WO2023168968A1 - Procédé de préparation d'un mélange maître de couleur de colorant végétal de polyamide d'origine biologique - Google Patents

Procédé de préparation d'un mélange maître de couleur de colorant végétal de polyamide d'origine biologique Download PDF

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Publication number
WO2023168968A1
WO2023168968A1 PCT/CN2022/130468 CN2022130468W WO2023168968A1 WO 2023168968 A1 WO2023168968 A1 WO 2023168968A1 CN 2022130468 W CN2022130468 W CN 2022130468W WO 2023168968 A1 WO2023168968 A1 WO 2023168968A1
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Prior art keywords
plant dye
bio
pamam
plant
parts
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PCT/CN2022/130468
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English (en)
Chinese (zh)
Inventor
陈群
纪俊玲
彭勇刚
陈海群
汪媛
何光裕
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常州大学
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Publication of WO2023168968A1 publication Critical patent/WO2023168968A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • D01F1/06—Dyes
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides

Definitions

  • the invention belongs to the field of textile technology, and particularly relates to a preparation method of bio-based polyamide plant dye masterbatch.
  • Bio-based polyamide uses renewable biomass as raw material and obtains monomers for synthetic polyamide through biological, chemical and physical means, including bio-based lactam, bio-based dibasic acid, bio-based diamine, etc., and then Polymer materials synthesized through polymerization reactions. Compared with petroleum-based materials, bio-based materials reduce carbon dioxide emissions and dependence on petroleum. At the same time, the production process is more environmentally friendly and meets the sustainable development needs of society. In recent years, developed countries such as the United States, Germany, and the European Union have proposed that they should vigorously develop the bioeconomy and achieve economic and social transformation.
  • color bio-based polyamide PA
  • finished product dyeing liquid dyeing
  • liquid dyeing Compared with the dyeing method, dope dyeing eliminates the traditional dyeing and finishing process, has low energy consumption and less pollution, and basically realizes the green production of fiber.
  • the fiber has high color intensity, uniform color and bright color, and has broad development prospects.
  • the colorants used in liquid coloring are mainly synthetic pigments. Plant dyes are extracted from flowers, grass, trees, stems, leaves, fruits, seeds, bark, roots, etc. of natural plants. They have soft colors and are ecologically friendly. In addition to pigments, plant dyes often contain sugars, proteins, oils, inorganic substances and other ingredients.
  • the patent CN113637189A (a method for preparing polylactic acid plant dye masterbatch) uses the phase change material tetradecane as the solvent to extract the plant dyes, and uses polyester as the wall material to micronize the obtained plant dyes. Encapsulation uses the endothermic regulation and temperature-regulating effect of phase change materials and the coating effect of microcapsules to improve the thermal stability of plant dyes.
  • this technology can only extract fat-soluble pigments, and the resulting plant dye microcapsules only have good compatibility with polyester carriers. At present, there are no reports on polyamide plant dye masterbatch developed using water-soluble plant dyes.
  • the present invention provides a method for preparing bio-based polyamide plant dye masterbatch.
  • the method uses dendritic polyamide-amine (PAMAM) polymer as a carrier and utilizes its internal voids.
  • PAMAM dendritic polyamide-amine
  • the hydrogen bonding between the nitrogen and oxygen atoms in the cavity structure and the plant dyes, as well as the electrostatic interaction between the high-density -NH 2 and the plant dyes form a complex.
  • PAMAM dendritic polyamide-amine
  • the hydrogen bonding between the nitrogen and oxygen atoms in the cavity structure and the plant dyes, as well as the electrostatic interaction between the high-density -NH 2 and the plant dyes form a complex.
  • Through ether washing the plant dyes with poor binding force to the PAMAM polymer are dissolved into the complex.
  • the non-pigment components are partially removed, and then the resulting PAMAM-plant dye complex is evenly mixed with the bio-based polyamide carrier and antioxidant, and then the poly
  • the invention provides a method for preparing bio-based polyamide plant dye masterbatch, which includes the following steps:
  • the mass ratio of plant dyes to G5.0 PAMAM dendrimers is 1:1.
  • the plant dye described in step (1) is one or more of indigo, chestnut shell, gardenia yellow, green tea, gallnut, and mulberry.
  • Vegetable dyes are provided by Changzhou Meisheng Biomaterials Co., Ltd. Tg test shows that these vegetable dyes can withstand high temperatures above 200°C
  • caprolactam and hexamethylenediamine adipate salt according to parts by weight, wherein the caprolactam is 80 to 95 parts, the hexamethylene adipate salt is 5 to 20 parts, and the total parts of caprolactam and hexamethylene adipate salt are 100 parts, then add PAMAM-vegetable dye complex and mix evenly, vacuum dry in a 100°C oven for 8-10 hours, add it to the reaction kettle, introduce nitrogen to replace the air, gradually raise the temperature to 200-220°C, and then As the reaction proceeds, the pressure gradually increases to 1.0-1.2MPa, react under this pressure for 0.5-1.5h, then release the pressure to normal pressure, continue the reaction for 2-4h and discharge the material, and obtain the plant dye-copolyamide 6/66 composite ;
  • step (2) accounts for 10-30% of the total mass of caprolactam and hexamethylene adipate salt.
  • step (3) In parts by weight, add 10-30 parts of the plant dye-copolyamide 6/66 compound obtained in step (2), 69-90 parts of bio-based polyamide, and 0.5-1.0 parts of antioxidant into the mixer Mix evenly, then add it to a twin-screw extruder for melt blending, extrusion, water cooling, and pelletizing.
  • bio-based polyamide described in step (3) is one of PA56, PA 1010, PA 610, PA 1012, PA 410, PA 10T, and PA 6.
  • the antioxidant described in step (3) is one of antioxidants 1010 and 1168.
  • the temperature of the twin-screw extruder in step (3) Section 1 # 205-210°C, Section 2 # 225-230°C, Section 3 # -4 # 230-235°C, Section 5 # 225-230°C.
  • the present invention utilizes the hydrogen bonding and electrostatic interaction between -NH2 on PAMAM and plant dyes, as well as the inclusion effect of the internal cavity of PAMAM on plant dyes to prepare PAMAM-plant dye complexes.
  • PAMAM-plant dye complexes Through washing, non-pigments that are weakly combined with PAMAM are The components are partially removed, and then the PAMAM-plant dye complex is used as a functional monomer and added to the preparation process of copolyamide 6/66.
  • the PAMAM end-NH 2 can participate in the copolymerization reaction to improve the stability of the plant dye and its interaction with the polyamide carrier. Compatibility; screen bio-based polyamides to prepare plant dye masterbatch to achieve green production.
  • PAMAM to include plant dyes and use them as functional monomers to add them to the preparation process of copolyamide 6/66 to improve the thermal stability of plant dyes and their compatibility with polyamide resins, and avoid the problem of Thermal decomposition of components with poor thermal stability in plant dyes; improves the uniformity of dispersion of plant dyes in the polyamide matrix, and can further improve the mechanical properties of the fiber.
  • indigo plant dye 10 parts of indigo plant dye, 89.5 parts of bio-based polyamide PA56, and 0.5 parts of antioxidant 1010 into the mixer and mix evenly, then add it to a twin-screw extruder for melt blending, extrusion, and extrusion.
  • the machine temperatures are: 1 # section 205°C, 2 # section 225°C, 3 # -4 # sections 230°C, 5 # section 225°C, water cooling and pelletizing.
  • G2.0 PAMAM dendrimers are less branched than G5.0, and do not contain as many cavities as G5.0. After saturated adsorption, the plant dyes are on the surface of the dendrimers, and the main interaction with the plant dyes is electrostatic binding. , after it is finally made into masterbatch, it is easy to migrate, so the thermal stability is not as good as G5.0. And if the algebra is too high, the solution viscosity will be high, which is not conducive to dye dissolution and adsorption.
  • the bio-based polyamide PA56 and the color masterbatch obtained in the present invention are evenly mixed in a weight ratio of 95:5. After vacuum drying at 130°C for 36 hours, the blend is melt-spun and drafted using a single-screw spinning machine. Obtain the colored polyamide fiber, twist it, and weave it into garters for color measurement; then according to the ISO105X11 standard test method, heat the garters at 190°C for 60 seconds and then measure the color, and measure ⁇ E and discoloration and staining. grade. The higher the discoloration rating, the better the temperature resistance of the masterbatch; the higher the staining rating, the better the migration color fastness.
  • n is the number of measurement points.
  • the garters (Examples 2-4) woven after spinning the masterbatch of the present invention are deeply colored (high K/S value), have good color uniformity (low S value), and are hot-press resistant. Excellent color fastness.
  • Comparative Example 2 uses G2.0 PAMAM instead of G5.0 PAMAM.
  • the amount of plant dyes coated in the PAMAM-plant dye compound obtained is less, and the color of the woven stockings is light; due to the preparation process of the PAMAM-plant dye compound, The amount of uncoated vegetable dyes is larger, and the color fastness of the woven garters is also poor.
  • Comparative Example 4 directly uses PAMAM-vegetable dye complex and copolyamide 6/66 melt blending for granulation.
  • PAMAM-vegetable dye complex does not participate in the polymerization of polyamide.
  • the plant dye is easy to migrate after being heated. As a result, the woven garters will become discolored and stained seriously when heated and pressed.
  • the color masterbatch prepared by the present invention is beneficial to the dispersion and heat resistance.
  • the dispersion and heat resistance affect the mechanical properties of the fiber, and the breaking strength is much higher than that of the comparative example.
  • the plant dye does not have the inclusion effect of PAMAM, and its thermal stability is not as good as that of the present invention.
  • the strength of the obtained fiber is greatly reduced.
  • Comparative Example 2 uses G2.0 PAMAM instead of G5.0 PAMAM. Its coating degree of plant dyes is not as good as that of the present invention, and the strength of the resulting fiber is slightly inferior to that of the present invention.
  • Comparative Example 3 directly uses PAMAM-plant dye complex to prepare color masterbatch.
  • Comparative Example 4 uses PAMAM-vegetable dye complex and copolyamide 6/66 melt blending for granulation. The combination between the two is not as uniform and strong as that of the present invention, and the strength of the resulting fiber is also slightly lower.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyamides (AREA)

Abstract

Procédé de préparation d'un mélange maître de couleur de colorant végétal de polyamide d'origine biologique. Dans le procédé, un colorant végétal est utilisé comme agent colorant, et un effet d'encapsulation de la cavité PAMAM G5.0 sur des colorants végétaux est utilisé pour préparer un composé de colorant végétal PAMAM. Le composé est utilisé comme monomère fonctionnel et ajouté à un procédé de préparation d'un copolyamide 6/66, de façon à améliorer la stabilité thermique du colorant végétal et sa compatibilité avec un support polyamide. Le mélange maître de couleur obtenu présente une résistance à la coloration élevée, une bonne dispersibilité et une stabilité élevée.
PCT/CN2022/130468 2022-11-02 2022-11-08 Procédé de préparation d'un mélange maître de couleur de colorant végétal de polyamide d'origine biologique WO2023168968A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211361265.5A CN115678271B (zh) 2022-11-02 2022-11-02 一种生物基聚酰胺植物染料色母粒的制备方法
CN202211361265.5 2022-11-02

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WO2023168968A1 true WO2023168968A1 (fr) 2023-09-14

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006115547A2 (fr) * 2005-04-20 2006-11-02 Dendritic Nanotechnologies, Inc. Polymeres dendritiques avec fonctionnalite interieure et amplification renforcees
KR20120098381A (ko) * 2011-02-28 2012-09-05 한국생명공학연구원 광변색화합물로 가교된 덴드리머 나노클러스터 구조에 기반한 고대비 생체 이미징을 위한 가역성 형광 스위치
CN104109373A (zh) * 2013-04-18 2014-10-22 兰鲲 一种由改性纳米二氧化钛增韧尼龙材料及其制备方法
CN106633049A (zh) * 2016-12-06 2017-05-10 常州大学 一种还原染料耐臭氧牢度提升剂及其制备方法和应用
CN111909494A (zh) * 2020-08-11 2020-11-10 常州大学 一种天然染料色母粒的制备方法
CN114479442A (zh) * 2021-12-30 2022-05-13 上海普利特复合材料股份有限公司 一种耐冷冻液耐析出阻燃生物基聚酰胺组合物及其制备方法
CN114685818A (zh) * 2020-12-31 2022-07-01 中国纺织科学研究院有限公司 一种聚酰胺色母粒载体树脂的制备方法及聚酰胺色母粒

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006115547A2 (fr) * 2005-04-20 2006-11-02 Dendritic Nanotechnologies, Inc. Polymeres dendritiques avec fonctionnalite interieure et amplification renforcees
KR20120098381A (ko) * 2011-02-28 2012-09-05 한국생명공학연구원 광변색화합물로 가교된 덴드리머 나노클러스터 구조에 기반한 고대비 생체 이미징을 위한 가역성 형광 스위치
CN104109373A (zh) * 2013-04-18 2014-10-22 兰鲲 一种由改性纳米二氧化钛增韧尼龙材料及其制备方法
CN106633049A (zh) * 2016-12-06 2017-05-10 常州大学 一种还原染料耐臭氧牢度提升剂及其制备方法和应用
CN111909494A (zh) * 2020-08-11 2020-11-10 常州大学 一种天然染料色母粒的制备方法
CN114685818A (zh) * 2020-12-31 2022-07-01 中国纺织科学研究院有限公司 一种聚酰胺色母粒载体树脂的制备方法及聚酰胺色母粒
CN114479442A (zh) * 2021-12-30 2022-05-13 上海普利特复合材料股份有限公司 一种耐冷冻液耐析出阻燃生物基聚酰胺组合物及其制备方法

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