CN114085429A - Microcapsule flame retardant and preparation method and application thereof - Google Patents

Microcapsule flame retardant and preparation method and application thereof Download PDF

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CN114085429A
CN114085429A CN202111673449.0A CN202111673449A CN114085429A CN 114085429 A CN114085429 A CN 114085429A CN 202111673449 A CN202111673449 A CN 202111673449A CN 114085429 A CN114085429 A CN 114085429A
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parts
flame retardant
acid
antioxidant
microcapsule
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张乃斌
刘翊超
李磊
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Beijing Puhongbin Chemical Material Co ltd
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Beijing Puhongbin Chemical Material Co ltd
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    • 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
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a microcapsule flame retardant, and a preparation method and application thereof. The flame retardant comprises, by weight, 5-20 parts of shell materials and 80-95 parts of core materials, wherein the core materials comprise 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid-binding agent and 1-4 parts of ultraviolet agent; the shell material is urea-formaldehyde resin. The components in the microcapsule flame retardant are reasonably proportioned, the microcapsule flame retardant is more uniformly dispersed in a polymer matrix material, the flame retardant property of a high polymer material can be obviously improved by a very small addition amount, the generation of toxic and harmful smoke in a combustion process is inhibited, the flame retardant efficiency is greatly improved, the flame retardant effect is more durable, and the problems of high temperature stability and poor aging resistance of a conventional flame retardant can be solved, so that the microcapsule flame retardant is widely applied to the flame retardance of polymer matrix materials such as polyethylene, polypropylene, polyvinyl chloride, poly-1-butylene, polycarbonate, ethylene-vinyl acetate copolymer, polyester or polystyrene.

Description

Microcapsule flame retardant and preparation method and application thereof
Technical Field
The invention relates to the technical field of flame retardants, and particularly relates to a microcapsule flame retardant and a preparation method and application thereof.
Background
In recent decades, the application of polymer materials has been rapidly advanced, and the polymer materials have attracted much attention in various fields, and the yield of polymer materials has increased year by year. Compared with metal materials and inorganic materials, the high polymer materials have unique physical properties and processability, particularly Polystyrene (PS), and are widely applied to the fields of building heat preservation and the like due to low price and easy processing and forming. The most widely used polymer materials at present are expandable polystyrene EPS and extruded polystyrene foam XPS, and the PS foam material is widely applied to the fields of building external wall insulation and the like due to the excellent heat insulation performance, low price and simple and easy implementation of forming equipment. However, most of high polymer materials such as Polystyrene (PS) are composed of carbon and hydrogen elements, are extremely combustible in nature, have a limit oxygen index of only about 18 percent, belong to combustible materials, have large smoke generation amount during combustion, and are easy to generate molten drops to ignite other materials, so that the materials are extremely easy to cause fire in stacking and construction. Statistically, more than 80% of fire-deaths are suffocated deaths due to smoke escaping routes or inhalation of toxic gases. Therefore, it is important to research that the PS foam is flame-retardant and smoke-suppressing so that the PS foam is not combustible when exposed to open flame or can be self-extinguished when isolating a fire source.
At present, the building energy-saving heat-insulating high polymer material which is largely used mainly adopts Hexabromocyclododecane (HBCD) as a flame-retardant auxiliary agent, but the auxiliary agent is already listed in a forbidden list of the Stockholm international convention due to persistent organic pollution; at present, the domestic building energy-saving field urgently needs the green environment-friendly alternative flame retardant to be applied to high polymer materials, which is very key for the nation to realize the aim of building an environment-friendly and resource-saving society; the only products that can currently replace HBCD are brominated styrene-butadiene-styrene block copolymer (brominated SBS) and methyl octabromoether. Brominated SBS is a brominated flame retardant, has good thermal stability, and is researched to have small bearing capacity and generally not thermally degraded under the process conditions of melting a mixture, injecting into a mold and extruding foam, and the process temperature can reach more than 230 ℃. In addition to thermal stability, the brominated SBS polymer has good compatibility with foaming agents used for foaming and has an increased ability to melt fabricated articles when foamed, while the brominated SBS is a stable high molecular weight polymer whose structure makes it less prone to absorption by organisms, eliminating concerns about the environment. Methyl octabromoether belongs to an additive flame retardant, has the characteristics of low dosage, good flame retardant effect, small influence on the physical properties of materials and the like, can show good flame retardant property in PS foam materials, polypropylene, other styrene resins and other high polymer materials, has the flame retardant effect higher than that of bromine aromatic flame retardants, has good thermal stability, can ensure safe processing equipment and excellent product performance, and is suitable for plastic products processed at higher temperature.
