CN115181435B - 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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CN115181435B
CN115181435B CN202210783994.3A CN202210783994A CN115181435B CN 115181435 B CN115181435 B CN 115181435B CN 202210783994 A CN202210783994 A CN 202210783994A CN 115181435 B CN115181435 B CN 115181435B
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carbon black
flame
retardant
pigment
polyester
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CN115181435A (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
    • 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
    • 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
    • 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
    • C08K5/52—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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
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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
    • 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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    • 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
    • C09C3/003—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
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/043—Drying, calcination
    • 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
    • C09C3/08—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
    • 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
    • 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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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

The invention discloses a surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chips, and belongs to the technical field of fine chemical engineering. The surface modification method of the carbon black flame-retardant pigment for the in-situ polymerized polyester chip comprises the following steps: mixing the isocyanate carbon black, the organic solvent and the 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 the reaction product to obtain the carbon black flame-retardant pigment; wherein the structure of the flame retardant is one or more of phosphate, phosphonate, phosphaphenanthrene and phosphine oxide structures. The carbon black flame-retardant pigment has smaller initial particle size, smaller particle size change after being stored for 30 days, long storage period and good storage stability. The filter pressing value of the polyester fiber prepared by the carbon black flame-retardant pigment is low and reaches below 0.7 MPa; the spinnability is good; the flame retardant property is good, and the limiting oxygen index reaches more than 28%.

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 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: dyeing in the polymerization stage and dyeing in the spinning stage. The polymerization stage dyeing is also called as an in-situ polymerization dyeing method, and is a method for preparing the colored PET fiber by adding a colorant in a polycondensation stage of a synthetic PET macromolecule, preparing the colored PET slice and then melt-spinning the colored PET slice. The in-situ polymerization dyeing method is the earliest method for realizing industrial production of the polyester fiber stock solution coloring, and the method has low production cost and can realize mass production, and can also solve the problem of poor compatibility of pigment particles in the stock solution coloring polyester in a matrix.
The fiber has excellent administration performance and functional application, so that the product competitiveness is improved. At present, PET flame-retardant products are developed in a competitive phase all over the world, but the prior flame-retardant PET master batches often have a plurality of problems in practical application, such as: some polyester fibers prepared from flame-retardant PET master batches can generate dense smoke and toxic and harmful gases when burnt, so that the use requirement is difficult to reach; some flame-retardant PET master batches have excellent flame-retardant performance, but the flame retardant is added to seriously damage the polyester structure, and seriously block the spinneret orifices, so that the mechanical properties of the fibers are reduced, and the fibers are difficult to form.
Disclosure of Invention
In order to solve the problems, the invention provides a surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chips, which ensures that the obtained carbon black flame-retardant pigment can not only improve the dispersion performance of the carbon black flame-retardant pigment in polyester fibers, but also endow flame-retardant performance, achieve the effect of halogen-free flame retardance, and solve the problems of poor spinnability, high filtering pressure and poor flame retardance of the traditional flame-retardant master batch.
The first object of the invention is to provide a surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips, which comprises the following steps:
mixing the isocyanate carbon black, the organic solvent and the 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 the reaction product to obtain the carbon black flame-retardant pigment;
wherein the structure of the flame retardant is one or more of phosphate, phosphonate, phosphaphenanthrene and phosphine oxide structures.
In one embodiment of the invention, the flame retardant comprises one or more of trihydroxyethyl phosphate, phenylphosphonic acid and trimethylol phosphine oxide.
In one embodiment of the present invention, the organic solvent is one of toluene, acetone, and butanone.
In one embodiment of the invention, the mass ratio of the isocyanate carbon black to the flame retardant is 1:2 to 5.
In one embodiment of the present invention, the ratio of the amount of the isocyanated carbon black to the organic solvent is 1 to 20g:350mL.
In one embodiment of the invention, the mechanical stirring speed is 200-400 r/min.
