CN115181435A - Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chip - Google Patents

Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chip Download PDF

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CN115181435A
CN115181435A CN202210783994.3A CN202210783994A CN115181435A CN 115181435 A CN115181435 A CN 115181435A CN 202210783994 A CN202210783994 A CN 202210783994A CN 115181435 A CN115181435 A CN 115181435A
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carbon black
flame
retardant
pigment
polyester
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CN115181435B (en
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王冬
付少海
宋伟广
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Jiangnan University
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Jiangnan University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
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    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • 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
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    • C08K9/04—Ingredients treated with organic substances
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/003—Flushing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
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    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • 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
    • D01F1/04—Pigments
    • 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
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • 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
    • D01F6/92—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 polyesters
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    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a surface modification method of a carbon black flame-retardant pigment for in-situ polymerization polyester chips, belonging to the technical field of fine chemical engineering. The surface modification method of the carbon black flame retardant pigment for the in-situ polymerization polyester chip comprises the following steps: mixing isocyanated carbon black, an organic solvent and a flame retardant, carrying out ice-bath reaction for 30-60 min under mechanical stirring, heating to 100-120 ℃, and continuing to react for 30-60 min; after the reaction is finished, filtering, washing and drying a reaction product to obtain the carbon black flame-retardant pigment; wherein the structure of the flame retardant is one or more of phosphate ester, phosphonate ester, phosphaphenanthrene and phosphine oxide structures. The carbon black flame-retardant pigment has the advantages of small initial particle size, small change of the particle size after 30 days of storage, long storage period and good storage stability. The polyester fiber prepared by the carbon black flame-retardant pigment has a low filter pressing value which is below 0.7 MPa; the spinnability is good; the flame retardant property is good, and the limited oxygen index reaches more than 28 percent.

Description

Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chip
Technical Field
The invention relates to a surface modification method of a carbon black flame retardant pigment for in-situ polymerization polyester chips, belonging to the technical field of fine chemical engineering.
Background
The stock solution coloring method can be subdivided into: polymerization stage dyeing and spinning stage dyeing. The polymerization stage dyeing is also called in-situ polymerization dyeing method, and is a method for preparing colored PET fibers by adding a coloring agent in a condensation polymerization stage of synthesizing PET macromolecules, preparing colored PET slices and then carrying out melt spinning on the colored PET slices. The in-situ polymerization dyeing method is the earliest method for realizing industrial production of the dope dyeing of the polyester fiber, has low production cost, can be produced in large batch, and can solve the problem of poor compatibility of pigment particles in the dope dyeing polyester on a matrix.
The fiber is endowed with functional application while ensuring excellent wearability, so as to improve the competitiveness of products. At present, PET flame-retardant products are developed in competition all over the world, but the existing flame-retardant PET master batch often has a plurality of problems in practical application, such as: some polyester fibers prepared from the flame-retardant PET master batch can generate dense smoke and toxic and harmful gases during combustion, and the use requirements are difficult to meet; some flame-retardant PET master batches have excellent flame-retardant performance, but the flame-retardant PET master batches seriously damage the polyester structure and seriously block spinneret orifices, so that the mechanical property of the fiber is reduced and the fiber is difficult to form.
Disclosure of Invention
In order to solve the problems, the invention provides a surface modification method of a carbon black flame-retardant pigment for in-situ polymerization polyester chips, so that the obtained carbon black flame-retardant pigment can be used for preparing in-situ polymerization polyester fibers, the dispersion performance of the carbon black flame-retardant pigment in the polyester fibers can be improved, the flame-retardant performance can be endowed, the halogen-free flame-retardant effect is achieved, and the problems of poor spinnability, high filtration pressure and poor flame-retardant effect of the traditional flame-retardant master batch are solved.
The first purpose of the invention is to provide a surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chip, which comprises the following steps:
mixing isocyanated carbon black, an organic solvent and a flame retardant, carrying out ice-bath reaction for 30-60 min under mechanical stirring, heating to 100-120 ℃, and continuing to react for 30-60 min; after the reaction is finished, filtering, washing and drying a reaction product to obtain the carbon black flame-retardant pigment;
wherein the structure of the flame retardant is one or more of phosphate ester, phosphonate ester, phosphaphenanthrene and phosphine oxide structures.
