CN115536906B - Modified hydrotalcite flame retardant and application thereof - Google Patents
Modified hydrotalcite flame retardant and application thereof Download PDFInfo
- Publication number
- CN115536906B CN115536906B CN202211121334.5A CN202211121334A CN115536906B CN 115536906 B CN115536906 B CN 115536906B CN 202211121334 A CN202211121334 A CN 202211121334A CN 115536906 B CN115536906 B CN 115536906B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- hydrotalcite
- precipitate
- modified
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
-
- 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
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/29—Protection against damage caused by extremes of temperature or by flame
- H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a modified hydrotalcite flame retardant which is prepared by intercalating phytic acid and guanidine sulfamate into magnesium aluminum hydrotalcite. The guanidine sulfamate and the phytate are introduced into the interlayer of hydrotalcite by combining a roasting restoration method and ion exchange to prepare the composite intercalation modified hydrotalcite flame retardant, and the hydrotalcite flame retardant contains a large amount of phosphorus and nitrogen atoms and has excellent flame retardant effect. Meanwhile, the chemical modification grafting hexachlorocyclotriphosphazene on the outer layer of the hydrotalcite improves the compatibility of the hydrotalcite and the organic phase, and is beneficial to improving the dispersibility of the hydrotalcite when the hydrotalcite is used as a flame retardant to be added into the organic phase. The invention also provides a smoke-suppressing flame-retardant cable material obtained by applying the modified hydrotalcite flame retardant to the cable material preparation, and the flame-retardant effect and smoke-suppressing performance of the cable material can be effectively improved by adding a proper amount of the modified hydrotalcite flame retardant, and the modified hydrotalcite flame retardant can be stably dispersed in a cable material system and has stable flame retardant performance.
Description
Technical Field
The invention relates to the technical field of hydrotalcite, in particular to a modified hydrotalcite flame retardant and application thereof.
Background
Hydrotalcite (LDH) is a novel inorganic functional material with layered double hydroxide composite metal oxide, and is widely applied to the fields of flame retardance, catalysis, adsorption and the like. Particularly, research and development and application in flame retardance are paid great attention in recent years, and the magnesium aluminum hydrotalcite flame retardant material has the function of Al (OH) 3 And Mg (OH) 2 The flame retardant has the advantages of flame retardance, avoids the defects of the flame retardant, the smoke abatement, the filling, the thermal stability and the like, and is an efficient, environment-friendly and smoke abatement type nontoxic and non-toxicHalogen flame retardants. When used as flame-retardant smoke suppressants, the alkaline nature of LDHs can adsorb acidic gases such as hydrogen sulfide, sulfur dioxide, etc. generated when thermally cracking the substrate material at the beginning of combustion. This property is one of the origins of hydrotalcite-like compounds in reducing the amount of smoke released.
With the rapid development of economy, wires and cables are widely applied in various industries and fields, and the frequent occurrence of electric fire accidents, the flame retardation problem of the wires and cables gradually attracts attention in all countries of the world. The cable releases a large amount of smoke and toxic and corrosive gas when burning, which are dangerous factors in fire, and prevent people from safely evacuating and extinguishing fire in fire, so that life and property are seriously lost, and the quality requirements on cable sheathing materials are increasingly increased along with the development of communication industry, automobile industry and computer industry. The plastic for wire and cable insulation and sheath is commonly called cable material, which comprises rubber, plastic, nylon and other varieties, and these materials are all high polymer materials, and have the defects of inflammability and great smoke generation during combustion. It is common practice in the industry to add flame retardants and magnesium/aluminum hydroxide to these binders to obtain the smokeless flame retardant properties of the cable material. However, such inorganic substances have the disadvantage of poor compatibility with organic substances of the cable material and of being prone to precipitation, which ultimately leads to a decrease in the flame retardant properties of the cable material. Hydrotalcite has a certain flame retardant effect, but LDHs also has the defects of inorganic flame retardants, the flame retardant efficiency is lower, the addition amount is larger, and the LDHs cannot be well dispersed in a polymer matrix due to the strong surface hydrophilicity. Therefore, the LDHs is organically modified, and the improvement of the dispersibility and the flame-retardant effect of the LDHs in the polymer matrix is of great significance in improving the performance of the cable material.
Disclosure of Invention
The invention aims to provide a modified hydrotalcite flame retardant and application thereof, wherein the hydrotalcite is used as one of the additive raw materials of flame-retardant cable materials and has an outstanding effect on smoke suppression and flame retardance of cables. The hydrotalcite is subjected to different anion intercalation modification, so that the flame retardant capability of the hydrotalcite is improved, and meanwhile, the outer surface of the hydrotalcite is subjected to grafting modification, so that the compatibility of the hydrotalcite and an organic phase can be improved, the hydrotalcite is more completely dispersed, and the mechanical property of the cable material is improved.
In order to achieve the above purpose, the invention provides a modified hydrotalcite flame retardant which is prepared by intercalating phytic acid and guanidine sulfamate into magnesium aluminum hydrotalcite. The preparation method comprises the following steps:
s1, preparing CO by adopting urea method 3 2- Magnesium-aluminum hydrotalcite which is interlayer anion, wherein the Mg/Al molar ratio of the magnesium-aluminum hydrotalcite is 1.5-2.5; the preferred molar ratio is 2.
S2, taking a proper amount of magnesium aluminum hydrotalcite in a muffle furnace, and calcining for 4-4.5 hours to obtain a double metal composite oxide LDO;
s3, respectively dissolving sodium phytate and guanidine sulfamate in the solution for removing CO 2 Stirring for 5min to obtain sodium phytate solution and guanidine sulfamate solution;
s4, fully dispersing the LDO (double metal composite oxide) in a nitrogen environment to remove CO 2 Adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding a sodium phytate solution, and continuously reacting for 3 hours to obtain a precipitate 1;
s5: filtering the precipitate 1 to remove CO 2 Repeatedly washing the precipitate 1 to neutrality, and carrying out surface grafting modification on the precipitate to obtain a precipitate 2;
s6, removing CO by centrifuging the precipitate 2 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant.
