0 × 10 -5 mol/g.
在螺杆挤出机中的入口处，向聚酰胺聚合物中连续添加经过计量的二元酸的酸酐，进入螺杆挤出机中混合熔融、纺丝、卷取。 At the inlet of the screw extruder, an acid anhydride of a metered dibasic acid is continuously added to the polyamide polymer, and is mixed and melted, spun, and wound up in a screw extruder.
通过容积式粉体微量添加装置向聚酰胺聚合物中连续添加经过计量的二元酸的酸酐。 An acid anhydride of a metered dibasic acid is continuously added to the polyamide polymer by a volumetric powder micro-addition device.
聚酰胺在与二元酸反应前先经过与对苯二甲酸共聚合。 The polyamide is copolymerized with terephthalic acid prior to reaction with the dibasic acid.
将与对苯二甲酸共聚合得到的聚酰胺 6 切片导入到设置在螺杆挤出机进料口正上方的料仓的同时，通过开口配管向料仓中连续添加羧酸或者其衍生物 ； 所说开口配管设置在从料仓内切片堆积部分的下方起向上至切片堆积高度的 10% ～ 50% 位置处正上方竖直向下的位置。 Polyamide 6 obtained by copolymerization with terephthalic acid The slice is introduced into the silo disposed directly above the feed port of the screw extruder, and the carboxylic acid or its derivative is continuously added to the silo through the open pipe; The opening pipe is disposed from a position below the slice stacking portion in the silo up to a position vertically upward from 10% to 50% of the stacking height.
本发明的 防黄变 聚酰胺纤维的制造方法，是在螺杆挤出机中的入口处，向常规聚酰胺聚合物中连续添加经过计量的二元酸的酸酐，进入螺杆挤出机中混合熔融、纺丝、卷取。 Anti-yellowing of the present invention The polyamide fiber is produced by continuously adding a metered acid anhydride of a dibasic acid to a conventional polyamide polymer at an inlet in a screw extruder, and mixing, melting, spinning, and coiling into a screw extruder. .
优选通过容积式粉体微量添加装置向常规聚酰胺聚合物中连续添加经过计量的二元酸的酸酐。 The anhydride of the metered dibasic acid is preferably continuously added to the conventional polyamide polymer by a volumetric powder micro-addition device.
根据本发明，提供了一种降低聚酰胺纤维中成纤聚合物聚酰胺的分子链末端氨基含量的方法，包括用酸酐处理常规聚酰胺的方法。 According to the present invention, there is provided a method of reducing the molecular chain terminal amino group content of a fiber-forming polymer polyamide in a polyamide fiber, comprising a method of treating a conventional polyamide with an acid anhydride.
即在纺丝机的螺杆挤出机的熔融阶段，向常规聚酰胺进行微量酸酐固体的添加，使酸酐与常规聚酰胺熔融反应，达到控制成纤聚合物聚酰胺的分子链的末端氨基含量的目的，确保聚酰胺纤维在运输、使用中不发生黄变，具有优良的黄变抑制性能，同时又能够保证纤维的使用寿命及使用领域不受限制；同时，在纺丝阶段通过粉体装置添加封端剂，又使得聚酰胺纤维中成纤聚合物聚酰胺的分子链的末端氨基含量不会过分降低至影响染色的程度。使得本发明在保证纤维抑制黄变效果的同时，能够保证纤维不收氨基末端基封锁的影响，依然具有良好的染色性能。 That is, in the melting stage of the screw extruder of the spinning machine, the addition of trace anhydride solids to the conventional polyamide is carried out, and the acid anhydride is melt-reacted with the conventional polyamide to control the terminal amino group content of the molecular chain of the fiber-forming polymer polyamide. The purpose is to ensure that the polyamide fiber does not yellow during transportation and use, has excellent yellowing inhibition performance, and at the same time ensures the fiber life and the field of use is not limited; at the same time, it is added through the powder device during the spinning stage. The blocking agent further causes the terminal amino group content of the molecular chain of the fiber-forming polymer polyamide in the polyamide fiber to not be excessively reduced to the extent that the dyeing is affected. The invention can ensure the fiber to inhibit the yellowing effect, and can ensure the fiber does not receive the amino terminal group blockage, and still has good dyeing performance.