Although the two novel flame retardants have obvious advantages, brominated SBS has free small molecular fragments, methyl octabromoether molecules contain eight bromine atoms on an aliphatic chain, in the material, the bromine atoms are easy to generate hydrogen bromide elimination reaction with hydrogen atoms on adjacent aliphatic carbons within a processing temperature range, the hydrogen bromide further catalyzes the breakage of other bromine carbon bonds on the methyl octabromoether molecules after being generated, so that the heat stability of the methyl octabromoether is reduced, the material added with the methyl octabromoether is easy to degrade and discolor due to overheating in the processing process, the physicochemical properties of a high polymer material are damaged in the production process of blending, melting and extruding the material with the high polymer material, and the generated hydrogen bromide is corrosive to production equipment, so a matched heat stabilizing system is required to be introduced in the process of preparing the flame-retardant high polymer material by using the brominated SBS and the methyl octabromoether as the flame retardants, thereby ensuring the processing performance, the molding stability and the flame retardant property of the high polymer material.
At present, there are some researches on the synthesis of brominated SBS and methyl octabromoether, such as patent applications CN111116782A, CN107474165B, CN109762121A, CN109796315A, and CN112830868A, which are dedicated to reducing the generation of free bromine during the synthesis process, so as to improve the thermal stability of the flame retardant, but the chain scission and decomposition of the flame retardant inevitably occur during the thermal processing process, which easily affects the moldability of the polymer material, reduces the compatibility with the polymer material (polymer matrix), causes the processing performance and mechanical property of the polymer material to be obviously reduced, and is difficult to meet the industrial requirements of higher and higher performance requirements of the polymer material.
The existing stearate heat stabilizer has a certain effect on improving the thermal stability of the brominated flame retardant, but cannot meet the requirement on the thermal stability of the two materials of the brominated SBS and the methyl octabromoether at present, so that a new thermal stability system which has a better thermal stability effect and does not influence the physical and chemical properties of a high polymer material and a flame retardant with high thermal stability still need to be developed.
Patent CN112852015A discloses a composite brominated flame retardant with high thermal stability and a flame-retardant polystyrene material foam thereof, which is a technology for obtaining high thermal stability without influencing the foaming of the polystyrene material by adding a specific composite flame-retardant system into polystyrene; firstly, preparing a composite flame retardant containing a thermal stabilization system, a hydrobromic acid absorbent and an antioxidant, and realizing the thermal stabilization of the flame retardant in the processing process of the polystyrene foam material; and then the composite flame retardant is melted and blended with polystyrene, a foaming agent is added, and the mixture is extruded and molded to form the foaming XPS material, the flame-retardant polystyrene foam material obtained by the flame-retardant system has good molding and foaming process performance, the extruded and foamed polystyrene (XPS) realizes good flame-retardant performance under the condition of low addition of the flame retardant, and the physical and mechanical properties of the material and the color of the appearance of the product are maintained. Compared with the application of adopting a stearate heat stabilizer by simple assumption, the hydrogen bromide absorbent is creatively added into the composite system, so that the bromine flame retardant is more efficiently thermally stabilized. However, the method adopts the composite flame retardant containing the thermal stabilization system, the hydrobromic acid absorbent and the antioxidant, which is only physical blending, and is easy to disperse unevenly during XPS/EPS melt extrusion, thereby affecting the mechanical property, the heat insulation property and the flame retardant property of the material.