Preferably, in the step S5, the precipitate 1 is surface-modified with a silane coupling agent and hexachlorocyclotriphosphazene, wherein the mass ratio of the silane coupling agent to the precipitate 1 is 2:1, wherein the mass ratio of the hexachlorocyclotriphosphazene to the precipitate 1 is 5-8: 1.
preferably, the specific steps of surface modification of the precipitate 1 are: s501: the silane coupling agent was dissolved in 10: ethanol and water of the precipitate 1 are obtained into a mixed solution, and the precipitate 1 is added into the mixed solution after washing and continuously stirred until the precipitate 1 is completely dispersed; s502: adding acetic acid to regulate the pH value of the mixed solution to 3-4; s503: heating the mixed solution to 85-90 ℃ in a nitrogen atmosphere, continuously stirring and reacting for 24 hours, and drying to obtain a solid 1; s504: dissolving the solid 1 in tetrahydrofuran to obtain suspension, and uniformly dispersing hexachlorocyclotriphosphazene and ethylenediamine tetraacetic acid in the tetrahydrofuran solution to obtain a combined acid reagent, wherein the mass ratio of hexachlorocyclotriphosphazene to ethylenediamine tetraacetic acid is 1:1, adding an acid-binding reagent into the suspension in a nitrogen environment, heating to 65 ℃, and stirring for reaction for 6 hours to obtain a precipitate 2.
Preferably, in the step S2, the muffle furnace is heated up stepwise at 10 ℃/min, and the calcination temperature is kept at 500-550 ℃.
Preferably, the mass ratio of the sodium phytate to the guanidine sulfamate is 3:1, the feeding mass ratio of the magnesium aluminum hydrotalcite to the sum of the sodium phytate and the guanidine sulfamate is 1:1 to 3.
The invention also provides application of the modified hydrotalcite flame retardant, and the modified hydrotalcite flame retardant is used for preparing a smoke-suppressing flame-retardant cable material.
Preferably, the smoke suppression flame retardant cable material comprises the following raw materials in parts by weight: 50-65 parts of modified ethylene-vinyl acetate copolymer, 15-20 parts of low-density polyethylene resin, 5-10 parts of ethylene-octene copolymer, 3-10 parts of modified hydrotalcite flame retardant, 1-2 parts of antioxidant, 2-4 parts of dispersing agent, 1-2 parts of anti-aging agent, 2-5 parts of zinc oxide and 1-3 parts of lubricant.
Preferably, the modified ethylene-vinyl acetate copolymer is prepared by grafting maleic anhydride with an ethylene-vinyl acetate copolymer, and the grafting ratio of the ethylene-vinyl acetate copolymer and the maleic anhydride is 100:5 to 7.
Preferably, the preparation method of the ethylene-vinyl acetate copolymer grafted maleic anhydride comprises the following steps: dissolving maleic anhydride, dicumyl peroxide and styrene in an acetone solution, adding an ethylene-vinyl acetate copolymer while stirring until the mixture is fully mixed, and placing the solution in a baking oven with the constant temperature of 60 ℃ for 12 hours to completely volatilize the acetone to obtain a solid; and adding the solid into a single screw extruder for granulating to obtain the modified ethylene-vinyl acetate copolymer, wherein the temperature of a feeding section of the single screw extruder is 60-70 ℃, the temperature of a melting section is 140-160 ℃, and the temperature of a homogenizing section is 150 ℃.
Preferably, the preparation method of the smoke suppression flame retardant cable material comprises the following steps: mixing the modified ethylene-vinyl acetate copolymer, the low-density polyethylene resin and the ethylene-octene copolymer in proportion for 20min at 120-130 ℃, adding the modified hydrotalcite flame retardant, the antioxidant, the dispersing agent, the anti-aging agent, the zinc oxide and the lubricant, and mixing for 40min at the constant temperature of 120 ℃ to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the smoke suppression flame retardant cable material.
The invention has the beneficial effects that: the invention provides a modified hydrotalcite flame retardant, which is prepared by introducing guanidine sulfamate and phytate into hydrotalcite interlayers through a roasting recovery method and ion exchange, wherein the hydrotalcite flame retardant contains a large amount of phosphorus and nitrogen atoms and has an excellent flame retardant effect. Meanwhile, the chemical modification grafting hexachlorocyclotriphosphazene on the outer layer of the hydrotalcite greatly improves the compatibility of the hydrotalcite and the organic phase, and is beneficial to improving the dispersibility of the hydrotalcite when the hydrotalcite is used as a flame retardant to be added into the organic phase. The invention also provides a smoke-suppressing flame-retardant cable material obtained by applying the modified hydrotalcite flame retardant to the preparation of the cable material, the flame-retardant effect and smoke-suppressing performance of the cable material can be effectively improved by adding a proper amount of the modified hydrotalcite flame retardant, the modified hydrotalcite flame retardant can be stably dispersed in a cable material system, and the flame-retardant performance of the cable material is stable.