适合本发明使用的常规聚酰胺是一般称作术语'尼龙'的那些和含有沿着主聚合物链的酰胺健(-CO-NH-)的长链合成聚合物．这些聚酰胺的实例包括由内酰胺或氨基己酸聚合得到的均聚酰胺和共聚酰胺以及由二胺和二羧酸的混合物或内酰胺得到的共聚产物。典型的聚酸胺包括尼龙6[聚(ε己内酰胺)]、尼龙6/6（聚己二酞己二胺）。聚酰胺也可以是尼龙 6 或尼龙6/6与尼龙盐的共聚物，该尼龙盐通过二羧酸成分，(如对苯二甲酸、间苯二甲酸、己二酸或癸二酸)与二胺,(如六亚甲基二胺、间二甲苯二胺（methaxylene diamine）或l,4-双氨基甲基环己烷)反应得到。优选的常规聚酰胺是尼龙6或尼龙6/6，即聚己内酰胺或聚己二酸己二胺，最优选尼龙6，即聚己内酰。 Conventional polyamides suitable for use in the present invention are those generally referred to as the term 'nylon' and long-chain synthetic polymers containing the amide (-CO-NH-) along the main polymer chain. Examples of such polyamides include homopolyamides and copolyamides obtained by polymerization of lactams or aminocaproic acid, and copolymerization products obtained from a mixture of diamines and dicarboxylic acids or lactams. Typical polyamines include nylon 6 [poly(ε caprolactam)], nylon 6/6 (polyhexamethylene hexamethylene diamine). Polyamide can also be nylon 6 Or a copolymer of nylon 6/6 with a nylon salt that passes a dicarboxylic acid component, such as terephthalic acid, isophthalic acid, adipic acid or sebacic acid, with a diamine, such as hexamethylene Diamine, m-xylenediamine Diamine) or l,4-bisaminomethylcyclohexane) is obtained by reaction. A preferred conventional polyamide is nylon 6 or nylon 6/6, i.e., polycaprolactam or polyhexamethylene adipate, most preferably nylon 6, i.e., polycaprolactam.
本发明的目的、效果、特征和优点从下面对其优选实施方案的详细描述中将变得更加明显。为了促进对本发明本质的理解，下面描述本发明的特定实施方案并且使用特定的语言描述它们。然而应该理解的是，使用该特定的语言不是对本发明范围的限制，并且应认为所述本发明本质的改变、改进、等价物以及进一步应用对于本发明所属技术领域中的普通技术人员而言一般能想到。 The objects, effects, features and advantages of the present invention will become more apparent from the detailed description of the preferred embodiments. In order to facilitate an understanding of the essence of the invention, specific embodiments of the invention are described below and described in a particular language. It should be understood, however, that the use of the specific language is not intended to limit the scope of the invention, and the invention is intended to be think.
通过上述物质、方法制得的聚酰胺纤维所形成的编织物具有良好的耐黄变性能，同时、又能够保证聚酰胺纤维本身的染色性能。 The knitted fabric formed by the polyamide fiber obtained by the above materials and methods has good yellowing resistance and at the same time ensures the dyeing property of the polyamide fiber itself.
氨基末端基的含量通过将大约2.0g聚合物溶解在大约60ml苯酚-甲醇的混合物(68:32)中来测定。在大约25℃下通过电势滴定法用大约0.2N的HCI滴定该溶液，其中终点通过急剧的电势增加来确定。 The content of the amino terminal group was determined by dissolving about 2.0 g of the polymer in about 60 ml of a mixture of phenol-methanol (68:32). The solution was titrated with about 0.2 N of HCI by potentiometric titration at about 25 °C, where the endpoint was determined by a sharp increase in potential.
聚酰胺纤维的防止黄变性能分为，抗香兰素黄变性能、NOx黄变性能、抗苯酚黄变性能，具有良好的黄变抑制效果，保证纤维的白度；同时，本发明所制成的纤维对比未末端氨基封锁的尼龙纤维，具有优良的耐热性能。 The anti-yellowing property of polyamide fiber is divided into anti-vanillin yellowing property, NOx yellowing property, anti-phenol yellowing property, good yellowing inhibition effect, and ensuring whiteness of fiber; The resulting fibers have excellent heat resistance compared to non-terminal amino-blocked nylon fibers.