In one embodiment of the present invention, the method for preparing the isocyanated carbon black comprises the following steps:
performing 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 liquid, reacting for 30-60 min under ice bath condition, heating to 80-120 ℃ and continuing to react for 30-60 min; removing unreacted diisocyanate by rotary evaporation after the reaction is completed to obtain the isocyanate carbon black;
wherein the liquid phase oxidant is one of hydrogen peroxide solution, nitric acid solution, saturated ammonium persulfate solution, perchloric acid, sodium hypochlorite solution and 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 carried out for 0.5 to 10 hours at 25 to 100 ℃, and more preferably for 3 to 5 hours at 50 to 80 ℃; 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 one of Toluene Diisocyanate (TDI) and isophorone diisocyanate (IPDI); the mass ratio of diisocyanate to oxidized carbon black is 18-25: 50; the rotary steaming temperature is 75-85 ℃; the particle size of the carbon black is 1-50 mu m.
In one embodiment of the present invention, the flame retardant has the following structure:
the second purpose of the invention is the carbon black flame-retardant pigment prepared by the method.
A third object of the present invention is to provide a method for preparing flame retardant black polyester chips, comprising the steps of:
(1) Uniformly mixing the carbon black flame-retardant pigment, the polyester type dispersing agent and the polyol, and grinding to obtain a black flame-retardant pigment dispersion;
(2) And adding a black flame-retardant pigment dispersion before esterification of the polyester, 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 being polyol.
In one embodiment of the invention, the polyol described in step (1) is ethylene glycol.
In one embodiment of the present invention, the polyester dispersant in step (1) is SUA-300 dispersant (Shimami technology); the weight average molecular weight is 5000 to 45000, more preferably 8000 to 38000, still more preferably 10000 to 25000; the number average molecular weight is 1000 to 15000, more preferably 2500 to 12000, still more preferably 4000 to 10000.
In one embodiment of the invention, the milling in step (1) comprises ball milling, sand milling, attritor milling or two-roll or three-roll milling.
In one embodiment of the present invention, the step (2) of adding the black flame retardant pigment dispersion to polymerize before esterification of the polyester is specifically:
the method comprises the steps of mixing refined terephthalic acid and ethylene glycol, and then reacting in a first esterification kettle and a second esterification kettle to obtain polyester esterified oligomer, wherein zinc acetate serving as a catalyst is added in the second esterification kettle, the dosage is generally about 0.05 percent (relative to the weight of DMT), then adding black flame-retardant pigment dispersion into the polyester esterified oligomer, and sequentially passing through a pre-polycondensation kettle and a final polycondensation kettle to prepare flame-retardant black polyester chips according to the national standard GB/T14190-2017 fiber-grade Polyester (PET) chip test method.
The fourth purpose of the invention is to obtain the flame-retardant black polyester chip.
The fifth object of the invention is to provide a flame-retardant black polyester fiber, which is obtained by melt direct spinning of the flame-retardant polyester chips.
The sixth purpose of the invention is to apply the carbon black flame-retardant pigment, the flame-retardant black polyester chips and the flame-retardant black polyester fibers 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 carbon black can be well dispersed in the in-situ polymerized polyester chip, and the flame retardant property of the carbon black pigment is improved; 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 the 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 pigment can be more uniformly dispersed in a resin carrier, so that the dispersion uniformity and compatibility of the pigment are improved when the dope-dyed fibers are prepared, the phenomena of pigment particle aggregation and the like are avoided, the problems of overhigh filter pressing value, poor spinnability, uneven pigment particle distribution in the fibers and the like in the follow-up spinning are solved, and the quality of the dope-dyed fibers is improved.
(3) The carbon black flame-retardant pigment prepared by the invention has smaller initial particle size, smaller particle size change after 30 days of storage, long storage period and good storage stability.
(4) The filter pressing value of the polyester fiber prepared by the carbon black flame-retardant pigment is low and reaches below 0.7 MPa; the spinnability is good; the flame retardant property is good, and the limiting oxygen index reaches more than 28%.