Detailed Description
The embodiments described below are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a modified hydrotalcite flame retardant which is prepared by intercalating phytic acid and guanidine sulfamate into magnesium aluminum hydrotalcite. The preparation method comprises the following steps:
s1, urine is adoptedPreparation of CO by plain method 3 2- Magnesium aluminum hydrotalcite which is interlayer anion, wherein the Mg/Al molar ratio of the magnesium aluminum hydrotalcite is 2;
s2, taking a proper amount of magnesium aluminum hydrotalcite in a muffle furnace, and calcining for 4-4.5 hours to obtain a bimetal composite oxide LDO, wherein the muffle furnace is heated at a stage of 10 ℃/min, and the calcining temperature is kept at 500-550 ℃;
s3, respectively dissolving sodium phytate and guanidine sulfamate in the solution for removing CO 2 Stirring for 5min to obtain a sodium phytate solution and a guanidine sulfamate solution, wherein the mass ratio of the sodium phytate to the guanidine sulfamate is 3:1, a step of;
s4, fully dispersing the LDO (double metal composite oxide) in a nitrogen environment to remove CO 2 And heating to 80 ℃, wherein the feeding mass ratio of the magnesium aluminum hydrotalcite to the sum of the sodium phytate and the guanidine sulfamate is 1: 1-3, adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding a sodium phytate solution, and continuously reacting for 3 hours to obtain a precipitate 1;
s5: filtering the precipitate 1 to remove CO 2 Repeatedly washing the precipitate 1 to neutrality, and carrying out surface grafting modification on the precipitate to obtain a precipitate 2;
s6, removing CO by centrifuging the precipitate 2 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant.
The sulfamic acid compound contains N and S in the molecule, has the characteristics of low smoke, low toxicity and high efficiency, and has certain flame retardant property. The oxide obtained by calcining hydrotalcite has a structural memory effect and can be reconstructed. When the heat treated product is contacted with an aqueous solution containing various anions, it has an original hydrotalcite structure under mild conditions. According to the invention, a certain amount of dilute nitric acid is added before guanidine sulfamate is intercalated into hydrotalcite, so that part of nitrate also enters into hydrotalcite interlayers, and then nitrate among hydrotalcite interlayers is replaced by adding sodium phytate, so that phytate is also successfully intercalated into hydrotalcite interlayers to obtain the modified hydrotalcite flame retardant intercalated with the composite flame retardant.
Preferably, in the above step S5, the precipitate 1 is surface-modified with a silane coupling agent and hexachlorocyclotriphosphazene. The mass ratio of the silane coupling agent to the precipitate 1 is 2:1, wherein the mass ratio of the hexachlorocyclotriphosphazene to the precipitate 1 is 5-8: 1. the specific steps of carrying out surface modification on the precipitate 1 are as follows: s501: the silane coupling agent was dissolved in 10: ethanol and water of the precipitate 1 are obtained into a mixed solution, and the precipitate 1 is added into the mixed solution after washing and continuously stirred until the precipitate 1 is completely dispersed; s502: adding acetic acid to regulate the pH value of the mixed solution to 3-4; s503: heating the mixed solution to 85-90 ℃ in a nitrogen atmosphere, continuously stirring and reacting for 24 hours, and drying to obtain a solid 1; s504: dissolving the solid 1 in tetrahydrofuran to obtain suspension, and uniformly dispersing hexachlorocyclotriphosphazene and ethylenediamine tetraacetic acid in the tetrahydrofuran solution to obtain a combined acid reagent, wherein the mass ratio of hexachlorocyclotriphosphazene to ethylenediamine tetraacetic acid is 1:1, adding an acid-binding reagent into the suspension in a nitrogen environment, heating to 65 ℃, and stirring for reaction for 6 hours to obtain a precipitate 2.
The magnesium aluminum hydrotalcite has large specific surface area and high surface activity, and is easy to aggregate under the action of intermolecular van der Waals force when being added into a polymer matrix, so that stress points are caused in a continuous resin matrix, and the physical properties of the composite material are reduced. Hydrotalcite surface modification is of great importance for enhancing its dispersibility and compatibility in polymers. Hexachlorocyclotriphosphazene has the characteristics of organic matters and inorganic matters, meanwhile, nitrogen and phosphorus atoms in the hexachlorocyclotriphosphazene are alternately linked into a six-membered ring main chain through single double bonds, and the synergistic effect of phosphorus and nitrogen also enables the hexachlorocyclotriphosphazene to have flame retardance and self-extinguishing property. The P-N bond energy in the phosphazene molecular structure is higher, the stability is higher, the P-Cl bond energy is lower, and Cl atoms with higher reactivity are easy to replace. The invention utilizes the condensation reaction of the silane coupling agent containing the amino group and the hydroxyl on the surface of hydrotalcite, introduces the amino group on the surface of hydrotalcite, then reacts with hexachlorocyclotriphosphazene, grafts hexachlorocyclotriphosphazene on the surface of hydrotalcite through chemical bonds, and achieves the aim of modifying LDH.
The invention also provides application of the modified hydrotalcite flame retardant, and the modified hydrotalcite flame retardant is used for preparing a smoke-suppressing flame-retardant cable material.
Preferably, the smoke suppression flame retardant cable material comprises the following raw materials in parts by weight: 50-65 parts of modified ethylene-vinyl acetate copolymer, 15-20 parts of low-density polyethylene resin, 5-10 parts of ethylene-octene copolymer, 3-10 parts of modified hydrotalcite flame retardant, 1-2 parts of antioxidant, 2-4 parts of dispersing agent, 1-2 parts of anti-aging agent, 2-5 parts of zinc oxide and 1-3 parts of lubricant. According to the cable material, a proper amount of modified hydrotalcite flame retardant is added into a resin matrix, N-free radicals generated by the heated decomposition of guanidine sulfamate among hydrotalcite layers can be combined with O-free radicals in air to play a role of gas-phase flame retardance, meanwhile, the composite material can be promoted to form compact carbon, and in the combustion process, the effective carbon is a barrier of heat, oxygen and other volatile gases, so that the composite material plays a role of condensed phase flame retardance. The phytate in the hydrotalcite contains six phosphate groups, has carbide which promotes the formation of carbon in the combustion process to form a compact structure, and can form a layer of stable compound which is not easy to burn when the cable material is combusted to cover the surface of a combustible material by being matched with guanidine sulfamate to form a physical isolation layer, so that the amount of released smoke is reduced.