具体实施例方式 Specific embodiment
下面结合实施例对本发明作进一步的说明。 The present invention will be further described below in conjunction with the embodiments.
实施例 1 ： Example 1
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.3wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T聚酰胺尼龙6纤维。所得聚酰胺尼龙6的末端氨基含量为2.22×10-5mol/g,并含有如下所示的含氮末端结构。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T polyamide nylon. 6 fiber. The obtained polyamide nylon 6 had a terminal amino group content of 2.22 × 10 -5 mol/g and contained a nitrogen-containing terminal structure as shown below.
Figure PCTCN2010079930-appb-I000002
，R 1 为碳原子为 2 的饱和脂肪族烃基。
Figure PCTCN2010079930-appb-I000002
R 1 is a saturated aliphatic hydrocarbon group having 2 carbon atoms.
实施例 2 ： Example 2:
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.3wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到33T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为1.96×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 33T nylon 6 fiber. . The obtained polyamide nylon 6 had a terminal amino group content of 1.96 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 3 ： Example 3:
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.3wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到84T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为1.86×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.3 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 84T nylon 6 fiber. . The obtained polyamide nylon 6 had a terminal amino group content of 1.86 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 4 ： Example 4:
将末端氨基的含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.6wt%的癸二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为2.58×10-5mol/g,并含有如下所示的含氮末端结构。A polyamide nylon 6 (poly(ε-caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 × 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder. The device added 0.6wt% of a sebacic acid anhydride additive to the N6 slice, and the two melt-mixed and reacted in a screw extruder. The spinning box of 255° C. was sprayed through a spinneret, cooled and wound to obtain 56T nylon 6 . fiber. The obtained polyamide nylon 6 had a terminal amino group content of 2.58 × 10 -5 mol/g and contained a nitrogen-containing terminal structure as shown below.
Figure PCTCN2010079930-appb-I000003
，R 1 为碳原子为8的饱和脂肪族烃基。
Figure PCTCN2010079930-appb-I000003
R 1 is a saturated aliphatic hydrocarbon group having 8 carbon atoms.
实施例 5 ： Example 5:
将末端氨基的含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.5wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为2.18×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 × 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder. The device added 0.5 wt% of succinic anhydride additive to the N6 section, and the two were melt-mixed and reacted in a screw extruder. The spinning box was sprayed through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber. The obtained polyamide nylon 6 had a terminal amino group content of 2.18 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 6 ： Example 6:
将末端氨基的含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.21wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为2.65×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) section (BASF400N) having a terminal amino group content of 4.2 × 10 -5 mol/g was fed to the spinner extruder screw inlet by using a small amount of powder. The device added 0.21% by weight of succinic anhydride additive to the N6 slice, and the two were melt mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber. The obtained polyamide nylon 6 had a terminal amino group content of 2.65 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 7 ： Example 7:
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.63wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为2.11×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.63 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun, spun, and wound through a spinneret at 255 ° C to obtain 56T nylon 6 fiber. . The obtained polyamide nylon 6 had a terminal amino group content of 2.11 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 8 ： Example 8:
将末端氨基含量为5.4×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(东丽T100)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.3wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过275℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为2.65×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) slice (Toray T100) having a terminal amino group content of 5.4×10 -5 mol/g was fed by using a small amount of powder before being fed to the screw extruder inlet of the spinning machine. The material device added 0.3wt% of succinic anhydride additive to the N6 slice, and the two melt-mixed and reacted in a screw extruder. The spinning box was sprayed through a spinneret at 275 ° C, cooled, and wound to obtain 56T nylon. 6 fiber. The obtained polyamide nylon 6 had a terminal amino group content of 2.65 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
实施例 9 ： Example 9:
将末端氨基含量为3.5×10-5mol/g的聚酰胺尼龙66(聚己二酸己二胺)切片在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N66切片添加0.3wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过285℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙66纤维。所得聚酰胺尼龙66末端氨基含量为2.31×10-5mol/g，所含含氮末端结构同实施例1。A polyamide nylon 66 (polyhexamethylene adipamide) having a terminal amino group content of 3.5 × 10 -5 mol/g was sliced before being fed into the extruder screw extruder inlet by using a micro powder feeding device. The N66 section was added with 0.3 wt% of succinic anhydride additive, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 285 ° C, cooled, and wound to obtain 56T nylon 66 fiber. The obtained polyamide nylon 66 had a terminal amino group content of 2.31 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
比较 例 1 ： Comparison Example 1:
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出、冷却、卷绕得到56T尼龙6纤维。所得聚酰胺尼龙6末端氨基含量为3.97×10-5mol/g, ，所含含氮末端结构同实施例1。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret at 255 ° C, cooled, and wound to obtain 56T nylon 6 fiber. The obtained polyamide nylon 6 had a terminal amino group content of 3.97 × 10 -5 mol/g, and the nitrogen-containing terminal structure was the same as in Example 1.