In one embodiment of the present invention, the flame retardant comprises one or more of trihydroxyethyl phosphate, phenylphosphonic acid, and tris (hydroxymethyl) phosphine oxide.
In an embodiment of the present invention, the organic solvent is one of toluene, acetone, and butanone.
In one embodiment of the present invention, the mass ratio of the isocyanated carbon black to the flame retardant is 1:2 to 5.
In one embodiment of the present invention, the amount ratio of the isocyanated carbon black to the organic solvent is 1 to 20g:350mL.
In one embodiment of the present invention, the rotation speed of the mechanical stirring is 200 to 400r/min.
In one embodiment of the present invention, the preparation method of the isocyanated carbon black comprises:
carrying out oxidation modification on carbon black by adopting a liquid-phase oxidant to obtain oxidized carbon black; then dispersing the oxidized carbon black in an organic solvent to obtain an oxidized carbon black dispersion liquid; adding diisocyanate into the oxidized carbon black dispersion, reacting for 30-60 min under an ice bath condition, and then heating to 80-120 ℃ to continue reacting for 30-60 min; after the reaction is finished, removing unreacted diisocyanate by rotary evaporation to obtain the isocyanate carbon black;
the liquid-phase oxidant is one of a hydrogen peroxide solution, a nitric acid solution, a saturated ammonium persulfate solution, perchloric acid, a sodium hypochlorite solution and a potassium permanganate solution; the dosage ratio of the carbon black to the liquid phase oxidant is 1-50 g:100mL, more preferably 5 to 50g:100mL, more preferably 10 to 50g:100mL; the oxidation modification is oxidation modification at 25-100 ℃ for 0.5-10 h, and is further preferably oxidation modification at 50-80 ℃ for 3-5 h; the organic solvent is one of toluene, acetone and butanone; the dosage ratio of the oxidized carbon black to the organic solvent is 10-40 g:100mL; the diisocyanate is one of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (HMDI), and more preferably, the diisocyanate is one of Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the mass ratio of diisocyanate to oxidized carbon black is 18-25: 50; the temperature of rotary evaporation is 75-85 ℃; the particle size of the carbon black is 1 to 50 μm.
In one embodiment of the present invention, the flame retardant has the following structure:
Figure BDA0003718016680000021
the second object of the present invention is a carbon black flame retardant pigment prepared by the method of the present invention.
The third purpose of the invention is to provide a method for preparing flame-retardant black polyester chips, which comprises the following steps:
(1) Uniformly mixing the carbon black flame-retardant pigment, the polyester dispersant and the polyhydric alcohol, and grinding to obtain a black flame-retardant pigment dispersoid;
(2) Adding a black flame-retardant pigment dispersoid before polyester esterification, and polymerizing to obtain the flame-retardant black polyester.
In one embodiment of the present invention, the mass concentration of the carbon black flame retardant pigment in the black flame retardant pigment dispersion in the step (1) is 18 to 25%, and the amount of the polyester type dispersant is 15 to 20% of the mass of the carbon black flame retardant pigment; the balance of polyhydric alcohol.
In one embodiment of the present invention, the polyol in step (1) is ethylene glycol.
In one embodiment of the present invention, the polyester type dispersant in the step (1) is SUA-300 dispersant (world name science); the weight average molecular weight is 5000 to 45000, more preferably 8000 to 38000, and still more preferably 10000 to 25000; the number average molecular weight is 1000 to 15000, more preferably 2500 to 12000, and still more preferably 4000 to 10000.
In one embodiment of the present invention, the grinding in step (1) comprises ball milling, sand milling, attritor milling or two-or three-roll milling.