Preferably, the modified ethylene-vinyl acetate copolymer is prepared by grafting maleic anhydride with an ethylene-vinyl acetate copolymer, and the grafting ratio of the ethylene-vinyl acetate copolymer and the maleic anhydride is 100:5 to 7. The preparation method of the ethylene-vinyl acetate copolymer grafted maleic anhydride comprises the following steps: dissolving maleic anhydride, dicumyl peroxide and styrene in an acetone solution, adding an ethylene-vinyl acetate copolymer while stirring until the mixture is fully mixed, and placing the solution in a baking oven with the constant temperature of 60 ℃ for 12 hours to completely volatilize the acetone to obtain a solid; and adding the solid into a single screw extruder for granulating to obtain the modified ethylene-vinyl acetate copolymer, wherein the temperature of a feeding section of the single screw extruder is 60-70 ℃, the temperature of a melting section is 140-160 ℃, and the temperature of a homogenizing section is 150 ℃. The melt grafting method is adopted to graft maleic anhydride on the ethylene-vinyl acetate copolymer, so that the compatibility of a resin matrix and a flame retardant can be improved, the interface energy of the resin matrix and the flame retardant is reduced, the dispersion of a disperse phase and the interface cohesiveness are improved, the materials can be mixed more fully, and the comprehensive mechanical property of the cable material is improved. Meanwhile, the modified ethylene-vinyl acetate copolymer can also improve the polarity of the modified ethylene-vinyl acetate copolymer after grafting, and the polarity difference between the modified ethylene-vinyl acetate copolymer and fuel oil is enlarged, so that the oil resistance of the flame-retardant cable material is improved. The modified ethylene-vinyl acetate copolymer has polar group introduced to raise the dispersivity of inorganic stuffing in the resin matrix, reduce the probability of bubble, crack and other defects, and raise the breakdown strength of cable material.
Preferably, the preparation method of the smoke suppression flame retardant cable material comprises the following steps: mixing the modified ethylene-vinyl acetate copolymer, the low-density polyethylene resin and the ethylene-octene copolymer in proportion for 20min at 120-130 ℃, adding the modified hydrotalcite flame retardant, the antioxidant, the dispersing agent, the anti-aging agent, the zinc oxide and the lubricant, and mixing for 40min at the constant temperature of 120 ℃ to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the smoke suppression flame retardant cable material.
Example 1
Preparation of CO by urea method 3 2- The magnesium-aluminum hydrotalcite is interlayer anion, wherein the Mg/Al molar ratio of the magnesium-aluminum hydrotalcite is 2, 1g of the magnesium-aluminum hydrotalcite is weighed and calcined in a muffle furnace at 500 ℃ for 4 hours to obtain 1g of the bimetal composite oxide LDO. Weighing 0.75g of sodium phytate and 0.25g of guanidine sulfamate, respectively, and dissolving in 50ml of CO-eliminating solution 2 Stirring for 5min in deionized water to obtain sodium phytate solution and guanidine sulfamate solution. Under the nitrogen environment, the 1g of the double metal composite oxide LDO is fully dispersed to 100ml for CO removal 2 And (3) heating to 80 ℃, adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding the sodium phytate solution, and continuously reacting for 3 hours to obtain 1g of precipitate 1. Performing surface grafting modification on the precipitate 1 to obtain a precipitate 2, and centrifugally separating the precipitate 2 to remove CO 2 Repeatedly washing with deionized water until pH value of supernatant is 6.8-7, and drying at low temperature to obtain modified waterTalc flame retardant.
Example 2
Preparation of CO by urea method 3 2- The magnesium-aluminum hydrotalcite is interlayer anion, wherein the Mg/Al molar ratio of the magnesium-aluminum hydrotalcite is 2, 1g of the magnesium-aluminum hydrotalcite is weighed and calcined in a muffle furnace at 500 ℃ for 4 hours to obtain 1g of the bimetal composite oxide LDO. Weighing 2.25g of sodium phytate and 0.75g of guanidine sulfamate, respectively, and dissolving in 80ml of the solution for CO removal 2 Stirring for 5min in deionized water to obtain sodium phytate solution and guanidine sulfamate solution. Under the nitrogen environment, the 1g of the double metal composite oxide LDO is fully dispersed to 100ml for CO removal 2 And (3) heating to 80 ℃, adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding the sodium phytate solution, and continuously reacting for 3 hours to obtain 1g of precipitate 1. Performing surface grafting modification on the precipitate 1 to obtain a precipitate 2, and centrifugally separating the precipitate 2 to remove CO 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant.
The specific steps of the above examples 1 and 2 for carrying out surface grafting modification on the precipitate 1 to obtain the precipitate 2 are as follows: 2g of silane coupling agent was dissolved in 10: ethanol and water of the precipitate 1 are obtained into a mixed solution, and the precipitate 1 is added into the mixed solution after washing and continuously stirred until the precipitate 1 is completely dispersed; adding acetic acid to adjust the pH of the mixed solution to 3-4, heating the mixed solution to 85-90 ℃ under the nitrogen atmosphere, continuously stirring and reacting for 24 hours, and drying to obtain a solid 1; dissolving the solid 1 in 20ml of tetrahydrofuran to obtain a suspension, uniformly dispersing 6g of hexachlorocyclotriphosphazene and 6g of ethylenediamine tetraacetic acid in 30ml of tetrahydrofuran to obtain a combined acid reagent, adding the combined acid reagent into the suspension in a nitrogen environment, heating to 65 ℃, and stirring for reaction for 6 hours to obtain a precipitate 2.