比较 例 2 ： Comparison Example 2:
将末端氨基含量为4.2×10-5mol/g的聚酰胺尼龙6(聚(ε己内酰胺))切片(BASF400N)在喂入纺丝机螺杆挤出机入口之前，通过使用微量粉体喂料装置向N6切片添加0.7wt%的丁二酸酐添加剂，两者在螺杆挤出机中熔融混合、反应，通过255℃的纺丝箱体经喷丝板喷出，纺丝压力下降严重，从喷丝板孔发生滴料现象，无法卷取。A polyamide nylon 6 (poly(ε-caprolactam)) slice (BASF400N) having a terminal amino group content of 4.2×10 -5 mol/g was passed through a micro-powder feeding device before being fed to the screw extruder inlet of the spinning machine. 0.7 wt% of succinic anhydride additive was added to the N6 section, and the two were melt-mixed and reacted in a screw extruder, and spun through a spinneret through a spinning box of 255 ° C, and the spinning pressure was seriously reduced from the spinning The hole in the plate hole is smeared and cannot be taken up.
实施例 1 0 ： Example 1 0 :
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，然后经面板回转式粉体微量添加装置，通过设置在从料仓内切片堆积部分的下方起向上至切片堆积高度的 40% 位置处正上方竖直向下的开口配管向相对该切片料仓添加 0.3wt% 丁二酸酐，两者共同喂入螺杆挤出机，且在螺杆挤出机中混合熔融并反应，通过 255 ℃ 的纺丝箱体后经喷丝板喷出、冷却、卷绕得到 52Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 2.22 × 10-5mol/g 。The polyamide 6 slice copolymerized with terephthalic acid is put into a slicing silo directly above the inlet of the extruder of the melt spinning machine, and then placed in the silo through the panel rotary powder micro-adding device. From the bottom of the slice stacking portion up to 40% of the stacking height of the slice, the vertically downwardly open opening pipe adds 0.3% by weight of succinic anhydride to the sliced silo, and the two are fed together into the screw extruder, and The mixture was melted and reacted in a screw extruder, passed through a spinning box at 255 ° C, and then spouted through a spinneret, cooled, and wound to obtain 52Den polyamide 6 fibers. The resulting polyamide 6 fiber had a terminal amino group content of 2.22 × 10 -5 mol/g.
实施例 11 ： Example 11:
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，然后经面板回转式粉体微量添加装置，通过开口配管向相对该切片料仓添加 0.3wt% 丁二酸酐，两者共同喂入螺杆挤出机，且在螺杆挤出机中混合熔融并反应，通过 255 ℃ 的纺丝箱体后经喷丝板喷出、冷却、卷绕得到 31Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 1.96 × 10-5mol/g 。The polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the feed inlet of the extruder of the melt spinning machine, and then passed through the open tube to the opposite section through a panel rotary powder micro-adding device. The silo is added with 0.3% by weight of succinic anhydride, and the two are fed together into a screw extruder, and are mixed and melted in a screw extruder and reacted. After passing through a spinning box at 255 ° C, the spinneret is sprayed and cooled. Winding to obtain 31Den polyamide 6 fiber. The resulting polyamide 6 fiber had a terminal amino group content of 1.96 × 10 -5 mol/g.
实施例 12 ： Example 12:
同实施例 1 ，制得 74Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 1.86 × 10-5mol/g 。In the same manner as in Example 1, 74Den polyamide 6 fiber was obtained. The resulting polyamide 6 fiber had a terminal amino group content of 1.86 × 10 -5 mol/g.