In one embodiment of the present invention, the step (2) of adding the black flame-retardant pigment dispersion for polymerization before polyester esterification specifically comprises:
mixing purified terephthalic acid and ethylene glycol, reacting in a first esterification kettle and a second esterification kettle to obtain a polyester esterified oligomer, adding a catalyst zinc acetate in the second esterification kettle, wherein the using amount of the zinc acetate is about 0.05% (based on the weight of DMT), adding a black flame-retardant pigment dispersion into the polyester esterified oligomer, sequentially passing through a pre-polycondensation kettle and a final polycondensation kettle, and preparing the flame-retardant black polyester slice according to the national standard GB/T14190-2017 fiber-grade Polyester (PET) slice test method.
The fourth purpose of the invention is to obtain the flame-retardant black polyester chip prepared by the method.
The fifth purpose of the invention is to provide a flame-retardant black polyester fiber which is obtained by adopting the flame-retardant polyester chip of the invention to carry out melt direct spinning.
The sixth purpose of the invention is the application of the carbon black flame-retardant pigment, the flame-retardant black polyester chip and the flame-retardant black polyester fiber in functional textiles.
The invention has the beneficial effects that:
(1) According to the invention, the flame retardant is grafted on the surface of the carbon black, so that the flame retardant property of the carbon black pigment is improved while the carbon black is well dispersed in the in-situ polymerized polyester chip; in addition, the invention adopts the polyester dispersant to disperse and grind the carbon black in a polyol system, reduces the particle size of the carbon black and is beneficial to the application in-situ polymerization of polyester fibers.
(2) When the surface modified carbon black flame retardant pigment is used for preparing in-situ polymerized polyester chips, the flame retardant pigment can be uniformly dispersed in a resin carrier, so that the dispersion uniformity and compatibility of the pigment during preparation of the dope dyed fiber are improved, the phenomena of pigment particle agglomeration and the like are avoided, the problems of overhigh filter pressing value, poor spinnability, non-uniform distribution of pigment particles in the fiber and the like in subsequent spinning are solved, and the quality of the dope dyed fiber is improved.
(3) The carbon black flame-retardant pigment prepared by the method disclosed by the invention is small in initial particle size, small in particle size change after being stored for 30 days, long in storage period and good in storage stability.
(4) The polyester fiber prepared by using the carbon black flame-retardant pigment has a low filter pressing value which is below 0.7 MPa; the spinnability is good; the flame retardant property is good, and the limited oxygen index reaches more than 28 percent.
Drawings
FIG. 1 is an SEM image of a polyester fiber produced from a polyester chip containing a carbon black flame retardant pigment in an amount of 2% by mass, wherein (a) is the polyester fiber produced from the polyester chip containing the carbon black flame retardant pigment of example 1, (b) is the polyester fiber produced from the polyester chip containing the carbon black flame retardant pigment of example 2, (c) is the polyester fiber produced from the polyester chip containing the carbon black flame retardant pigment of example 3, and (d) is the polyester fiber produced from the polyester chip containing the carbon black of comparative example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
The test method comprises the following steps:
testing of particle size distribution: measured using a Nano-ZS90 laser particle sizer, and tested for particle size after standing for 30 days at ambient temperature.
And (3) testing the filtration performance: adding 500g of PET slices into a flushing device, enabling a melt pressure curve to run stably, and recording initial pressure P 0 (ii) a Then 4000g of flame-retardant black polyester chips are added, 500g of PET chips are added after the materials are used up, and the highest pressure P in the test process is recorded max It is known that the content of black pigment in the flame-retardant black polyester chip is 80g, and the pressure difference Δ P = P max -P 0 . A10 μm filter screen was used for the experiment. By this test, spinnability of flame-retardant black polyester chips was evaluated.
Fiber surface morphology observation: the prepared polyester fibers were placed on aluminum foils, treated with gold spraying under an accelerating voltage of 30kV, and the surface morphology of the samples was observed with a Zeiss Sigma500 scanning electron microscope. Compared with the polyester fiber precursor without pigment under the same process, the V represents the surface morphology basically similar to that of the polyester fiber precursor, the A represents a little particles, and the gamma represents obvious particles.