Comparative example 1
Preparation of CO by urea method 3 2- The magnesium-aluminum hydrotalcite is interlayer anion, wherein the Mg/Al molar ratio of the magnesium-aluminum hydrotalcite is 2, 1g of the magnesium-aluminum hydrotalcite is weighed and calcined in a muffle furnace at 500 ℃ for 4 hours to obtain 1g of the bimetal composite oxide LDO. Weighing 0.75g of sodium phytate and 0.25g of sulfamic acidGuanidine is dissolved in 50ml of the solution for CO removal 2 Stirring for 5min in deionized water to obtain sodium phytate solution and guanidine sulfamate solution. Under the nitrogen environment, the 1g of the double metal composite oxide LDO is fully dispersed to 100ml for CO removal 2 And (3) heating to 80 ℃, adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding the sodium phytate solution, and continuously reacting for 3 hours to obtain 1g of precipitate 1. CO removal for centrifugation of precipitate 1 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant.
Comparative example 2
Preparation of CO by urea method 3 2- The magnesium-aluminum hydrotalcite is interlayer anion, wherein the Mg/Al molar ratio of the magnesium-aluminum hydrotalcite is 2, 1g of the magnesium-aluminum hydrotalcite is weighed and calcined in a muffle furnace at 500 ℃ for 4 hours to obtain 1g of the bimetal composite oxide LDO. 1g guanidine sulfamate was weighed out and dissolved in 100ml to remove CO 2 Stirring for 5min in deionized water to obtain sodium phytate solution and guanidine sulfamate solution. Under the nitrogen environment, the 1g of the double metal composite oxide LDO is fully dispersed to 100ml for CO removal 2 And heating to 80 ℃, adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, and continuously stirring to react for 8 hours to obtain 1g of precipitate 1. Performing surface grafting modification on the precipitate 1 to obtain a precipitate 2, and centrifugally separating the precipitate 2 to remove CO 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant. Among them, the procedure of comparative example 2 in which the surface graft modification of precipitate 1 was carried out to obtain precipitate 2 was identical to that of example.
The modified hydrotalcite flame retardants prepared in examples 1 and 2 and comparative examples 1 and 2 were added to acrylonitrile-butadiene-styrene copolymer (ABS resin) to prepare composite materials, and performance test was performed thereon.
The preparation method of the composite material comprises the following steps: taking 5g of modified hydrotalcite flame retardant, 1g of stearic acid, 1g of dispersing agent and 93g of ABS resin, putting into a high-speed dispersing machine for stirring
And (3) carrying out melt blending granulation by a double-screw extruder for 30min, drying the obtained granules by blowing at 100 ℃ for 10h, and then injecting the dried granules into a standard cone sample to obtain the ABS/modified hydrotalcite flame retardant composite material, and carrying out performance test on the composite material, wherein the test result is shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, compared with the pure ABS resin, the composite material added with the modified hydrotalcite flame retardant has certain enhancement in tensile strength and impact strength, which proves that the loading of the modified hydrotalcite flame retardant is beneficial to improving the mechanical property of the resin. Meanwhile, the elongation at break of the resin matrix loaded with the modified hydrotalcite flame retardant is slightly reduced, but the influence is small, which indicates that hydrotalcite intercalation with guanidine sulfamate and phytate plays a certain role in the dispersion of hydrotalcite, and the grafting of hexachlorocyclotriphosphazene on the surface of hydrotalcite is more beneficial to improving the compatibility of hydrotalcite and the resin matrix. In the aspect of flame retardance, the composite modified hydrotalcite flame retardant is beneficial to improving the UL-94 flame retardant grade, and the limiting oxygen index LOI value of the flame retardant is also greatly improved, so that the modified hydrotalcite flame retardant has obvious flame retardant effect on the ABS resin. From the data in ABS/LDHs (example 1) and ABS/LDHs (comparative example 1), it can be seen that hexachlorocyclotriphosphazene has dual identities of "surface modifier" and "synergistic flame retardant", which improves both the compatibility between hydrotalcite and polymer and can further enhance the flame retardant properties of hydrotalcite. From the data in ABS/LDHs (example 1) and ABS/LDHs (comparative example 2), it can be seen that the mechanical properties and flame retardant effects of the composite intercalation of guanidine sulfamate and phytate into hydrotalcite interlayers are better than those obtained by intercalation of a single substance.
The following tests were conducted on the application of the modified hydrotalcite flame retardant and the preparation of smoke suppression flame retardant cable materials.
Example 3
The embodiment provides a smoke-suppressing flame-retardant cable material, which comprises the following raw materials in parts by weight: 60 parts of modified ethylene-vinyl acetate copolymer, 20 parts of low-density polyethylene resin, 10 parts of ethylene-octene copolymer, 3 parts of modified hydrotalcite flame retardant, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
Example 4
The embodiment provides a smoke-suppressing flame-retardant cable material, which comprises the following raw materials in parts by weight: 60 parts of modified ethylene-vinyl acetate copolymer, 20 parts of low-density polyethylene resin, 8 parts of ethylene-octene copolymer, 5 parts of modified hydrotalcite flame retardant, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
Example 5
The embodiment provides a smoke-suppressing flame-retardant cable material, which comprises the following raw materials in parts by weight: 60 parts of modified ethylene-vinyl acetate copolymer, 17 parts of low-density polyethylene resin, 8 parts of ethylene-octene copolymer, 8 parts of modified hydrotalcite flame retardant, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
Example 6
The embodiment provides a smoke-suppressing flame-retardant cable material, which comprises the following raw materials in parts by weight: 60 parts of modified ethylene-vinyl acetate copolymer, 16 parts of low-density polyethylene resin, 7 parts of ethylene-octene copolymer, 10 parts of modified hydrotalcite flame retardant, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
The preparation steps of the smoke-suppressing flame-retardant cable material described in the above examples 3 to 6 are as follows: mixing the modified ethylene-vinyl acetate copolymer, the low-density polyethylene resin and the ethylene-octene copolymer in proportion for 20min at 125 ℃, adding the modified hydrotalcite flame retardant, the antioxidant, the dispersing agent, the anti-aging agent, the zinc oxide and the lubricant, and mixing for 40min at the constant temperature of 120 ℃ to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the smoke suppression flame retardant cable material.
