WO2025001200A1 - 改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法 - Google Patents

改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法 Download PDF

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WO2025001200A1
WO2025001200A1 PCT/CN2024/078094 CN2024078094W WO2025001200A1 WO 2025001200 A1 WO2025001200 A1 WO 2025001200A1 CN 2024078094 W CN2024078094 W CN 2024078094W WO 2025001200 A1 WO2025001200 A1 WO 2025001200A1
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flame retardant
flame
formula
modified
retardant
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French (fr)
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汪志勇
孙翔
李通
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
    • D06M13/447—Phosphonates or phosphinates containing nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M17/00—Producing multi-layer textile fabrics
    • D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
    • D06M17/10—Polyurethanes polyurea
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the present invention belongs to the technical field of flame retardants, and in particular relates to a modified flame retardant compound, a modified flame retardant, a flame retardant modified coating adhesive, a composite cloth and a preparation method thereof.
  • Cotton, polyester and other fiber fabrics are widely used in various industries around the world, such as clothing, curtains, fabric furniture, as well as shopping malls, airports, entertainment venues, and interior decoration of transportation vehicles. While fiber fabrics bring convenience to people's lives, they also bring fire hazards to people due to their flammability.
  • the flame-retardant fabrics currently used, such as firefighting suits, have poor thermal insulation properties despite their flame-retardant properties, and cannot effectively prevent flames and insulate heat in fires.
  • One aspect of the present disclosure provides a modified flame retardant compound, the specific structure of which is shown in formula (I):
  • the compound represented by formula (I) is obtained by introducing a Si-(OMe) 3 group into the compound represented by formula (II);
  • a modified flame retardant comprising:
  • a blending agent blended with the mixture being selected from one or more of phosphoric acid, ammonium salt, magnesium salt, and melamine;
  • the ammonium salt is ammonium chloride
  • the magnesium salt is selected from one or more of magnesium chloride and magnesium sulfate.
  • a flame retardant modified coating adhesive comprising the following components in parts by weight:
  • the sum of the weight parts of all components is 100, and the modifier is selected from one or more of graphite, fiber, silicon oxide, calcium oxide, and titanium oxide.
  • a method for preparing a flame retardant modified coating adhesive comprising:
  • the modifier is then added into the mixed solution, and the mixture is dispersed and stirred evenly again to obtain a flame retardant modified coating adhesive.
  • a method for preparing a flame retardant and heat insulating composite fabric comprising:
  • multiple pieces of fabric to be treated are immersed in an aqueous solution of a modified flame retardant, and after the immersion treatment, they are pre-dried at 55-65°C and dried at 100-120°C to obtain multiple pieces of flame retardant fabric, wherein the mass ratio of the modified flame retardant to water is 1:10-30;
  • the fabric to be treated includes any one of cotton, non-woven, polyester, nylon, and fiber cloth, and the multiple flame-retardant and heat-insulating fabrics stacked in sequence are different from each other;
  • the thickness of the thermal insulation layer is 0.1-3.5 mm.
  • a flame retardant and heat insulating composite cloth is provided, which is prepared by the method for preparing the flame retardant and heat insulating composite cloth.
  • the present disclosure provides a modified flame retardant compound, a modified flame retardant, a flame retardant modified coating adhesive, a composite cloth and a preparation method thereof, which have at least one of the following beneficial effects:
  • Si-(OMe) 3 is introduced into the compound represented by formula (II) to obtain the compound represented by formula (I).
  • the compound represented by formula (I) can be used as a flame retardant because the P and Si elements in the compound have good flame retardancy.
  • the P and Si elements in the compounds represented by formula (I) and formula (II) have good flame retardancy, and the selected melamine and magnesium elements also have good flame retardancy.
  • Formula (I) and formula (II) are mixed with at least one blending agent selected from phosphoric acid, ammonium salt, magnesium salt, and melamine to obtain a modified flame retardant.
  • the modified flame retardant improves the flame retardancy of the fabric and the bonding strength between the flame retardant and the fabric.
  • the prepared flame retardant modified coating adhesive has good heat insulation ability and good flame retardancy.
  • a plurality of fabrics to be treated are immersed in a modified flame retardant, and a flame retardant modified coating adhesive is applied on both sides of the fabric containing the modified flame retardant, and then the plurality of fabrics are stacked and assembled in sequence to obtain a series of combined composite fabrics.