Limiting oxygen index test: the oxygen index was measured according to GB/T8924-2005, using JF-3 oxygen index instrument from Nanjing instruments and Equipment Ltd. Before measurement, a scale mark needs to be drawn at a position 50mm away from one end of ignition, then the other end of the scale mark is arranged on a test piece clamp, a sample strip is kept vertical, debugging is carried out according to a pre-judged limit oxygen value of a measured material during measurement, and the flow and the oxygen concentration cannot be changed at will in the test process.
Theoretical formula of oxygen index: LOI = [ O ] 2 ]/([O 2 ]+[N 2 ])×100％
In the formula: LOI is limiting oxygen index; [ O ] 2 ]Oxygen flow (L/min); [ N ] 2 ]The flow rate of nitrogen (L/min) was used.
Example 1
A surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips comprises the following steps:
sequentially adding 50g of commercially available carbon black (the particle size is 15 mu m) and 300mL of hydrogen peroxide solution with the volume concentration of 30% into a500 mL three-neck flask, setting the temperature to be 70 ℃, reacting for 4 hours, cooling, filtering and washing until the pH value of a leachate is 7; drying the filter cake at 80 ℃ to obtain the oxidized carbon black;
weighing 50g of oxidized carbon black, adding the oxidized carbon black into a three-neck flask filled with 300mL of toluene, and dispersing to obtain oxidized carbon black dispersion liquid; adding 18g of Toluene Diisocyanate (TDI) into the oxidized carbon black dispersion liquid, reacting for 30min under an ice bath condition, and then heating to 120 ℃ to continue reacting for 30min; after the reaction is finished, removing unreacted toluene diisocyanate by rotary evaporation at 80 ℃ to obtain the isocyanate carbon black;
adding 350mL of toluene, 10g of isocyanated carbon black and 50g of trihydroxyethyl phosphate into a three-neck flask for mixing, carrying out ice bath reaction for 30min under mechanical stirring at 200r/min, heating to 120 ℃, and continuing to react for 60min; and cooling, filtering, washing and drying the reaction product to obtain the carbon black flame-retardant pigment.
Example 2
A surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips comprises the following steps:
sequentially adding 50g of commercially available carbon black (the particle size is 15 mu m) and 100mL of nitric acid solution with the volume concentration of 68% into a500 mL three-neck flask, setting the temperature to be 25 ℃, reacting for 2 hours, cooling, filtering and washing with water until the pH value of a leachate is 7; drying the filter cake at 80 ℃ to obtain the oxidized carbon black;
weighing 50g of oxidized carbon black, adding the oxidized carbon black into a three-neck flask filled with 300mL of acetone, and dispersing to obtain oxidized carbon black dispersion liquid; adding 23g of isophorone diisocyanate (IPDI) into the oxidation carbon black dispersion liquid, reacting for 40min under an ice bath condition, then heating to 110 ℃, and continuing to react for 30min; after the reaction is finished, removing unreacted isophorone diisocyanate (IPDI) by rotary evaporation at 80 ℃ to obtain the isocyanated carbon black;
adding 350mL of acetone, 10g of isocyanated carbon black and 50g of phenylphosphonic acid into a three-neck flask, mixing, carrying out ice-bath reaction for 30min under mechanical stirring at 200r/min, heating to 120 ℃, and continuing to react for 60min; and cooling, filtering, washing and drying the reaction product to obtain the carbon black flame-retardant pigment.
Example 3
A surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips comprises the following steps:
sequentially adding 50g of commercially available carbon black (the particle size is 15 mu m) and 100mL of saturated ammonium persulfate solution into a500 mL three-neck flask, setting the temperature to be 60 ℃, reacting for 3h, cooling, filtering and washing with water until the pH value of a leachate is 7; drying the filter cake at 80 ℃ to obtain the oxidized carbon black;
weighing 50g of oxidized carbon black, adding the oxidized carbon black into a three-neck flask filled with 300mL of butanone, and dispersing to obtain oxidized carbon black dispersion liquid; adding 25g of diphenylmethane-4,4 '-diisocyanate (4,4' -MDI) into the oxidized carbon black dispersion liquid, reacting for 40min under an ice bath condition, and then heating to 110 ℃ to continue reacting for 30min; after the reaction is finished, removing unreacted diphenylmethane-4,4 '-diisocyanate (4,4' -MDI) by rotary evaporation at 80 ℃ to obtain the isocyanated carbon black;
adding 350mL of toluene, 10g of isocyanated carbon black and 50g of tris (hydroxymethyl) phosphine oxide into a three-neck flask, mixing, carrying out ice-bath reaction for 30min under mechanical stirring at 200r/min, heating to 120 ℃, and continuing to react for 60min; and cooling, filtering, washing and drying the reaction product to obtain the carbon black flame-retardant pigment.
Comparative example 1
Commercially available carbon black (particle size 15 μm) was used as it is.
Comparative example 2
The trihydroxyethyl phosphate as a flame retardant in example 1 was adjusted to ammonium polyphosphate, and the rest was the same as in example 1 to obtain a carbon black flame retardant pigment.
Comparative example 3
10g of isocyanated carbon black and 50g of trihydroxyethyl phosphate flame retardant are simply and physically mixed to obtain the carbon black flame retardant pigment.
Comparative example 4
Adding 350mL of toluene, 10g of commercially available carbon black and 50g of trihydroxyethyl phosphate into a three-neck flask, mixing, carrying out ice-bath reaction for 30min under mechanical stirring at 200r/min, heating to 120 ℃, and continuing to react for 60min; and cooling, filtering, washing and drying the reaction product to obtain the carbon black flame-retardant pigment.
Comparative example 5
The reaction of the isocyanated carbon black and the flame retardant in example 1 was adjusted to be directly heated to 120 ℃ for 60min, and the rest was kept the same as example 1, to obtain a carbon black flame retardant pigment.
Comparative example 6
The hydrogen peroxide solution in example 1 was omitted and the rest was the same as in example 1 to obtain a carbon black flame retardant pigment.
50g of the carbon black flame-retardant pigment of examples 1 to 3 and the carbon black obtained in comparative examples 1 to 6, 8g of SUA-300 dispersant (world name technology) and 200g of ethylene glycol were each dispersed in a milling jar for 30 minutes, and 300g of glass beads were added and milled for 2 hours to obtain a pigment dispersion.
The obtained dispersion was subjected to a particle size distribution test and a particle size distribution test after being left at normal temperature for 30 days, and the test results were as follows:
as can be seen from table 1: the carbon black flame retardant pigments subjected to the modification treatment in examples 1 to 3 had a small initial particle diameter and a small change in particle diameter after 30 days of storage. The carbon black without modification has larger grain diameter, short preservation period and poor storage stability.
Table 1 particle diameter of carbon black pigment dispersions prepared in examples 1 to 3 and comparative example 1
Figure BDA0003718016680000071
Example 4
A method for preparing flame-retardant black polyester chips comprises the following steps:
(1) 50g of the carbon black pigment prepared in examples 1 to 3 and comparative examples 1 to 6, 8g of SUA-300 dispersant (world name science) and 200g of ethylene glycol were dispersed in a milling jar for 30min, and 300g of glass beads were added to mill for 2h to obtain a pigment dispersion;
(2) Mixing purified terephthalic acid and ethylene glycol, and reacting in a first esterification kettle and a second esterification kettle to obtain a polyester esterified oligomer, wherein a catalyst zinc acetate is added in the second esterification kettle, the using amount is generally 0.05% (relative to the weight of DMT (dimethyl terephthalate)), then a black flame-retardant pigment dispersion is added into the polyester esterified oligomer, and the polyester esterified oligomer is sequentially subjected to a pre-polycondensation kettle and a final polycondensation kettle and then prepared into colored slices according to the national standard GB/T14190-2017 fiber-grade Polyester (PET) slice test method to obtain the flame-retardant black polyester slices; wherein the mass percentage of the carbon black flame-retardant pigment in the flame-retardant black polyester chip is 2 percent.