Comparative example 3
The embodiment provides a smoke-suppressing flame-retardant cable material, which comprises the following raw materials in parts by weight: 60 parts of ethylene-vinyl acetate copolymer, 20 parts of low-density polyethylene resin, 10 parts of ethylene-octene copolymer, 3 parts of modified hydrotalcite flame retardant, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
The preparation method comprises the following steps: mixing ethylene-vinyl acetate copolymer, low-density polyethylene resin and ethylene-octene copolymer at 125 ℃ for 20min, adding modified hydrotalcite flame retardant, antioxidant, dispersant, anti-aging agent, zinc oxide and lubricant, and mixing at 120 ℃ for 40min to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the smoke suppression flame retardant cable material.
Comparative example 4
The embodiment provides a cable material, which comprises the following raw materials in parts by weight: 63 parts of modified ethylene-vinyl acetate copolymer, 20 parts of low-density polyethylene resin, 10 parts of ethylene-octene copolymer, 1 part of antioxidant, 2 parts of dispersing agent, 1 part of anti-aging agent, 2 parts of zinc oxide and 1 part of lubricant.
The preparation method comprises the following steps: mixing the modified ethylene-vinyl acetate copolymer, the low-density polyethylene resin and the ethylene-octene copolymer in proportion for 20min at 125 ℃, adding an antioxidant, a dispersing agent, an anti-aging agent, zinc oxide and a lubricant, and mixing for 40min at the constant temperature of 120 ℃ to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the cable material.
The cable materials prepared in examples 3-6 and comparative examples 3, 4 above were subjected to the following performance tests:
tensile strength: according to GB/T1040.3-2006 test;
vertical combustion grade: tested according to GB/T2408-2008;
LOI: according to GB/T2406.1-2008 test;
smoke density: according to GB/T8323.2-2008 test, a flameless combustion mode is adopted, the test radiation intensity is 25KW/m, and the test time is 20min;
the results of the above test are shown in Table 2.
TABLE 2
| Tensile Strength/MPa | Vertical combustion rating | LOI％ | Smoke density/Dm | |
| Example 3 | 14.5 | V-0 | 27.3 | 17.2 |
| Example 4 | 16.9 | V-0 | 28.9 | 16.7 |
| Example 5 | 15.8 | V-0 | 30.2 | 16.4 |
| Example 6 | 14.6 | V-0 | 31.6 | 15.3 |
| Comparative example 3 | 11.3 | V-0 | 27.4 | 17.1 |
| Comparative example 4 | 13.1 | Failed to pass | 15.4 | 43.5 |
According to the detection data of examples 3-6 and comparative examples 3 and 4, the smoke suppression flame retardant cable material provided by the invention can achieve good flame retardant effect by adding the modified hydrotalcite flame retardant, the vertical burning grade reaches V-0, and the limiting oxygen index is more than 27%. From the data of comparative example 3, it is known that the mechanical properties of the material can be enhanced by graft modification of the ethylene-vinyl acetate copolymer, and from the data of comparative example 4, the main flame retarding effect of the modified hydrotalcite flame retardant in the cable material is known.
The present invention has been described in detail with reference to the embodiments, and it should be noted that the specific features described in the above embodiments may be modified in combination by any suitable means without contradiction, and the present invention will not be described in any way. Further, other modifications and combinations of the features of the invention, as well as other variations and combinations of the features of the invention, are also contemplated as being within the scope of the invention.
Claims (8)
1. The modified hydrotalcite flame retardant is characterized by being prepared by intercalating phytic acid and guanidine sulfamate into magnesium aluminum hydrotalcite, and the preparation method comprises the following steps:
s1, preparing CO by adopting urea method 3 2- Magnesium aluminum hydrotalcite which is interlayer anions, wherein the Mg/Al molar ratio of the magnesium aluminum hydrotalcite is 1.5-2.5;
s2, taking a proper amount of magnesium aluminum hydrotalcite in a muffle furnace, and calcining for 4-4.5 hours to obtain a double metal composite oxide LDO;
s3, respectively dissolving sodium phytate and guanidine sulfamate in the solution for removing CO 2 Stirring for 5min to obtain sodium phytate solution and guanidine sulfamate solution;
s4, fully dispersing the LDO (double metal composite oxide) in a nitrogen environment to remove CO 2 Adding dilute nitric acid to adjust the pH value of the solution to 6, adding the guanidine sulfamate solution while stirring, continuously stirring to react for 6 hours, adding a sodium phytate solution, and continuously reacting for 3 hours to obtain a precipitate 1;
s5: filtering the precipitate 1 to remove CO 2 Repeatedly washing the deionized water until the deionized water is neutral, and carrying out surface grafting modification on the precipitate 1 to obtain a precipitate 2, wherein a silane coupling agent and hexachlorocyclotriphosphazene are adopted for carrying out surface modification on the precipitate 1, and the mass ratio of the silane coupling agent to the precipitate 1 is 2:1, the mass ratio of the hexachlorocyclotriphosphazene to the precipitate 1 is 5-8: 1, a step of;
s6, removing CO by centrifuging the precipitate 2 2 Repeatedly washing the solution until the pH value of the supernatant is 6.8-7, and drying at low temperature to obtain the modified hydrotalcite flame retardant.