  • the formed composite fabric has flame retardant properties while basically maintaining its softness. When the flame continues to burn, the composite fabric will not burn within a certain period of time, and the composite fabric will not smolder after leaving the fire.
  • the modified coating adhesive in the composite fabric can absorb a large amount of heat to undergo phase change when the flame is directly burned, and at the same time foam and expand to form a porous carbonized layer that is dozens of times thicker than the original coating layer.
  • the porous carbonized layer absorbs a large amount of heat during the foaming process, so that the formed porous carbonized layer has high thermal insulation performance and can constitute a thermal insulation barrier, so that the composite fabric has flame retardancy and thermal insulation capabilities, and is expected to be applied to flame retardant and thermal insulation scenes.
  • FIG1 is an infrared spectrum of a modified flame retardant compound in an embodiment of the present disclosure
  • FIG2 is an infrared spectrum of the modified flame retardant in the embodiment of the present disclosure.
  • FIG3 is a thermogravimetric-differential thermal scanning curve of the modified flame retardant in an embodiment of the present disclosure
  • FIG4 is an infrared spectrum of the flame retardant modified coating adhesive in the embodiment of the present disclosure.
  • FIG5 is a thermogravimetric-differential thermal scanning curve of the flame retardant modified coating adhesive in an embodiment of the present disclosure
  • FIG6 is a schematic diagram of vertical flame spraying of a flame retardant and heat insulating composite fabric in an embodiment of the present disclosure
  • FIG7 is a graph showing the temperature variation of the back side of the composite cloth under a flame of 1300° C. over time in Example 1 of the present disclosure
  • FIG8 is a graph showing the variation of the quality of the composite fabric over time when tested by a cone calorimeter in Example 1 of the present disclosure
  • FIG9A is a scanning electron microscope image of a block region of a thick carbonized portion of the flame retardant modified coating adhesive of the composite cloth in Example 1 of the present disclosure at a scale of 5 microns;
  • FIG9B is a scanning electron microscope image of the flame retardant modified coating adhesive of the composite cloth in Example 1 of the present disclosure at a scale of 5 microns in the pore area of the thick carbonized part after spraying;
  • 9C is a scanning electron microscope image of the flame retardant modified coating adhesive of the composite cloth in Example 1 of the present disclosure at a scale of 10 microns in the thick carbonized partial layer structure area after spraying.
  • the present disclosure proposes a modified flame retardant compound, a modified flame retardant, a flame retardant modified coating adhesive, a composite cloth and a preparation method thereof, wherein a compound shown in formula (I) is obtained by introducing Si-(OMe) 3 groups on the basis of the original compound shown in formula (II), and the P and Si elements in the compound shown in formula (I) have good flame retardancy.
  • the compounds shown in formula (I) and formula (II) are blended with blending agents such as phosphoric acid, ammonium salt, magnesium salt, and melamine to obtain a modified flame retardant.
  • a water-based polyurethane with good foaming expansibility, flame retardancy and compatibility is reacted with a modifier, ammonium polyphosphate flame retardant, a carbonizing agent, a defoaming agent, etc. to obtain a modified coating adhesive with flame retardancy.
  • the modified flame retardant and the flame retardant modified coating adhesive are used to treat the fabric to be treated, so that the fabric has both flame retardancy and heat insulation.
  • Si-(OMe) 3 is introduced into the compound of formula (II) to obtain the compound of formula (I).
  • the compound of formula (I) can be used as a flame retardant because the P and Si elements in the compound have good flame retardancy.
  • a second aspect of the present disclosure provides a method for preparing a compound represented by formula (I) in a modified flame retardant, comprising: Compound A Compound B Reaction to obtain the compound shown in formula (I)
  • the method for preparing the compound represented by formula (I) is as follows: under the conditions of an organic solvent and a catalyst, compound A and compound B are mixed to form a flame retardant mixed liquid, a pH regulator is added to the flame retardant mixed liquid, and the mixture is reacted at a preset temperature to obtain the compound represented by formula (I).
  • the organic solvent is selected from methanol
  • the catalyst is selected from calcium oxide
  • the molar ratio of compound A to compound B is 1:1 to 1:1.2, such as 1:1.02
  • the preset reaction temperature is 50-70°C, such as 60°C
  • the pH regulator adjusts the pH of the flame retardant mixed liquid to be neutral, and the pH is 6-7.