实施例 13 ： Example 13:
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，然后经面板回转式粉体微量添加装置向相对该聚酰胺 6 切片添加 0.5wt% 丁二酸酐，其余同实施例 1 ，制得 52Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 2.18 × 10-5mol/g 。The polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and then added to the polyamide 6 slice via a panel rotary powder micro-addition device. 0.5 wt% of succinic anhydride, the remainder of which was the same as in Example 1, to obtain 52Den polyamide 6 fibers. The resulting polyamide 6 fiber had a terminal amino group content of 2.18 × 10 -5 mol/g.
实施例 14 ： Example 14:
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，然后经面板回转式粉体微量添加装置向相对该聚酰胺 6 切片添加 0.7wt% 癸二酸，其余同实施例 1 ，制得 52Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 2.31 × 10-5mol/g 。The polyamide 6 slice copolymerized with terephthalic acid was placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and then added to the polyamide 6 slice via a panel rotary powder micro-addition device. 0.7 wt% of sebacic acid, the remainder of the same as in Example 1, to obtain 52Den polyamide 6 fibers. The obtained polyamide 6 fiber had a terminal amino group content of 2.31 × 10 -5 mol/g.
比较例 3 ： Comparative Example 3:
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，且不添加任何添加剂直接纺丝制得 52Den 聚酰胺 6 纤维。所得聚酰胺 6 纤维末端氨基含量为 3.97 × 10-5mol/g 。The polyamide 6 chips copolymerized with terephthalic acid were placed in a slicing silo directly above the extruder feed port of the melt spinning machine, and directly spun without adding any additives to obtain 52Den polyamide 6 fibers. The obtained polyamide 6 fiber had a terminal amino group content of 3.97 × 10 -5 mol/g.
比较例 4 ： Comparative Example 4:
将与对苯二甲酸共聚合的聚酰胺 6 切片投入熔融纺丝机的挤出机进料口正上方的切片料仓，然后经面板回转式粉体微量添加装置向相对该聚酰胺 6 切片添加 1.0wt% 丁二酸酐，其余同实施例 1 ，但此时纺丝压力下降严重，从喷丝板孔发生滴料现象，无法卷取。 Polyamide 6 copolymerized with terephthalic acid The slice was placed in a section silo directly above the feed inlet of the extruder of the melt spinning machine, and then 1.0 wt% of succinic anhydride was added to the polyamide 6 section via a panel rotary powder micro-addition device, and the rest of the same example 1 However, at this time, the spinning pressure is seriously degraded, and a dripping phenomenon occurs from the orifice of the spinneret, and it is impossible to take up.
实施例、比较例的具体参数、效果的见表1、表2。 The specific parameters and effects of the examples and comparative examples are shown in Tables 1 and 2.
表1、2中，'○'表示性能良好，'×'表示性能不良。 In Tables 1 and 2, '○' indicates good performance, and '×' indicates poor performance.
表1 Table 1
聚合物 polymer 添加剂/
添加量(wt%)additive/
Add amount (wt%) 		原氨基含量
(10-5mol/g)Original amino content
(10 -5 mol/g) 		纤维纤度
(dtex)Fiber denier
(dtex) 		氨基含量
(10-5mol/g)Amino content
(10 -5 mol/g) 		抗香兰素黄变性能 Anti-vanillin yellowing performance 抗NOx黄变性能 Anti-NOx yellowing performance 抗苯酚黄变性能 Anti-phenol yellowing performance
实施例1 Example 1 N6 N6 丁二酸酐/0.3 Succinic anhydride / 0.3 4.2 4.2 56 56 2.22 2.22 ○ ○ ○ ○ ○ ○
实施例2 Example 2 N6 N6 丁二酸酐/0.3 Succinic anhydride / 0.3 4.2 4.2 33 33 1.96 1.96 ○ ○ ○ ○ ○ ○