2. The modified hydrotalcite flame retardant according to claim 1, wherein: the specific steps of carrying out surface modification on the precipitate 1 are as follows:
s501: the silane coupling agent was dissolved in 10: ethanol and water of the precipitate 1 are obtained into a mixed solution, and the precipitate 1 is added into the mixed solution after washing and continuously stirred until the precipitate 1 is completely dispersed;
s502: adding acetic acid to adjust the pH of the mixed solution to 3-4;
s503: heating the mixed solution to 85-90 ℃ in a nitrogen atmosphere, continuously stirring and reacting for 24 hours, and drying to obtain a solid 1;
s504: dissolving the solid 1 in tetrahydrofuran to obtain suspension, and uniformly dispersing hexachlorocyclotriphosphazene and ethylenediamine tetraacetic acid in the tetrahydrofuran solution to obtain a combined acid reagent, wherein the mass ratio of hexachlorocyclotriphosphazene to ethylenediamine tetraacetic acid is 1:1, adding an acid-binding reagent into the suspension in a nitrogen environment, heating to 65 ℃, and stirring for reaction for 6 hours to obtain a precipitate 2.
3. The modified hydrotalcite flame retardant according to claim 1, wherein: in the step S2, the muffle furnace is heated up at a stage of 10 ℃/min, and the calcination temperature is kept at 500-550 ℃.
4. The modified hydrotalcite flame retardant according to claim 1, wherein: the mass ratio of the sodium phytate to the guanidine sulfamate is 3:1, the feeding mass ratio of the magnesium aluminum hydrotalcite to the sum of the sodium phytate and the guanidine sulfamate is 1: 1-3.
5. The application of the modified hydrotalcite flame retardant is characterized in that: the modified hydrotalcite flame retardant according to any one of claims 1 to 4 for preparing a smoke-suppressing flame-retardant cable material.
6. The use of the modified hydrotalcite flame retardant according to claim 5, wherein: the smoke suppression flame retardant cable material comprises the following raw materials in parts by weight: 50-65 parts of modified ethylene-vinyl acetate copolymer, 15-20 parts of low-density polyethylene resin, 5-10 parts of ethylene-octene copolymer, 3-10 parts of modified hydrotalcite flame retardant, 1-2 parts of antioxidant, 2-4 parts of dispersing agent, 1-2 parts of anti-aging agent, 2-5 parts of zinc oxide and 1-3 parts of lubricant, wherein the modified ethylene-vinyl acetate copolymer is prepared by grafting maleic anhydride with ethylene-vinyl acetate copolymer, and the grafting ratio of the ethylene-vinyl acetate copolymer to the maleic anhydride is 100: 5-7.
7. The use of the modified hydrotalcite flame retardant according to claim 6, wherein: the preparation method of the ethylene-vinyl acetate copolymer grafted maleic anhydride comprises the following steps: dissolving maleic anhydride, dicumyl peroxide and styrene in an acetone solution, adding an ethylene-vinyl acetate copolymer while stirring until the mixture is fully mixed, and placing the solution in a baking oven with the constant temperature of 60 ℃ for 12 hours to completely volatilize the acetone to obtain a solid; and adding the solid into a single-screw extruder for granulating to obtain the modified ethylene-vinyl acetate copolymer, wherein the temperature of a feeding section of the single-screw extruder is 60-70 ℃, the temperature of a melting section is 140-160 ℃, and the temperature of a homogenizing section is 150 ℃.
8. The use of the modified hydrotalcite flame retardant according to claim 6, wherein: the preparation method of the smoke suppression flame retardant cable material comprises the following steps: mixing the modified ethylene-vinyl acetate copolymer, the low-density polyethylene resin and the ethylene-octene copolymer in proportion for 20min at 120-130 ℃, adding the modified hydrotalcite flame retardant, the antioxidant, the dispersing agent, the anti-aging agent, the zinc oxide and the lubricant, and mixing for 40min at the constant temperature of 120 ℃ to obtain a mixture; and (3) placing the mixture into a double-screw extruder for extrusion granulation to obtain the smoke suppression flame retardant cable material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211121334.5A CN115536906B (en) | 2022-09-15 | 2022-09-15 | Modified hydrotalcite flame retardant and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211121334.5A CN115536906B (en) | 2022-09-15 | 2022-09-15 | Modified hydrotalcite flame retardant and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115536906A CN115536906A (en) | 2022-12-30 |
| CN115536906B true CN115536906B (en) | 2023-09-19 |
Family
ID=84727960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211121334.5A Active CN115536906B (en) | 2022-09-15 | 2022-09-15 | Modified hydrotalcite flame retardant and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115536906B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082822B (en) * | 2023-01-17 | 2023-11-21 | 盛鼎高新材料有限公司 | Preparation method of high-temperature-resistant halogen-free flame-retardant polyurethane elastomer |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103865296A (en) * | 2014-02-26 | 2014-06-18 | 北京化工大学 | Sulfamic acid group intercalation modified hydrotalcite and preparation method thereof |
| WO2015028047A1 (en) * | 2013-08-27 | 2015-03-05 | Fundacion Imdea Materiales | A halogen free flame retardant polymeric composition comprising a modified layered double hydroxide nanofiller |
| JP2017078014A (en) * | 2015-10-20 | 2017-04-27 | テイカ株式会社 | Layered double hydroxide in which hydrogen phosphate ion is intercalated, flame retardant containing layered double hydroxide, flame-retardant synthetic resin composition, and method for producing layered double hydroxide |