And (3) carrying out melt direct spinning on the flame-retardant black polyester chip by adopting a single-screw extruder to prepare the polyester fiber with the specification of 150D/36F.
The obtained chip and polyester fiber were subjected to performance tests, and the test results were as follows:
TABLE 2 test results
Example (b) Filter pressing value of slice (MPa) Surface morphology of fiber Limiting oxygen index (%)
Example 1 0.63 √ 30.5
Example 2 0.58 √ 31.3
Example 3 0.7 Δ 28
Comparative example 1 6.3 ╳ 22
Comparative example 2 4.5 ╳ 26.6
Comparative example 3 4.2 ╳ 26.2
Comparative example 4 5.8 ╳ 25.3
Comparative example 5 2.6 ╳ 27.3
Comparative example 6 5.4 ╳ 25.6
As can be seen from table 2: the surface-modified carbon black flame-retardant pigment dispersion prepared in examples 1 to 3 is excellent in storage stability and small in particle size; the prepared in-situ polymerization polyester chip has low filter pressing value and good spinnability, and the prepared polyester fiber has higher limit oxygen index and good flame retardant property. In comparative example 1, commercially available carbon black was used, which was poor in flame retardancy and poor in dispersion stability of unmodified carbon black; in comparative example 2, ammonium polyphosphate is used as a flame retardant, the reaction degree with the isocyanated carbon black is low, and the flame retardant is not completely grafted to the carbon black, so that the flame retardant property is poor; in comparative examples 3 to 4, the flame retardant cannot be completely grafted to the surface of carbon black by simple physical mixing, so that the flame retardant property is poor; in the comparative example 5, the temperature is directly heated to 120 ℃, so that the toluene in the solution is directly volatilized, the viscosity of the solution is increased, and the reaction is slowly carried out; in comparative example 6, the carbon black was not subjected to oxidation treatment, so that the number of reactive groups on the surface of the carbon black was reduced and the reaction with isocyanate was not completed, so that the dispersion stability and flame retardancy of the carbon black were lowered.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips is characterized by comprising the following steps:
mixing isocyanated carbon black, an organic solvent and a flame retardant, carrying out ice-bath reaction for 30-60 min under mechanical stirring, heating to 100-120 ℃, and continuing to react for 30-60 min; after the reaction is finished, filtering, washing and drying a reaction product to obtain the carbon black flame-retardant pigment;
wherein the structure of the flame retardant is one or more of phosphate ester, phosphonate, phosphaphenanthrene and phosphine oxide structures.
2. The method of claim 1, wherein the mass ratio of the isocyanated carbon black to the flame retardant is 1:2 to 5.
3. The method according to claim 1, wherein the amount ratio of the isocyanated carbon black to the organic solvent is 1 to 20g:350mL.
4. A carbon black flame retardant pigment prepared by the process of any of claims 1 to 3.
5. The method for preparing the flame-retardant black polyester chip is characterized by comprising the following steps of:
(1) Uniformly mixing the carbon black flame-retardant pigment, the polyester dispersant and the polyhydric alcohol according to claim 4, and grinding to obtain a black flame-retardant pigment dispersion;
(2) Adding a black flame-retardant pigment dispersoid before polyester esterification, and polymerizing to obtain the flame-retardant black polyester.
6. The method according to claim 5, wherein the mass concentration of the carbon black flame retardant pigment in the black flame retardant pigment dispersion of step (1) is 18 to 25%, and the amount of the polyester type dispersant is 15 to 20% of the mass of the carbon black flame retardant pigment; the balance of polyhydric alcohol.
7. The method according to claim 5, wherein the polyol in step (1) is ethylene glycol.
8. Flame retardant black polyester chip obtainable by the process according to any one of claims 5 to 7.
9. A flame-retardant black polyester fiber, which is obtained by melt direct spinning of the flame-retardant polyester chip according to claim 8.
10. The carbon black flame retardant pigment of claim 4, the flame retardant black polyester chip of claim 8, the use of the flame retardant black polyester fiber of claim 9 in functional textiles.
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