  • the third aspect of the present disclosure provides a modified flame retardant, comprising: a mixture of a compound represented by formula (I) and a compound represented by formula (II); and a co-mixing agent blended with the mixture, wherein the co-mixing agent is selected from one or more of phosphoric acid, ammonium salt, magnesium salt, and melamine; the ammonium salt is ammonium chloride, and the magnesium salt is selected from one or more of magnesium chloride and magnesium sulfate, wherein the structures of the compound represented by formula (I) and the compound represented by formula (II) are respectively as follows:
  • the Si and P elements in the compounds represented by formula (I) and formula (II) have good flame retardancy, and the selected melamine and magnesium elements also have good flame retardancy.
  • the compounds represented by formula (I) and formula (II) are mixed with at least one blending agent selected from phosphoric acid, ammonium salt, magnesium salt, and melamine to obtain a modified flame retardant.
  • the modified flame retardant improves the flame retardancy of the fabric while utilizing the solubility between the blending agents such as phosphoric acid, ammonium chloride, and magnesium sulfate and the compounds represented by formula (I) and formula (II), thereby improving the bonding strength between the flame retardant and the fabric.
  • the blending mass ratio of the co-mixing agent and the mixture is 1:20-50, and the mass ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1:1-3.
  • the modified flame retardant formed within this ratio range has good flame retardancy, wherein the blending mass ratio can be selected as 1:20, 1:30, 1:40, 1:50, etc., and the mass ratio of the compounds represented by formula (I) to formula (II) can be 1:1, 1:2, 1:3, etc.
  • FIG. 2 is an infrared spectrum of the modified flame retardant in the embodiment of the present disclosure
  • FIG. 3 is a thermogravimetric-differential thermal scanning curve of the modified flame retardant in the embodiment of the present disclosure.
  • the fourth aspect of the present disclosure provides a flame retardant modified coating adhesive, comprising the following components in parts by weight: 1-10 parts of a modifier, 20-50 parts of an aqueous polyurethane, 20-50 parts of an ammonium polyphosphate flame retardant, 10-30 parts of a charring agent, 0.1-0.5 parts of a wetting agent, 0.1-0.5 parts of a defoaming agent, 0.1-0.5 parts of a dispersant, 0.1-0.5 parts of an anti-settling agent, and 10-30 parts of a diluent; wherein the sum of the parts by weight of all components is 100, and the modifier is selected from at least one of graphite, fiber, silicon oxide, calcium oxide, and titanium oxide; the infrared spectrum of the obtained flame retardant modified coating adhesive is shown in Figure 4.
  • the selected water-based polyurethane is easily expanded, heat-insulated, and adhered during the reaction, and has good compatibility with the compounds represented by formula (I) and formula (II) and other components.
  • the selected modifier has a porous structure, high temperature resistance and flame retardancy, and the ammonium polyphosphate flame retardant has good flame retardancy and can be mixed with the modifier and water-based polyurethane.
  • the water-based polyurethane is doped with the modifier, the ammonium polyphosphate flame retardant, the carbon-forming agent, etc. to prepare a flame-retardant modified coating adhesive.
  • the flame-retardant modified coating adhesive has flame retardancy and heat insulation, and the various components in the coating adhesive are evenly dispersed.
  • the wetting agent is a combination of one or more of BYK-306, BYK-S706, BYK-361, BYK-359, and SN-4727A;
  • the defoaming agent is a combination of one or more of SN-6710, silicone defoaming agent, mineral oil, and polyether;
  • the carbonizing agent is a combination of one or more of glucose, starch, sucrose, cyclodextrin, pentaerythritol, and dipentaerythritol;
  • the dispersant is BYK-2150, BYK-330, BYK-341, BYK-307, BYK -2155, BYK-104S, SN-1728A, SN-1728, SN-1729, SN-1776, SN-1760, SN-1790A, SN-1791, SN-1790, SN-1792, SN-1798, or a combination thereof;
  • the anti-settling agent is a combination of one or more
  • FIG. 5 is a thermogravimetric-differential thermal scanning curve of the flame retardant modified coating adhesive in an embodiment of the present disclosure.