实施例3 Example 3 N6 N6 丁二酸酐/0.3 Succinic anhydride / 0.3 4.2 4.2 84 84 1.86 1.86 ○ ○ ○ ○ ○ ○
实施例4 Example 4 N6 N6 癸二酸酐/0.6 Azelaic anhydride / 0.6 4.2 4.2 56 56 2.58 2.58 ○ ○ ○ ○ ○ ○
实施例5 Example 5 N6 N6 丁二酸酐/0.5 Succinic anhydride / 0.5 4.2 4.2 56 56 2.18 2.18 ○ ○ ○ ○ ○ ○
实施例6 Example 6 N6 N6 丁二酸酐/0.21 Succinic anhydride / 0.21 4.2 4.2 56 56 2.65 2.65 ○ ○ ○ ○ ○ ○
实施例7 Example 7 N6 N6 丁二酸酐/0.63 Succinic anhydride / 0.63 4.2 4.2 56 56 2.11 2.11 ○ ○ ○ ○ ○ ○
实施例8 Example 8 N6 N6 丁二酸酐/0.3 Succinic anhydride / 0.3 5.4 5.4 56 56 2.65 2.65 ○ ○ ○ ○ ○ ○
实施例9 Example 9 N66 N66 丁二酸酐/0.3 Succinic anhydride / 0.3 3.5 3.5 56 56 2.31 2.31 ○ ○ ○ ○ ○ ○
比较例1 Comparative example 1 N6 N6 丁二酸酐/0 Succinic anhydride / 0 4.2 4.2 56 56 3.97 3.97 × × × × × ×
比较例2 Comparative example 2 N6 N6 丁二酸酐/0.7 Succinic anhydride / 0.7 4.2 4.2 无法成纤 Unable to fiber
表 2 ： Table 2 :
聚合物 polymer 添加剂 /
添加量 (wt%)additive/
Add amount (wt%) 		纤维纤度
(dtex)Fiber denier
(dtex) 		氨基含量
(10-5mol/g)Amino content
(10 -5 mol/g) 		抗香兰素
黄变Anti-vanillin yellowing 		抗 NOx
黄变Anti-NOx
Yellowing 		抗苯酚
黄变Antiphenol phenol yellowing
实施例 1 0 Example 1 0 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 丁二酸酐 /0.3 Succinic anhydride /0.3 52 52 2.22 2.22 ○ ○ ○ ○ ○ ○
实施例 11 Example 11 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 丁二酸酐 /0.3 Succinic anhydride /0.3 31 31 1.96 1.96 ○ ○ ○ ○ ○ ○
实施例 12 Example 12 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 丁二酸酐 /0.3 Succinic anhydride /0.3 74 74 1.86 1.86 ○ ○ ○ ○ ○ ○
实施例 13 Example 13 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 丁二酸酐 /0.5 Succinic anhydride /0.5 52 52 2.18 2.18 ○ ○ ○ ○ ○ ○
实施例 14 Example 14 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 癸二酸酐 /0.7 Azelaic anhydride /0.7 52 52 2.31 2.31 ○ ○ ○ ○ ○ ○
比较例 3 Comparative example 3 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 无 no 52 52 3.97 3.97 × × × × × ×
比较例 4 Comparative example 4 与对苯二甲酸共聚合的 N6 N6 copolymerized with terephthalic acid 丁二酸酐 /1.0 Succinic anhydride /1.0 52 52 - - - - - - - -
( '○'：性能良好，'×'：性能不良 ) ( '○': good performance, '×': poor performance)

Claims (1)

1 、 一种 防黄变 聚酰胺纤维，其特征在于：成纤聚合物聚酰胺分子链的末端含有1.0×10-5 ~ 3.0 ×10-5mol/g的末端氨基含量以及如下所示含氮末端结构：1 . An anti-yellowing polyamide fiber, characterized in that the end of the molecular chain of the fiber-forming polymer polyamide contains a terminal amino group content of 1.0×10 -5 to 3.0 × 10 -5 mol/g and a nitrogen-containing terminal structure as shown below :
Figure PCTCN2010079930-appb-I000004
Figure PCTCN2010079930-appb-I000004
且R 1 为碳原子为 2 ~ 20 的饱和或不饱和的脂肪族烃基；所述成纤聚合物聚酰胺分子链的含氮末端结构由 C2 ～ C 2 0 的羧酸或者其衍生物 与聚酰胺聚合物分子链的末端氨基通过发生化学反应而形成。And R 1 is a saturated or unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms; the nitrogen-containing terminal structure of the molecular chain of the fiber-forming polymer polyamide is composed of a C 2 -C 2 0 carboxylic acid or a derivative thereof The terminal amino group of the polyamide polymer molecular chain is formed by a chemical reaction.