Patent CN112980046A provides a special high thermal stability flame retardant for EPS/XPS and a preparation method thereof, which solves the technical problem of poor mixing compatibility of brominated styrene butadiene aromatic copolymer and methyl octabromoether with styrene resin base material, the flame retardant is a blend of a thermal stabilizer, brominated styrene butadiene aromatic copolymer and methyl octabromoether, and is prepared by mixing styrene butadiene aromatic copolymer (SBS) with tetrabromobisphenol a bis (methallyl) ether, and under the protection of the thermal stabilizer, the co-synthesis of brominated styrene butadiene aromatic copolymer (SBS) and methyl octabromoether is realized by two-stage bromination. The method synchronously prepares brominated styrene butadiene aromatic copolymer (SBS) and methyl octabromoether, realizes the complete and uniform mixing of the brominated styrene butadiene aromatic copolymer (SBS) and the methyl octabromoether by using a homogeneous phase inverse solvent crystallization mode and assisting a heat stabilizer, improves the compatibility of a flame retardant material and a styrene resin base material, improves the product bulk density, and is easy to be mixed with resin particles in the XPS processing process. Meanwhile, the two flame retardants are protected by the heat stabilizer, so that the product performance is remarkably improved, and the heat stability is high. Although the method realizes the simultaneous preparation of the two flame retardants and simplifies the production process, the thermal stability is not greatly improved, and the material is degraded to a higher degree in the high-temperature processing process.
In the process of implementing the invention, the inventor finds that the prior art has at least the following problems:
the common stearate heat stabilizer system has a simple mechanism, but has no worry about the flame retardant effect of the material with a complex processing technology, and cannot be popularized in a large area. The composite flame retardant consisting of the thermal stabilization system, the hydrobromic acid absorbent and the antioxidant is only physically blended, and is easy to disperse unevenly when a high polymer material is melted and extruded, so that the mechanical property, the heat preservation property and the flame retardant property of the material are influenced. The brominated SBS and the methyl octabromoether obtained by optimizing the production process have no qualitative improvement on the thermal stability of the flame retardant.
Disclosure of Invention
In order to solve the problems of uneven dispersion and poor high-temperature stability of the existing flame retardant in a polymer matrix material, the invention provides a microcapsule flame retardant, which comprises a shell material and a core material, wherein the weight ratio of the shell material to the core material is 5-20:80-95, and the core material comprises the following components in parts by weight: 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid-binding agent and 1-4 parts of ultraviolet agent;
illustratively, the core material may have 80, 85, 90, 95 parts of brominated SBS and/or methyl octabromoether; the heat stabilizer can be 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5 and 5 parts; the antioxidant can be 1, 1.3, 2, 2.5 and 3 parts, and the acid-binding agent can be 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5 and 8 parts; the ultraviolet agent can be 1, 1.5, 2, 2.5, 3, 3.5 and 4 parts. Illustratively, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95 parts of core material can be included in the flame retardant.
As a further aspect of the present invention, the flame retardant shell material includes urea formaldehyde resin. Illustratively, the flame retardant may include 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts of shell material.
In a further embodiment of the present invention, the heat stabilizer is a stearate, preferably at least one of calcium stearate, zinc stearate, and barium stearate.
In a further embodiment of the present invention, the antioxidant in the present invention is at least one of antioxidant 1010, antioxidant 626, antioxidant 168 and antioxidant 1076.
In a further embodiment of the present invention, the acid-binding agent is at least one of bisphenol a glycidyl ether, tetrabromobisphenol a glycidyl ether, brominated epoxy resin, tribromophenol glycidyl ether, divinylbenzene, and triallyl triazine Trione (TAIC).
As a further scheme of the invention, the ultraviolet agent in the invention is (3-10) by weight: 1 with a uv stabilizer.
In a second aspect of the present invention, there is also provided a preparation method of the above microcapsule flame retardant, comprising the steps of:
1) according to the weight parts, 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid binding agent and 1-4 parts of ultraviolet agent are stirred and dissolved in a solvent to form a core material solution;
2) adding water into a three-neck flask with a stirring thermometer, wherein the weight ratio of the water to the water is (1): (2-5) adjusting the pH value of the urea and formaldehyde solution to 8.0-9.5, heating to 60-90 ℃, and carrying out heat preservation reaction for 0.5-1 hour to form a urea formaldehyde pre-polymerization solution;
3) slowly adding 5-20 parts of urea formaldehyde pre-polymerization liquid prepared in the step (2) into 80-95 parts of the reaction system in the step (1), uniformly stirring, adding acid liquor to adjust the pH of the system to 4-6, heating the system to 60-100 ℃, continuously preserving heat and stirring for 1-2h, stopping stirring, washing and drying the solid obtained by filtering to obtain the microcapsule flame retardant
As a further embodiment of the present invention, the solvent in step 1) is water and/or an alcohol solvent; the mass concentration of formaldehyde in the formaldehyde solution in the step 2) is 37-42%.
As a further scheme of the invention, the acid solution in step 3) is at least one of phosphoric acid, oxalic acid, formic acid, ammonium chloride, acetic acid, citric acid and hydrochloric acid; the drying temperature in the step 3) is 100-130 ℃, and the drying time is 24-72 h.
In a third aspect of the invention, the invention also provides a use of the above microcapsule flame retardant in a polymer matrix material, specifically, the polymer matrix material is any one or more of polyethylene, polypropylene, polyvinyl chloride, poly-1-butylene, polycarbonate, ethylene-vinyl acetate copolymer, polyester or polystyrene.
The technical scheme provided by the embodiment of the invention has the following beneficial effects:
the heat stability of brominated SBS or methyl octabromoether can be improved through the synergistic effect of the heat stabilizer, the antioxidant, the acid-binding agent and the ultraviolet agent, and meanwhile, the urea resin is used as a shell material to microencapsulate the flame retardant by utilizing a two-step method in-situ polymerization reaction, so that the appearance state of the flame retardant is changed, the physical and chemical properties of the flame retardant are improved, and the microcapsule flame retardant with good heat resistance and anti-aging performance is obtained. In addition, because the shell material is in a closed state, the migration of the halogenated substances from the inside of the polymer matrix material to the surface is avoided, and the environmental problem caused by the halogenated substances can be solved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below. In the following examples, those whose operations are not subject to the conditions indicated, are carried out according to the conventional conditions or conditions recommended by the manufacturer. It should be understood that these embodiments and examples are given solely for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention, which is provided for the purpose of providing a more thorough understanding of the present disclosure. It is also understood that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, and that various changes and modifications may be effected therein by one of ordinary skill in the art without departing from the spirit and scope of the invention and the resulting equivalents are within the scope and range of equivalents of the present application. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention, and it is to be understood that the present invention may be practiced without one or more of these details.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments and examples only and is not intended to be limiting of the invention.
The invention provides a microcapsule flame retardant, which comprises a shell material and a core material, wherein the weight ratio of the shell material to the core material is 5-20:80-95, and the core material comprises the following components in parts by weight: 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid-binding agent and 1-4 parts of ultraviolet agent.
As a further aspect of the present invention, the shell material includes urea resin.
In a further embodiment of the present invention, the heat stabilizer is a stearate, preferably at least one of calcium stearate, zinc stearate, and barium stearate. The invention adopts stearate compounds, prevents hydrogen bromide from catalyzing and degrading the molecules of the brominated SBS and the methyl octabromoether by absorbing trace hydrogen bromide released in the heating and degrading process of the brominated SBS and the methyl octabromoether, thereby playing a role in stabilizing the brominated SBS and the methyl octabromoether.
In a further embodiment of the present invention, the antioxidant in the present invention is at least one of antioxidant 1010, antioxidant 626, antioxidant 168 and antioxidant 1076. The antioxidant can be directly purchased from the market for products with corresponding specifications. The antioxidant can effectively absorb oxygen free radicals, so that the breaking of bromine carbon bonds is avoided, the degradation of the brominated SBS and the methyl octabromoether can be delayed to generate hydrogen bromide, and the selected antioxidant has good compatibility with the brominated SBS and the methyl octabromoether, and is favorable for improving the comprehensive performance of the flame retardant.
In a further embodiment of the present invention, the acid-binding agent is at least one of bisphenol a glycidyl ether, tetrabromobisphenol a glycidyl ether, brominated epoxy resin, tribromophenol glycidyl ether, divinylbenzene, and triallyl triazine Trione (TAIC). The acid-binding agent can effectively and rapidly react with hydrogen bromide generated by side reaction in the material processing process, the hydrogen bromide is prevented from further attacking a carbon chain to cause chain segment degradation, and meanwhile, the acid-binding agent is used as epoxy resin or vinyl resin, has excellent compatibility with a polymer matrix material, and further improves the mechanical property of the material.
As a further scheme of the invention, the ultraviolet agent in the invention is prepared from (3-10) by weight: 1 with a uv stabilizer. The ultraviolet agent and other components act together, so that the aging resistance of the microcapsule flame retardant can be obviously improved, and the thermal stability of the microcapsule flame retardant can be improved to a certain extent.
Uv agents may be purchased directly from the market in the corresponding specifications, illustratively, the uv absorbers include, but are not limited to, Tinuvin 479, Tinuvin 460, Tinuvin 400, Tinuvin 405, Tinuvin1130, Tinuvin 384-2, Tinuvin 1164, Tinuvin 312, Tinuvin 320, Tinuvin 571, Tinuvin 1600, Tinuvin 1577, Tinuvin 360, Tinuvin 234, Tinuvin 329, Tinuvin 328, Tinuvin 326, Tinuvin 327; illustratively, the uv stabilizers Tinuvin 123, Tinuvin 791, Tinuvin 783, Tinuvin 770, Tinuvin 622, Tinuvin 292.
In a second aspect of the present invention, a preparation method of a microcapsule flame retardant is provided, which comprises the following steps: 1) according to the weight parts, 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid binding agent and 1-4 parts of ultraviolet agent are stirred and dispersed to be uniformly dissolved in water or alcohol solvent to form core material solution;
2) adding water into a three-neck flask with a stirring thermometer, wherein the weight ratio of the water to the water is (1): (2-5) adjusting the pH value of the urea and formaldehyde solution to 8.0-9.5, heating to 60-90 ℃, and carrying out heat preservation reaction for 0.5-1 hour to form a urea formaldehyde pre-polymerization solution;
3) slowly adding 5-20g of the urea formaldehyde pre-polymerization liquid prepared in the step (2) into 80-95g of the reaction system in the step (1), stirring and dispersing at 3000rpm/min for 25-40min, adding an acid liquid to adjust the pH value of the system to 4-6, heating the system to 60-100 ℃, continuing to keep the temperature and stirring for 1-2h, stopping stirring, washing the filtered solid with water, and drying at 130 ℃ for 24-72h to obtain the microcapsule flame retardant.
As a further aspect of the present invention, the acid solution includes, but is not limited to, phosphoric acid, oxalic acid, formic acid, ammonium chloride, acetic acid, citric acid, hydrochloric acid; the acid solution can effectively adjust the pH value of a system, is safe and nontoxic, is convenient to add, and is easy to wash and remove in the post-treatment process.
In the invention, the dispersion speed in the step 3) is controlled at 1500-3000rpm/min, so that the particle size and the morphology of the microcapsule generated by the reaction are regular, and the compatibility of the prepared microcapsule flame retardant in the polymer matrix material is greatly improved.
The method for preparing the microcapsule flame retardant belongs to a two-step in-situ polymerization method: the urea and formaldehyde dissolved or dispersed in the continuous phase react at the interface of the two phases to form insoluble high polymer to wrap the core material, thereby forming the microcapsule. Specifically, formaldehyde and urea are dehydrated to form a water-soluble prepolymer, then a core material is added to the water-soluble prepolymer for dispersion, then polycondensation reaction is carried out between the prepolymers under the condition that the system is acidic, a water-insoluble polycondensate urea-formaldehyde resin with a reticular cross-linked structure is formed, and the core material is coated to form the urea-formaldehyde resin microcapsule.