  • the fifth aspect of the present disclosure provides a method for preparing a flame retardant modified coating adhesive, comprising: adding a diluent to a reactor containing aqueous polyurethane, stirring until a vortex appears at the center of the liquid surface to fully dissolve the aqueous polyurethane; slowly adding a wetting agent, a defoamer, and a dispersant to the reactor to mix the added wetting agent, defoamer, and dispersant evenly; adding an ammonium polyphosphate flame retardant and a carbonizing agent to the reactor and mixing them evenly; then adding a modifier to the mixed solution, dispersing and stirring evenly again to obtain a flame retardant modified coating adhesive.
  • the aqueous polyurethane, the modifier, the ammonium polyphosphate flame retardant, the carbonizing agent, the defoamer, and the like can be evenly dispersed, which helps to obtain a flame retardant modified coating adhesive with moderate viscosity and evenly dispersed flame retardant.
  • the sixth aspect of the present disclosure provides a method for preparing a flame retardant and heat-insulating composite cloth, comprising: immersing multiple pieces of fabrics to be treated in an aqueous solution of the modified flame retardant in the above embodiment at 30-45°C, pre-baking at 55-65°C after the immersion treatment, and drying at 100-120°C to obtain multiple pieces of flame retardant fabrics; applying the flame retardant modified coating adhesive in the above embodiment on both sides of each piece of flame retardant fabric as a heat insulation layer to obtain a flame retardant and heat-insulating fabric; then, stacking the multiple pieces of flame retardant and heat-insulating fabrics in sequence, connecting the multiple pieces of flame retardant and heat-insulating fabrics to each other by utilizing the viscosity of the flame retardant modified coating adhesive, and obtaining a flame retardant and heat-insulating composite cloth after drying, wherein the immersion treatment time is 10-40min, the pre-baking time is 20-60min, the drying time is 10-40min, and the mass ratio
  • the thickness of the thermal insulation layer is 0.1-3.5 mm, preferably the thickness of the thermal insulation layer is 0.1-2 mm, so that the composite cloth has higher thermal insulation and air permeability while maintaining the softness of the composite cloth.
  • the fabric to be treated includes any one of cotton, non-woven, polyester, Viagra, and fiber cloth, and the multiple flame-retardant and heat-insulating fabrics stacked in sequence are different.
  • a flame-retardant and heat-insulating composite fabric is obtained by stacking cotton, non-woven, and polyester in sequence
  • a flame-retardant and heat-insulating composite fabric is obtained by stacking cotton, Viagra, and polyester in sequence.
  • soaking multiple pieces of fabric to be treated at 30-45°C helps to wet the fabric and evenly disperse the modified flame retardant on the fabric to be treated; then pre-drying at 55-65°C helps the modified flame retardant to penetrate into the fabric to be treated; finally, drying at 100-120°C removes excess moisture from the fabric to be treated.
  • a flame retardant and heat insulating composite cloth is provided.
  • the flame retardant and heat insulating composite cloth is obtained by the preparation method of the heat insulating composite cloth in the above embodiment.
  • a series of different flame retardant and heat insulating composite fabrics are obtained by using modified flame retardant and flame retardant modified coating adhesive in coordination, and then assembling different fabrics to be treated.
  • the flame retardant and heat insulating composite fabric formed has flame retardant properties on the basis of basically maintaining softness.
  • the composite fabric will not burn for a period of time and the composite fabric will not smolder after leaving the fire, indicating that the composite fabric has good flame retardant properties.
  • the composite fabric can absorb a large amount of heat to undergo phase change, and at the same time foam and expand to form a porous carbonized layer that is tens of times thicker than the original flame retardant modified coating adhesive.
  • the porous structure of the carbonized layer is used to improve its heat insulation performance, forming a heat insulation barrier.
  • the fabric treated with the flame retardant modified coating adhesive and the flame retardant modifier effectively reduces the possibility of fire caused by the fabric.
  • the composite fabric is made into firefighting clothing with good heat insulation to ensure the safety of firefighters.
  • the actual modified flame retardant needs to be compounded with a certain proportion of water when used.
  • the mass ratio of the modified flame retardant to water is 1:10-30.