Drawings
FIG. 1 is an SEM image of a polyester fiber prepared from a polyester chip having a mass fraction of 2% of the carbon black flame retardant pigment, wherein (a) is a polyester fiber prepared from a polyester chip having the carbon black flame retardant pigment of example 1, (b) is a polyester fiber prepared from a polyester chip having the carbon black flame retardant pigment of example 2, (c) is a polyester fiber prepared from a polyester chip having the carbon black flame retardant pigment of example 3, and (d) is a polyester fiber prepared from a polyester chip having the carbon black of comparative example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
The testing method comprises the following steps:
particle size distribution testing: the particle size was measured using a Nano-ZS90 laser particle sizer and tested after 30 days of standing at room temperature.
Filtration performance test: 500g PET slices are added into a flushing device to ensure that the melt pressure curve runs stably, and the initial pressure P is recorded 0 The method comprises the steps of carrying out a first treatment on the surface of the 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, the pressure difference Δp=p max -P 0 . The experiment used a 10 μm filter screen. The spinnability of the flame retardant black polyester chips was evaluated by this test.
And (3) observing the surface morphology of the fiber: the prepared polyester fibers were placed on aluminum foil, subjected to metal spraying treatment under an acceleration voltage of 30kV, and observed for the surface morphology of the sample by using a Zeiss Sigma500 type scanning electron microscope. In contrast to an unpigmented polyester fiber precursor under the same process, v represents a surface morphology substantially similar to that of the polyester fiber precursor, Δ represents a few particles, and gamma represents significant particles.
Limiting oxygen index test: oxygen index test was performed according to GB/T8924-2005 standard, using a JF-3 oxygen index instrument from Nanjing Lei Yiqi Equipment Co., ltd. Before starting measurement, a scale mark is firstly 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 and keeps a spline vertical, during measurement, debugging is firstly carried out according to a pre-judging limiting oxygen value of a measured material, and the flow and the oxygen concentration in the test process cannot be changed at will.
Oxygen index theoretical formula: LOI= [ O 2 ]/([O 2 ]+[N 2 ])×100％
Wherein: LOI is limiting oxygen index; [ O 2 ]Oxygen flow (L/min); [ N ] 2 ]Is the flow rate (L/min) of nitrogen.
Example 1
A surface modification method of carbon black flame retardant pigment for in-situ polymerization polyester chips comprises the following steps:
50g of commercial carbon black (particle size of 15 mu m) and 300mL of hydrogen peroxide solution with volume concentration of 30% are sequentially added into a500 mL three-neck flask, the temperature is set to be 70 ℃, the reaction is carried out for 4 hours, and cooling, filtering and water washing are carried out until the pH value of the leaching solution is 7; drying the filter cake at 80 ℃ to obtain oxidized carbon black;
weighing 50g of oxidized carbon black, and adding the oxidized carbon black into a three-neck flask filled with 300mL of toluene for dispersion to obtain oxidized carbon black dispersion liquid; then 18g of Toluene Diisocyanate (TDI) is added into the oxidized carbon black dispersion liquid to react for 30min under the ice bath condition, and then the temperature is raised to 120 ℃ to continue the reaction for 30min; removing unreacted toluene diisocyanate by rotary evaporation at 80 ℃ after the reaction is completed to obtain the isocyanate carbon black;
350mL of toluene, 10g of isocyanated carbon black and 50g of trihydroxyethyl phosphate are added into a three-neck flask to be mixed, and the mixture is subjected to ice bath reaction for 30min under mechanical stirring at 200r/min and then is heated to 120 ℃ to continue the reaction 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:
50g of commercial carbon black (particle size of 15 mu m) and 100mL of nitric acid solution with volume concentration of 68% are sequentially added into a500 mL three-neck flask, the temperature is set to be 25 ℃, the reaction is carried out for 2 hours, and cooling, filtering and water washing are carried out until the pH value of the leaching solution is 7; drying the filter cake at 80 ℃ to obtain oxidized carbon black;
weighing 50g of oxidized carbon black, and adding the oxidized carbon black into a three-neck flask filled with 300mL of acetone for dispersion to obtain oxidized carbon black dispersion liquid; adding 23g of isophorone diisocyanate (IPDI) into the oxidized carbon black dispersion liquid, reacting for 40min under the ice bath condition, and then heating to 110 ℃ for continuous reaction for 30min; removing unreacted isophorone diisocyanate (IPDI) by rotary evaporation at 80 ℃ after the reaction is completed to obtain the isocyanated carbon black;
350mL of acetone, 10g of isocyanated carbon black and 50g of phenylphosphonic acid are added into a three-neck flask to be mixed, and the mixture is heated to 120 ℃ for continuous reaction for 60min after ice bath reaction for 30min under mechanical stirring at 200 r/min; 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:
50g of commercial carbon black (particle size of 15 mu m) and 100mL of saturated ammonium persulfate solution are sequentially added into a500 mL three-neck flask, the temperature is set to be 60 ℃, the reaction is carried out for 3 hours, and cooling, filtering and water washing are carried out until the pH value of the leaching solution is 7; drying the filter cake at 80 ℃ to obtain oxidized carbon black;
weighing 50g of oxidized carbon black, and adding the oxidized carbon black into a three-neck flask filled with 300mL of butanone for dispersion to obtain oxidized carbon black dispersion liquid; then adding 25g of diphenylmethane-4, 4 '-diisocyanate (4, 4' -MDI) into the oxidized carbon black dispersion liquid, reacting for 40min under the ice bath condition, and then heating to 110 ℃ for continuous reaction for 30min; after the reaction is completed, removing unreacted diphenylmethane-4, 4 '-diisocyanate (4, 4' -MDI) by rotary evaporation at 80 ℃ to obtain the isocyanated carbon black;
350mL of toluene, 10g of isocyanated carbon black and 50g of trimethylol phosphine oxide are added into a three-neck flask to be mixed, and the mixture is subjected to ice bath reaction for 30min under mechanical stirring at 200r/min and then heated to 120 ℃ to continue the reaction 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 diameter: 15 μm) was directly used.
Comparative example 2
The flame retardant of example 1, trihydroxyethyl phosphate, was adjusted to ammonium polyphosphate, and the other was the same as in example 1 to obtain a carbon black flame retardant pigment.
Comparative example 3
10g of isocyanated carbon black was simply physically mixed with 50g of a tri-hydroxyethyl phosphate flame retardant to give a carbon black flame retardant pigment.
Comparative example 4
350mL of toluene, 10g of commercial carbon black and 50g of trihydroxyethyl phosphate are added into a three-neck flask to be mixed, and the mixture is subjected to ice bath reaction for 30min under mechanical stirring at 200r/min and then is heated to 120 ℃ to continue the reaction 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 other materials were kept the same as example 1, so as to obtain the carbon black flame retardant pigment.
Comparative example 6
The hydrogen peroxide solution of example 1 was omitted and the other was kept 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 (Shikoku technology) and 200g of ethylene glycol were respectively taken and dispersed in a milling jar for 30 minutes, and 300g of glass beads were added to mill for 2 hours to obtain pigment dispersions.
The obtained dispersion was subjected to a particle size distribution test and a particle size distribution test after standing at room temperature for 30 days, and the test results were as follows:
as can be seen from table 1: the carbon black flame-retardant pigment after the modification treatment in examples 1 to 3 was smaller in primary particle diameter and smaller in particle diameter change after 30 days of storage. The unmodified carbon black has larger particle diameter, short preservation period and poor storage stability.
Table 1 particle diameters of carbon black pigment dispersions prepared in examples 1 to 3 and comparative example 1
Example 4
A method for preparing flame retardant black polyester chips, comprising the steps of:
(1) 50g of the carbon black pigment prepared in examples 1 to 3 and comparative examples 1 to 6, 8g of SUA-300 dispersant (Shikoku technology) and 200g of ethylene glycol were respectively taken and dispersed in a grinding cylinder for 30min, and 300g of glass beads were added to grind for 2h to obtain a pigment dispersion;
(2) Mixing refined terephthalic acid and ethylene glycol, and then reacting in a first esterification kettle and a second esterification kettle to obtain polyester esterified oligomer, wherein zinc acetate serving as a catalyst is added in the second esterification kettle, the dosage is generally 0.05 percent (relative to the weight of DMT (dimethyl terephthalate)), then black flame-retardant pigment dispersoids are added into the polyester esterified oligomer, and after sequentially passing through a pre-polycondensation kettle and a final polycondensation kettle, the polyester esterified oligomer is prepared into colored slices according to the national standard GB/T14190-2017 fiber grade Polyester (PET) slice test method, and the flame-retardant black polyester slices are obtained; wherein the mass percentage of the carbon black flame retardant pigment in the flame retardant black polyester chip is 2%.
And (3) adopting a single-screw extruder to directly spin the melt of the flame-retardant black polyester chips to prepare the polyester fiber with the specification of 150D/36F.
And performing performance test on the obtained slice and polyester fiber, wherein the test result is as follows:
table 2 test results
Example(s) Filter-pressing value of slice (MPa) Surface morphology of fibers Limiting oxygen index of fiber (%)
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 dispersions prepared in examples 1 to 3 are excellent in storage stability and small in particle size; the prepared in-situ polymerized polyester chip has low filter pressing value and good spinnability, and the prepared polyester fiber has higher limiting oxygen index and good flame retardant property. The comparative example 1 uses commercially available carbon black, which has poor flame retardant properties and unmodified carbon black has poor dispersion stability; 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 performance is poor; in comparative examples 3 to 4, the flame retardant was not completely grafted to the surface of carbon black by simple physical mixing, so that the flame retardant performance was poor; in comparative example 5, toluene in the solution is directly volatilized by directly heating to 120 ℃, the viscosity of the solution is increased, and the reaction is slow; 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.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and 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 (8)

1. The surface modification method of the carbon black flame-retardant pigment for the in-situ polymerization polyester chip is characterized by comprising the following steps of:
performing 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 liquid, reacting for 30-60 min under the ice bath condition, and then heating to 80-120 ℃ for continuous reaction for 30-60 min; removing unreacted diisocyanate by rotary evaporation after the reaction is completed to obtain isocyanate carbon black;
mixing the isocyanate carbon black, the organic solvent and the 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 the reaction product to obtain the carbon black flame-retardant pigment;
wherein the flame retardant is one or more of trihydroxyethyl phosphate, phenylphosphonic acid and trimethylol phosphine oxide;
the mass ratio of the isocyanate carbon black to the flame retardant is 1: 2-5;
the dosage ratio of the isocyanate carbon black to the organic solvent is 1-20 g:350mL.
2. The carbon black flame retardant pigment prepared by the method of claim 1.
3. A method for preparing flame retardant black polyester chips, which is characterized by comprising the following steps:
(1) Uniformly mixing the carbon black flame-retardant pigment, the polyester dispersant and the polyol according to claim 2, and grinding to obtain a black flame-retardant pigment dispersion;
(2) And adding a black flame-retardant pigment dispersion before esterification of the polyester, and polymerizing to obtain the flame-retardant black polyester.
4. The method according to claim 3, wherein the mass concentration of the carbon black flame-retardant pigment in the black flame-retardant pigment dispersion in the step (1) is 18-25%, and the amount of the polyester dispersant is 15-20% of the mass of the carbon black flame-retardant pigment; the balance being polyol.
5. A process according to claim 3, wherein the polyol in step (1) is ethylene glycol.
6. The flame retardant black polyester chip prepared by the method of claim 4 or 5.
7. A flame retardant black polyester fiber, characterized in that the flame retardant polyester chip is obtained by melt direct spinning.
8. Use of the carbon black flame retardant pigment of claim 2, the flame retardant black polyester chip of claim 6, the flame retardant black polyester fiber of claim 7 in functional textiles.
CN202210783994.3A 2022-06-28 2022-06-28 Surface modification method of carbon black flame-retardant pigment for in-situ polymerization polyester chip Active CN115181435B (en)

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