2 、根据权利要求1所述的 防黄变 聚酰胺纤维，其特征在于： 所 述 C2 ～ C 2 0 的羧酸衍生物 为 乙二酸酐、丙二酸酐、丁二酸酐、戊二酸酐、己二酸酐、庚二酸酐、辛二酸酐、壬二酸酐、葵二酸酐或马来酸酐。The anti-yellowing polyamide fiber according to claim 1, wherein the C 2 -C 2 0 carboxylic acid derivative is oxalic anhydride, malonic anhydride, succinic anhydride, glutaric anhydride, and hexanic acid. Anhydride, pimelic anhydride, suberic anhydride, sebacic anhydride, alkalic anhydride or maleic anhydride.
3 、根据权利要求1所述的 防黄变 聚酰胺纤维，其特征在于：所述的与 C2 ～ C 2 0 的羧酸或者其衍生物 反应形成成纤聚合物聚酰胺分子链含氮末端结构的聚酰胺聚合物为与对苯二甲酸共聚合后的聚酰胺6或聚酰胺66。The anti-yellowing polyamide fiber according to claim 1, wherein the carboxylic acid or a derivative thereof is reacted with a C 2 -C 2 0 carboxylic acid or a derivative thereof to form a nitrogen-containing terminal structure of the fiber-forming polymer polyamide molecular chain. The polyamide polymer is polyamide 6 or polyamide 66 copolymerized with terephthalic acid.
4 、根据权利要求1、2或3所述的的 防黄变 聚酰胺纤维，其特征在于： C2 ～ C 2 0 的 羧酸及其衍生物的添加量为与 其 反应形成成纤聚合物聚酰胺分子链含氮末端结构的聚酰胺聚合物分子链的末端氨基摩尔含量的50 ~ 150% 。The anti-yellowing polyamide fiber according to claim 1, 2 or 3, wherein the C 2 -C 2 0 carboxylic acid and the derivative thereof are added in an amount to react with the fiber-forming polymer polyamide molecule. The polyamide polymer molecular chain having a nitrogen-containing terminal structure has a terminal amino group molar content of 50 to 150%.
5 、一种权利要求1所述的 防黄变 聚酰胺纤维的制造方法，其特征在于：在螺杆挤出机中的入口处，向聚酰胺聚合物中连续添加经过计量的羧酸或者其衍生物，进入螺杆挤出机中混合熔融、纺丝、卷取。5. A yellowing prevention according to claim 1. A method for producing a polyamide fiber, characterized in that a metered carboxylic acid or a derivative thereof is continuously added to a polyamide polymer at an inlet in a screw extruder, and is mixed and melted and spun into a screw extruder. , take.
6 、根据权利要求5所述 防黄变 聚酰胺纤维的制造方法，其特征在于：通过容积式粉体微量添加装置向聚酰胺聚合物中连续添加经过计量的羧酸或者其衍生物。6. Anti-yellowing according to claim 5 A method for producing a polyamide fiber, characterized in that a metered carboxylic acid or a derivative thereof is continuously added to a polyamide polymer by a volumetric powder micro-adding device.
7 、根据权利要求5或6所述 防黄变 聚酰胺纤维的制造方法，其特征在于：聚酰胺聚合物为与对苯二甲酸共聚合后的 聚酰胺6 或聚酰胺66。The method for producing an anti-yellowing polyamide fiber according to claim 5 or 6, wherein the polyamide polymer is polyamide 6 copolymerized with terephthalic acid. Or polyamide 66.
8 、根据权利要求 7 所述 防黄变 聚酰胺纤维的制造方法，其特征在于： 将与对苯二甲酸共聚合得到的聚酰胺 6 或聚酰胺66 切片导入到设置在螺杆挤出机进料口正上方的料仓的同时，通过开口配管向料仓中连续添加羧酸或者其衍生物 ； 所说开口配管设置在从料仓内切片堆积部分的下方起向上至切片堆积高度的 10% ～ 50% 位置处正上方竖直向下的位置。The method for producing an anti-yellowing polyamide fiber according to claim 7, wherein the polyamide 6 obtained by copolymerizing with terephthalic acid is used. Or the polyamide 66 slice is introduced into the silo disposed directly above the feed port of the screw extruder, and the carboxylic acid or its derivative is continuously added to the silo through the open pipe; The opening pipe is disposed from a position below the slice stacking portion in the silo up to a position vertically upward from 10% to 50% of the stacking height.
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