In a third aspect of the invention, there is also provided a use of the microencapsulated flame retardant described above in a polymeric matrix material.
As a further aspect of the present invention, the polymer matrix material includes, but is not limited to, polyethylene, polypropylene, polyvinyl chloride, poly-1-butene, polycarbonate, ethylene-vinyl acetate copolymer, polyester, or polystyrene.
Example 1:
the microcapsule flame retardant comprises the following core materials in parts by weight: 85 parts of brominated SBS, 5 parts of calcium stearate, 2 parts of antioxidant 1010, 6 parts of bisphenol A glycidyl ether, 2 parts of Tinuvin1130 and Tinuvin292 (mass ratio is 3:1), and stirring and dissolving the components in an alcohol solvent to form a core material solution.
Example 2:
the microcapsule flame retardant comprises the following core materials in parts by weight: 95 parts of methyl octabromoether, 2 parts of calcium stearate, 1 part of antioxidant 1010, 1 part of tetrabromobisphenol A glycidyl ether, and 1 part of Tinuvin1130 and Tinuvin292 (mass ratio of 4:1), and stirring and dissolving the components in an alcohol solvent to form a core material solution.
Example 3:
the microcapsule flame retardant comprises the following core materials in parts by weight: 60 parts of brominated SBS, 30 parts of methyl octabromoether, 3 parts of zinc stearate, 2 parts of antioxidant 626, 4 parts of tribromophenol glycidyl ether, and 1 part of Tinuvin1130 and Tinuvin292 (mass ratio of 5:1), and stirring and dissolving in an alcohol solvent to form a core material solution.
Example 4:
the microcapsule flame retardant comprises the following core materials in parts by weight: 80 parts of methyl octabromoether, 10 parts of brominated SBS, 3 parts of barium stearate, 3 parts of antioxidant 168, 2 parts of brominated epoxy resin, 2 parts of Tinuvin1130 and Tinuvin292 (mass ratio is 2:1), and stirring and dissolving in an alcohol solvent to form a core material solution.
Example 5:
the microcapsule flame retardant comprises the following core materials in parts by weight: 85 parts of methyl octabromoether, 4 parts of calcium stearate, 2 parts of antioxidant 1076, 5 parts of divinylbenzene, 4 parts of Tinuvin1130 and Tinuvin292 (mass ratio of 3.5:1), and stirring and dissolving the components in an alcohol solvent to form a core material solution.
Example 6:
the microcapsule flame retardant comprises the following core materials in parts by weight: 90 parts of methyl octabromoether, 5 parts of barium stearate, 2 parts of antioxidant 168, 2 parts of triallyl triazine Trione (TAIC), and 1 part of Tinuvin1130 and Tinuvin292 (mass ratio is 5.5:1), and stirring and dissolving the components in an alcohol solvent to form a core material solution.
In examples 1-6, urea formaldehyde pre-polymerization solutions were provided: adding water into a three-neck flask with a stirring thermometer, wherein the weight ratio of water to water is 1: 3, adjusting the pH value of the urea and formaldehyde solution to 8.5, heating to 70 ℃, and carrying out heat preservation reaction for 1 hour to form urea formaldehyde pre-polymerization solution;
preparing a microcapsule flame retardant: slowly adding 5g of the prepared urea formaldehyde pre-polymerization solution into 95g of the core material solution provided by each embodiment, stirring and dispersing for 30min at 2000rpm/min, adding an acid solution to adjust the pH value of the system to 4.5, heating the system to 80 ℃, continuing to keep the temperature and stirring for 1.5h, then stopping stirring, washing the filtered solid with water, and drying for 36h at 130 ℃ to obtain the microcapsule flame retardant.
The microencapsulated flame retardants obtained in examples 1 to 6 were mixed with PS and injection molded into standard EPS/XPS bars for correlation performance testing according to a process mature in the industry. Vertical burning was tested according to GB/T2408 + 1996 with sample size 125mm 12.5mm 1.6 mm; oxygen index was tested according to GB/T2408 + 1993 with sample size 85mm 10mm 1.6 mm; the combustion flame height test was carried out in accordance with the German DIN4102 standard. The detailed test data are shown in table 1.
Table 1 flame resistance test of different logistic packaging materials
Figure BDA0003450160580000091
From the above data, it can be seen that the microcapsule flame retardant prepared in examples 1-6 has good flame retardant effect and thermal stability, small addition amount, can solve the problems of uneven dispersion and high temperature stability of the composite flame retardant in the polymer matrix material, and has excellent anti-aging performance, and is particularly suitable for flame retardation of XPS and EPS materials.
The above-mentioned serial numbers of the embodiments of the present invention are merely for description and do not represent the merits of the embodiments.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The microcapsule flame retardant is characterized by comprising a shell material and a core material, wherein the weight ratio of the shell material to the core material is 5-20:80-95, and the core material comprises the following components in parts by weight: 80-95 parts of brominated SBS and/or methyl octabromoether, 1-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid-binding agent and 1-4 parts of ultraviolet agent.
2. The microencapsulated flame retardant of claim 1 wherein the shell material comprises a urea formaldehyde resin.
3. A microencapsulated flame retardant as defined by claim 1 wherein the heat stabilizer is a stearate salt, preferably at least one of calcium stearate, zinc stearate and barium stearate.
4. The microencapsulated flame retardant of claim 1, wherein the antioxidant is at least one of antioxidant 1010, antioxidant 626, antioxidant 168 and antioxidant 1076.
5. The microencapsulated flame retardant of claim 1 wherein the acid scavenger is at least one of bisphenol a glycidyl ether, tetrabromobisphenol a glycidyl ether, brominated epoxy resin, tribromophenol glycidyl ether, divinylbenzene, triallyl triazine trione.
6. The microencapsulated flame retardant of claim 1 wherein the uv agent is present in the weight ratio of (3-10): 1 with a uv stabilizer.
7. A preparation method of the microcapsule flame retardant of any one of claims 1 to 6, characterized by comprising the following steps:
according to the weight parts, 80-95 parts of brominated SBS and/or methyl octabromoether, 3-5 parts of heat stabilizer, 1-3 parts of antioxidant, 2-8 parts of acid-binding agent and 1-2 parts of ultraviolet agent are stirred and dissolved in a solvent to form a core material solution;
adding water into a three-neck flask with a stirring thermometer according to the weight ratio of (1): (2-5) adjusting the pH value of the urea and formaldehyde solution to 8.0-9.5, heating to 60-90 ℃, and carrying out heat preservation reaction for 0.5-1 hour to form a urea formaldehyde pre-polymerization solution;
slowly adding 5-20 parts of the urea formaldehyde pre-polymerization liquid prepared in the step (2) into 80-95 parts of the reaction system obtained in the step (1), uniformly stirring, adding an acid liquid to adjust the pH value of the system to 4-6, heating the system to 60-100 ℃, continuously keeping the temperature and stirring for 1-2h, stopping stirring, and washing and drying the solid obtained by filtering to obtain the microcapsule flame retardant.
8. The method for preparing a microencapsulated flame retardant as defined in claim 7, wherein the solvent in step 1) is water and/or an alcohol solvent; and/or the presence of a catalyst in the reaction mixture,
the mass concentration of formaldehyde in the formaldehyde solution in the step 2) is 37-42%.
9. The method for preparing a microencapsulated flame retardant as defined in claim 7, wherein the acid solution in step 3) is at least one of phosphoric acid, oxalic acid, formic acid, ammonium chloride, acetic acid, citric acid and hydrochloric acid; and/or the presence of a catalyst in the reaction mixture,
the drying temperature in the step 3) is 100-130 ℃, and the drying time is 24-72 h.
10. Use of a microencapsulated flame retardant as defined in any one of claims 1 to 6 in a polymeric matrix material which is any one or combination of polyethylene, polypropylene, polyvinyl chloride, poly-1-butene, polycarbonate, ethylene vinyl acetate, polyester or polystyrene.
CN202111673449.0A 2021-12-31 2021-12-31 Microcapsule flame retardant and preparation method and application thereof Pending CN114085429A (en)

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