| CN110105298A (en) * | 2019-04-29 | 2019-08-09 | 湘潭大学 | A kind of synthesis of nitrogenous sulphur synergistic flame-retardant compound and its preparation method of intercalation modifying hydrotalcite |
| CN110305370A (en) * | 2019-06-13 | 2019-10-08 | 湘潭大学 | A kind of phosphonitrile graft modification houghite fire retardant and preparation method thereof |
| CN112812371A (en) * | 2021-01-05 | 2021-05-18 | 湘潭大学 | Nitrogen-phosphorus-containing hydrotalcite-based flame retardant and preparation method thereof |
| CN113896988A (en) * | 2021-11-29 | 2022-01-07 | 安徽中通电缆科技有限公司 | Smokeless flame-retardant waterproof cable material |
| CN114621771A (en) * | 2022-04-02 | 2022-06-14 | 陕西科技大学 | Preparation method of phytic acid modified magnalium hydrotalcite/montmorillonite nano material |
-
2022
- 2022-09-15 CN CN202211121334.5A patent/CN115536906B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015028047A1 (en) * | 2013-08-27 | 2015-03-05 | Fundacion Imdea Materiales | A halogen free flame retardant polymeric composition comprising a modified layered double hydroxide nanofiller |
| CN103865296A (en) * | 2014-02-26 | 2014-06-18 | 北京化工大学 | Sulfamic acid group intercalation modified hydrotalcite and preparation method thereof |
| JP2017078014A (en) * | 2015-10-20 | 2017-04-27 | テイカ株式会社 | Layered double hydroxide in which hydrogen phosphate ion is intercalated, flame retardant containing layered double hydroxide, flame-retardant synthetic resin composition, and method for producing layered double hydroxide |
| CN110105298A (en) * | 2019-04-29 | 2019-08-09 | 湘潭大学 | A kind of synthesis of nitrogenous sulphur synergistic flame-retardant compound and its preparation method of intercalation modifying hydrotalcite |
| CN110305370A (en) * | 2019-06-13 | 2019-10-08 | 湘潭大学 | A kind of phosphonitrile graft modification houghite fire retardant and preparation method thereof |
| CN112812371A (en) * | 2021-01-05 | 2021-05-18 | 湘潭大学 | Nitrogen-phosphorus-containing hydrotalcite-based flame retardant and preparation method thereof |
| CN113896988A (en) * | 2021-11-29 | 2022-01-07 | 安徽中通电缆科技有限公司 | Smokeless flame-retardant waterproof cable material |
| CN114621771A (en) * | 2022-04-02 | 2022-06-14 | 陕西科技大学 | Preparation method of phytic acid modified magnalium hydrotalcite/montmorillonite nano material |
Non-Patent Citations (1)
| Title |
|---|
| 氮硫磷有机改性镁铝水滑石及其阻燃聚丙烯性能研究;张敏;《中国优秀硕士学位论文全文数据库 工程科技I辑》(第2期);B016-1225 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115536906A (en) | 2022-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110041612B (en) | Halogen-free flame-retardant polypropylene composite material compatibilized by oligomeric silsesquioxane and synergistic effect and preparation method thereof | |
| CN110746706B (en) | Low-smoke halogen-free ethylene propylene diene monomer composition and preparation method thereof | |
| CN109897273B (en) | Composite flame retardant graft-modified EVA (ethylene-vinyl acetate) foam material and preparation method thereof | |
| CN112876740B (en) | Phenylboronic acid grafted and modified zirconium phosphate-based flame retardant and preparation method thereof | |
| CN115536906B (en) | Modified hydrotalcite flame retardant and application thereof | |
| CN104250391A (en) | Silane crosslinking halogen-free flame retardant polyolefin composite material and preparation method thereof | |
| CN112662184B (en) | Flame-retardant silicone rubber material and preparation method thereof | |
| CN111040293B (en) | Intumescent flame-retardant polypropylene and preparation method thereof | |
| CN113621176B (en) | Single-molecule intumescent flame retardant MPPR (modified Polypropylene) and MPPR/POSS (polyhedral oligomeric silsesquioxane) composite synergistic halogen-free flame retardant polypropylene composite material | |
| CN113667277B (en) | Low-heat-release, low-smoke and high-flame-retardance epoxy resin material and preparation method thereof | |
| CN103694499A (en) | Migration resistant and high flame retardant halogen-free flame retardant system used for thermoplastic elastomers | |
| CN111647218A (en) | Ultra-soft low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof | |
| CN108503895B (en) | Preparation method of lanthanum-loaded organic phosphorus-modified nitrogen-doped graphene and flame-retardant modified ABS thereof | |
| CN108624027B (en) | High-efficiency halogen-free flame-retardant PC/ABS mixture for catalytic carbonization and preparation method thereof | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN115975370B (en) | Halogen-free flame retardant TPU and preparation method thereof | |
| CN116874878A (en) | Flame retardant for ethylene propylene diene monomer and preparation method thereof | |
| CN113583337B (en) | MPPR/POSS/GF composite synergistic halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN116376179A (en) | Flame-retardant rubber material, preparation method thereof and sealing strip | |
| CN111040249B (en) | Rubber-plastic flame-retardant additive and rubber-plastic material containing same | |
| CN113185796A (en) | 125 ℃ halogen-free flame-retardant cable material capable of self-crosslinking at room temperature and preparation method thereof | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| CN112477310A (en) | Thermoplastic resin composition and use thereof | |
| CN117229569B (en) | Efficient composite flame retardant for polypropylene and preparation method thereof | |
| CN114516989B (en) | EPDM halogen-free flame retardant rubber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |