WO2023168968A1

WO2023168968A1 - Preparation method for bio-based polyamide plant dye color master batch

Info

Publication number: WO2023168968A1
Application number: PCT/CN2022/130468
Authority: WO
Inventors: 陈群; 纪俊玲; 彭勇刚; 陈海群; 汪媛; 何光裕
Original assignee: 常州大学
Priority date: 2022-11-02
Filing date: 2022-11-08
Publication date: 2023-09-14
Also published as: CN115678271B; CN115678271A

Abstract

A preparation method for a bio-based polyamide plant dye color master batch. In the method, a plant dye is used as a coloring agent, and an encapsulation effect of G5.0 PAMAM cavity on plant dyes is used to prepare a PAMAM-plant dye compound. The compound is used as a functional monomer and added to a preparation process of a copolyamide 6/66, so as to improve the thermal stability of the plant dye and the compatibility thereof with a polyamide carrier. The obtained color master batch is high in coloring strength, good in dispersity and high in stability.

Description

Preparation method of bio-based polyamide plant dye masterbatch

Technical field

The invention belongs to the field of textile technology, and particularly relates to a preparation method of bio-based polyamide plant dye masterbatch.

Background technique

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. my country has pointed out that it is necessary to focus on the creation and application of new biological tools, build a core technology system for biomanufacturing such as bulk chemical products, chemical polymer materials, and bulk fermentation products, and continue to improve the economics and market competitiveness of bio-based products.

There are two main ways to color bio-based polyamide (PA): finished product dyeing and 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. At present, 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. When used in masterbatch production, some components with poor heat resistance decompose at high temperatures and will affect the color of the masterbatch; and many water-soluble components have poor compatibility with the masterbatch carrier, which affects the use of plant dyes in the masterbatch. Dispersion properties in granular carriers. In order to improve the thermal stability of plant dyes, 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. However, 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.

Contents of the invention

In order to overcome the shortcomings of the existing technology, 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. 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 polyamide plant dye masterbatch is obtained through a dry process.

The invention provides a method for preparing bio-based polyamide plant dye masterbatch, which includes the following steps:

(1) After weighing G5.0 PAMAM dendrimers and dissolving them in deionized water, use acetic acid to adjust the pH of the solution to 6-6.5. The maximum amount of plant dye added is the saturated amount of G5.0 PAMAM dendrimers. , that is, gradually add plant dyes until a very small amount of plant dye insoluble matter appears, stir for 1-2 hours in the dark, rotary evaporate at 60-80°C, 0.15-0.7KPa, and wash the viscous material with ether 3-5 times, 40 Vacuum dry at -60℃ for 12-24h to obtain PAMAM-plant dye complex;

As a preferred option, the mass ratio of plant dyes to G5.0 PAMAM dendrimers is 1:1.

Further, 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℃)

(2) Mix 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 ;

Further, the PAMAM-plant dye complex described in step (2) accounts for 10-30% of the total mass of caprolactam and hexamethylene adipate salt.

(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.

Further, the bio-based polyamide described in step (3) is one of PA56, PA 1010, PA 610, PA 1012, PA 410, PA 10T, and PA 6.

Further, the antioxidant described in step (3) is one of antioxidants 1010 and 1168.

Further, 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. 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.

The beneficial effects of the present invention are:

Use 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.

Detailed ways

The present invention will be described in further detail below with reference to specific embodiments. It should be understood that these examples are only for illustrating the present invention and do not limit the scope of the present invention in any way.

Example 1

(1) Accurately weigh 0.5g G5.0 PAMAM dendrimers (purchased from: Weihai Chenyuan Molecular New Materials Co., Ltd.) and dissolve it in 0.5L deionized water. Use acetic acid to adjust the pH of the solution to 6, and gradually add 0.5g Indigo plant dye, stir for 1 hour in the dark, rotary evaporate at 60°C and 0.15KPa, wash the viscous material three times with diethyl ether, and vacuum dry at 40°C for 24 hours to obtain PAMAM-plant dye complex;

(2) Mix caprolactam and hexamethylenediamine adipate salt at a mass ratio of 95:5, then add 10% of the PAMAM-plant dye complex accounting for the sum of the mass of caprolactam and hexamethylenediamine adipate salt, mix evenly, and mix at 100 ℃ oven, vacuum dry for 8 hours, add it to the reaction kettle, introduce nitrogen to replace the air, gradually raise the temperature to 200°C, as the reaction proceeds, the pressure gradually increases to 1.0MPa, react at this pressure for 1.5 hours, and then Release the pressure to normal pressure, continue the reaction for 4 hours and discharge the material to obtain a plant dye-copolyamide 6/66 compound;

(3) In parts by weight, add 10 parts of plant dye-copolyamide 6/66 compound, 89.5 parts of bio-based polyamide PA56, and 0.5 parts of antioxidant 1010 into the mixer and mix evenly, then add the twin-screw The extruder performs melt blending and extrusion. The extruder temperatures are: 1 ^# section 205℃, 2 ^# section 225℃, 3 ^# -4 ^# section 230℃, 5 ^# section 225℃, water cooling and pelletizing. That’s it.

Comparative example 1

In parts by weight, add 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.

Comparative example 2

(1) Accurately weigh 0.5g G2.0 PAMAM dendrimers and dissolve them in 0.5L deionized water, adjust the pH of the solution to 6 with acetic acid, gradually add 0.5g indigo plant dye, stir for 1 hour in the dark, and incubate at 60°C. Rotary evaporate under 0.15KPa conditions, wash the viscous material three times with diethyl ether, and vacuum dry at 40°C for 24 hours to obtain PAMAM-plant dye complex;

(3) In parts by weight, add 10 parts of plant dye-copolyamide 6/66 compound, 89.5 parts of bio-based polyamide PA56, and 0.5 parts of antioxidant 1010 into the mixer and mix evenly, then add the twin-screw The extruder performs melt blending and extrusion. The extruder temperatures are: 1 ^# section 205℃, 2 ^# section 225℃, 3 ^# -4 ^#

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.

Comparative example 3

(1) Accurately weigh 0.5g G5.0 PAMAM dendrimers (purchased from: Weihai Chenyuan Molecular New Materials Co., Ltd.) and dissolve it in 0.5L deionized water. Use acetic acid to adjust the pH of the solution to 6, and gradually add 0.5g Indigo plants were stirred for 1 hour in the dark, then rotary evaporated at 60°C and 0.15KPa. The viscous material was washed three times with diethyl ether and vacuum dried at 40°C for 24 hours to obtain PAMAM-plant dye complex;

(2) In terms of parts by weight, add 10 parts of PAMAM-vegetable dye complex, 89.5 parts of copolyamide 6/66, and 0.5 parts of antioxidant antioxidant 1010 into the mixer and mix evenly, then add it to a twin-screw extruder. Melt blending and extrusion, the extruder temperatures are: 1 ^# section 205℃, 2 ^# section 225℃, 3 ^# -4 ^# section 230℃, 5 ^# section 225℃, water cooling and pelletizing.

Comparative example 4

(2) Mix PAMAM-vegetable dye complex with copolyamide 6/66. The amount of PAMAM-vegetable dye complex added is 10% of the mass of copolyamide 6/66. Melt blending is used to obtain plant dye-copolyamide 6/66. composite materials;

(3) In terms of parts by weight, add 10 parts of plant dye-copolyamide 6/66 composite material, 89.5 parts of bio-based polyamide PA56, and 0.5 part of antioxidant antioxidant 1010 into the mixer, mix evenly, and add the twin-screw The extruder performs melt blending and extrusion. The extruder temperatures are: 1 ^# section 205℃, 2 ^# section 225℃, 3 ^# -4 ^# section 230℃, 5 ^# section 225℃, water cooling and pelletizing. That’s it.

Example 2

(1) Accurately weigh 1.0g G5.0 PAMAM dendrimers and dissolve them in 1.0L deionized water, adjust the pH of the solution to 6.5 with acetic acid, gradually add 1.0g chestnut shell plant dye, stir for 2 hours in the dark, and incubate at 80°C , rotary evaporate under 0.7KPa conditions, wash the viscous material 5 times with diethyl ether, and vacuum dry at 60°C for 12 hours to obtain PAMAM-plant dye complex;

(2) Mix caprolactam and hexamethylenediamine adipate salt at a mass ratio of 90:10, then add 30% of the PAMAM-plant dye complex accounting for the sum of the mass of caprolactam and hexamethylenediamine adipate salt, mix evenly, and mix at 100 ℃ oven, vacuum dry for 10 hours, add it to the reaction kettle, introduce nitrogen to replace the air, gradually raise the temperature to 220°C, as the reaction proceeds, the pressure gradually increases to 1.2MPa, react at this pressure for 0.5h, and then Release the pressure to normal pressure, continue the reaction for 2 hours and discharge the material, and obtain the plant dye-copolyamide 6/66 compound;

(3) In terms of parts by weight, add 30 parts of plant dye-copolyamide 6/66 compound, 69 parts of bio-based polyamide PA 1010, and 1.0 part of antioxidant 1168 into the mixer, mix evenly, and add twin-screw extrusion The machine is used for melt blending and extrusion. The extruder temperatures are: 1 ^# section 210℃, 2 ^# section 230℃, 3 ^# -4 ^# section 235℃, 5 ^# section 230℃, water cooling and pelletizing. .

Example 3

(1) Accurately weigh 0.8g G5.0 PAMAM dendrimers and dissolve them in 0.8L deionized water. Use acetic acid to adjust the pH of the solution to 6.2. Gradually add 0.8g gardenia yellow plant dye and stir for 1.5 hours in the dark. Rotary evaporate at 70°C and 0.4KPa, wash the viscous material 4 times with diethyl ether, and vacuum dry at 50°C for 18 hours to obtain PAMAM-plant dye complex;

(2) Mix caprolactam and hexamethylenediamine adipate salt at a mass ratio of 95:5, then add 20% of the PAMAM-plant dye complex accounting for the sum of the mass of caprolactam and hexamethylenediamine adipate salt, mix evenly, and mix at 100 °C oven, vacuum dry for 9 hours, add it to the reaction kettle, introduce nitrogen to replace the air, gradually raise the temperature to 210 °C, as the reaction proceeds, the pressure gradually increases to 1.1MPa, react at this pressure for 1.0h, and then Release the pressure to normal pressure, continue the reaction for 3 hours and discharge the material, and obtain the plant dye-copolyamide 6/66 compound;

(3) In terms of parts by weight, add 20 parts of the plant dye-copolyamide 6/66 compound, 79.2 parts of the bio-based polyamide PA 610, and 0.8 parts of the antioxidant 1010 into the mixer, mix evenly, and add the twin-screw extruder The machine is used for melt blending and extrusion. The extruder temperatures are: 1 ^# section 208℃, 2 ^# section 228℃, 3 ^# -4 ^# section 232℃, 5 ^# section 228℃, water cooling and pelletizing. .

Example 4

(1) Accurately weigh 0.6g G5.0 PAMAM dendrimers and dissolve them in 0.6L deionized water, adjust the pH of the solution to 6.3 with acetic acid, gradually add 0.6g green tea plant dye, stir in the dark for 1.2h, and incubate at 75°C , rotary evaporation under 0.5KPa conditions, the viscous material was washed three times with diethyl ether, and vacuum dried at 45°C for 16 hours to obtain PAMAM-plant dye complex;

(2) Mix caprolactam and hexamethylenediamine adipate salt at a mass ratio of 90:10, then add 15% of the PAMAM-plant dye complex accounting for the sum of the mass of caprolactam and hexamethylenediamine adipate salt, mix evenly, and mix at 100 ℃ oven, vacuum dry for 8.5h, add it to the reaction kettle, introduce nitrogen to replace the air, gradually raise the temperature to 215℃, as the reaction proceeds, the pressure gradually increases to 1.05MPa, react at this pressure for 0.5h, Then the pressure is released to normal pressure, and the reaction is continued for 3.5 hours to discharge the material to obtain a plant dye-copolyamide 6/66 compound;

(3) In terms of parts by weight, add 9.4 parts of the plant dye-copolyamide 6/66 compound, 90 parts of the bio-based polyamide PA 10T, and 0.6 parts of the antioxidant 1168 into the mixer and mix evenly, then add the twin-screw extruder The machine is used for melt blending and extrusion. The extruder temperatures are: 1 ^# section 206℃, 2 ^# section 226℃, 3 ^# -4 ^# section 235℃, 5 ^# section 226℃, water cooling and pelletizing. .

Example 5

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.

Color uniformity determination

Pick 8 random points on the same garter, measure the K/S value at the maximum absorption wavelength, and calculate the standard deviation S as follows:

In the formula: n is the number of measurement points.

The smaller the S value, the better the color uniformity.

Table 1 Color fastness to heat pressing of garters knitted after natural dye masterbatch spinning

As can be seen from Table 1, 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.

In Comparative Example 1, plant indigo is directly used to prepare the color masterbatch without PAMAM coating. The plant indigo has poor compatibility with the carrier, and the resulting color masterbatch has poor dispersion and poor heat resistance and stability.

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.

In Comparative Example 3, PAMAM-plant dye complex is directly used to prepare color masterbatch. Many plant dyes are adsorbed on the surface of PAMAM. Its compatibility with the base resin bio-based polyamide PA56 is poor, and its dispersion in the color masterbatch is poor. The stability is not as good as that of Example 1.

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. In the subsequent application process, 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.

Table 2 Properties of fibers obtained by adding plant dye masterbatch

It can be seen from Table 2 that 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. In Comparative Example 1, 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. Compared with the blank fiber without color masterbatch, 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. Its compatibility with the matrix resin bio-based polyamide PA56 is not as good as that of the present invention, and the strength of the resulting fiber is also poor. 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.

Claims

A method for preparing bio-based polyamide plant dye color masterbatch, which is characterized in that: using dendritic polyamide-amine polymer (PAMAM) as a carrier and plant dye as a colorant, a PAMAM-plant dye complex is prepared. Add PAMAM-vegetable dye complex to the in-situ polymerization reaction of copolyamide 6/66 to prepare the plant dye-copolyamide 6/66 complex, which is then mixed with a bio-based polyamide carrier and antioxidant, and then melted together Mix, extrude and granulate to obtain bio-based polyamide plant dye masterbatch.
The preparation method of a bio-based polyamide plant dye masterbatch according to claim 1, characterized in that: the specific steps are:

(1) Weigh the G5.0 PAMAM dendrimers and dissolve them in deionized water, adjust the pH of the solution to 6-6.5 with acetic acid, add plant dyes, stir in the dark for 1-2 hours, and heat at 60-80°C, 0.15-0.7 Rotary evaporate under KPa conditions, wash the viscous material 3-5 times with ether, and vacuum dry at 40-60°C for 12-24 hours to obtain PAMAM-plant dye complex;

(2) Mix 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, dry it in an oven under vacuum and then add it to the reaction kettle. After replacing the air with nitrogen, raise the temperature to 200-220°C. As the reaction proceeds, the pressure gradually increases. Raise 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, to obtain a plant dye-copolyamide 6/66 compound;

(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.
The preparation method of a bio-based polyamide plant dye masterbatch according to claim 2, characterized in that: the plant dye described in step (1) is indigo, chestnut shell, gardenia yellow, green tea, gallnut, One or more types of mulberries.
The preparation method of a bio-based polyamide plant dye masterbatch as claimed in claim 2, characterized in that: in step (1), the mass ratio of the plant dye to the G5.0 PAMAM dendrimers is 1:1.
The preparation method of a bio-based polyamide plant dye masterbatch as claimed in claim 2, characterized in that: the PAMAM-plant dye complex described in step (2) accounts for the mass of caprolactam and hexamethylene adipate salt 10-30% of the sum.
The preparation method of a bio-based polyamide plant dye masterbatch as claimed in claim 2, characterized in that: the bio-based polyamide described in step (3) is PA56, PA 1010, PA 610, PA 1012, One of PA 410, PA 10T, PA 6.
The preparation method of a bio-based polyamide plant dye masterbatch according to claim 2, characterized in that: the antioxidant described in step (3) is one of antioxidants 1010 and 1168.
The preparation method of a bio-based polyamide plant dye masterbatch according to claim 2, characterized in that: in step (3), the temperature of the twin-screw extruder is: 1 # section 205-210°C, 2 # section 225 -230℃, 3 # -4 # section 230-235℃, 5 # section 225-230℃.