  • the cotton is soaked in the modified flame retardant aqueous solution for 20 minutes, the soaking temperature is controlled at 30°C, after the soaking treatment is completed, it is pre-dried at 60°C for 20 minutes, and then dried in a 100°C oven for 15 minutes; the fiber is soaked in the modified flame retardant solution for 40 minutes, the soaking temperature is controlled at 45°C, after the soaking treatment is completed, it is pre-dried at 60°C for 60 minutes, and then Dry in an oven at 120°C for 30 minutes; soak the non-woven fabric in the modified flame retardant solution for 10 minutes, control the soaking temperature at 30°C, pre-bake at 60°C for 20 minutes after the soaking treatment, and then dry in an oven at 100°C for 10 minutes to obtain three different flame retardant fabrics.
  • the modified flame retardant aqueous solution includes: 5 parts by weight of the compound represented by formula (I), 10 parts by weight of the compound represented by formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.
  • the step of heat-insulating the corresponding flame-retardant fabric is as follows: the cotton cloth, fiber cloth and non-woven fabric containing the modified flame retardant are coated with a flame-retardant modified coating adhesive with a thickness of 0.1-1.0 mm on both sides.
  • the flame-retardant modified coating adhesive is prepared from the following raw materials in parts by weight: 7 parts by weight of a modifier (expanded graphite), 45 parts by weight of an aqueous polyurethane emulsion (E11 (product model) of Jiangsu Xingfeng Chemical Technology Co., Ltd.), 23 parts by weight of ammonium polyphosphate, 12 parts by weight of a carbonizing agent (pentaerythritol), 0.8 parts by weight of a wetting agent (BYK-S706 (product model) of German BYK brand), 0.3 parts by weight of a defoaming agent (mineral oil), 0.4 parts by weight of a dispersant (BYK-2150 (product model) of German BYK brand), 0.5 parts by weight of an anti-settling agent (bentonite), and 11 parts by weight of a diluent (water).
  • a modifier expanded graphite
  • E11 aqueous polyurethane emulsion
  • the adhesion of the flame retardant modified coating adhesive is utilized to bond the cotton cloth-fiber cloth-non-woven fabric together in the order of adhesion, thus obtaining the cotton cloth-fiber cloth-non-woven fabric flame retardant heat insulating composite fabric.
  • flame retardant modified coating glue can be applied on the front and back of the composite cloth with a thickness of 1-2mm. After the coating is completely dry, the composite cloth has high adhesion, will not fall off, will not crack, and has good flexibility.
  • the flame retardant fabric obtained in step (1) of the embodiment is directly measured by the vertical method, wherein the schematic diagram of vertical flame spraying of the flame retardant and heat insulating composite fabric is shown in FIG6 .
  • the average afterflame time of the cotton flame retardant fabric is less than 0.1s
  • the average smoldering time is 0.8s
  • the average carbonization length is 3.0mm.
  • Fiber cloth flame retardancy test At 20°C, in the atmosphere, a fiber cloth of 300cm ⁇ 80cm was placed in a vertical combustion tester, ignited, and the afterburning time, smoldering time and damaged length were tested. Five sets of parallel experiments were conducted. The specific experimental results are shown in Table 2.
  • the average afterflaming time of the fiber cloth flame retardant fabric is less than 0.1s
  • the average smoldering time is less than 0.1s
  • the average carbonization length is 1mm.
  • the average afterflame time of the non-woven flame retardant fabric is less than 0.1 s
  • the average smoldering time is 1.0 s
  • the average carbonization length is 4.0 mm.
  • Flame retardant heat insulation composite cloth test At 20°C, in the atmosphere, a flame retardant heat insulation composite cloth of size 30cm ⁇ 30cm, with an outermost heat insulation layer of 1.0mm. Two metal clips fixed the composite cloth and placed it vertically on the safety table of the fume hood. The thermal insulation performance was tested with a 1300°C flame, the test time was 5.0min, and 5 sets of parallel experiments were performed. The corresponding data were obtained. When the 1200-1300°C butane spray gun flame was aimed at the front of the composite cloth and the surface fell on the outer flame area with the highest temperature of the flame, the coating was heated and foamed, and the foaming height was 30 times higher than the original coating.
  • the mass loss of the composite fabric was measured using a cone calorimeter.
  • the specific steps were as follows: at 25°C, in an atmosphere, a flame retardant and heat insulating composite fabric of size 12 cm ⁇ 12 cm was tested at a radiation intensity of 50 kW/m 2 for 15 min, with a mass loss of 1.5 g and a mass loss rate per unit area of 0.116 g/m 2 /s.
  • the specific experimental results are shown in FIG8 .
  • the composite fabric prepared by modifying cotton, non-woven fabric, polyester, Vilan and fiber fabric with modified flame retardant and flame retardant modified coating adhesive has good flame retardant and heat insulation ability.
  • the surface of the composite fabric encounters fire, it will immediately change phase and absorb heat, and form a carbonized layer (as shown in Figure 9A, Figure 9B, Figure 9C), which has very good heat insulation performance.
  • the composite fabric has strong flexibility, light weight, and comfortable inner non-woven fabric; when heated, its outer surface can foam to isolate most of the heat, providing a relatively heat-insulating system for firefighters' rescue operations, and maximizing the safety of firefighters' lives.
  • the steps for preparing the polyester-vinyl alcohol-fiber cloth flame retardant and heat insulating composite cloth are as follows:
  • the modified flame retardant comprises: 5 parts by weight of the compound represented by formula (I), 10 parts by weight of the compound represented by formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.
  • the steps of heat-insulating the corresponding flame-retardant fabric are as follows: coating the polyester, nylon and fiber cloth with a flame-retardant modified coating adhesive with a thickness of 0.1-1.0 mm on both sides.
  • the flame-retardant modified coating adhesive is prepared from the following raw materials in parts by weight: 7 parts by weight of a modifier (expanded graphite), 45 parts by weight of an aqueous polyurethane emulsion (E11 (product model) of Jiangsu Xingfeng Chemical Technology Co., Ltd.), 23 parts by weight of ammonium polyphosphate, 12 parts by weight of a carbonizing agent (pentaerythritol), 0.8 parts by weight of a wetting agent (BYK-S706 (product model) of German BYK brand), 0.3 parts by weight of a defoaming agent (mineral oil), 0.4 parts by weight of a dispersant (BYK-2150 (product model) of German BYK brand), 0.5 parts by
  • Flame retardant heat insulation composite cloth test At 20°C, in the atmosphere, a flame retardant heat insulation composite cloth of size 30cm ⁇ 30cm, with the outermost heat insulation layer of 1.0mm, was fixed with two metal clips and placed vertically on the safety table of the fume hood. The heat insulation performance was tested with a 1300°C flame for 5.0min, and 5 groups of parallel experiments were conducted. The corresponding data were obtained.
  • the flame of a 1200-1300°C butane spray gun is aimed at the front of the composite cloth and the surface falls on the outer flame area with the highest temperature of the flame. The coating is heated and foamed, and the foaming height is 30 times higher than the original coating.
  • flame retardant modified coating glue can be applied on the front and back of the composite cloth.
  • the thickness can be 1-2mm. After the coating is completely dry, it has high adhesion, will not fall off, will not crack, and has good flexibility.
  • the modified flame retardant comprises: 5 parts by weight of the compound represented by formula (I), 10 parts by weight of the compound represented by formula (II), 0.04 parts by weight of phosphoric acid, 0.1 parts by weight of melamine, and 200 parts by weight of water.
  • the steps of subjecting the corresponding flame-retardant fabric to heat insulation treatment are as follows: coating the cotton cloth, vinyl and polyester with a flame-retardant modified coating adhesive with a thickness of 0.1-1.0 mm; and utilizing the adhesion of the flame-retardant modified coating adhesive to bond the cotton cloth-vinyl alcohol-polyester together in the order of adhesion, thereby obtaining a cotton cloth-vinyl alcohol-polyester flame-retardant heat-insulating composite cloth.
  • the flame retardant modified coating adhesive is prepared from the following raw materials in parts by weight: 7 parts by weight of a modifier (expanded graphite), 45 parts by weight of an aqueous polyurethane emulsion (E11 (product model) of Jiangsu Xingfeng Chemical Technology Co., Ltd.), 23 parts by weight of ammonium polyphosphate, 12 parts by weight of a carbonizing agent (pentaerythritol), 0.8 parts by weight of a wetting agent (BYK-S706 (product model) of the German BYK brand), 0.3 parts by weight of a defoaming agent (mineral oil), 0.4 parts by weight of a dispersant (BYK-2150 (product model) of the German BYK brand), 0.5 parts by weight of an anti-settling agent (bentonite), and 11 parts by weight of a diluent (water).
  • a modifier expanded graphite
  • E11 aqueous polyurethane emulsion
  • Flame retardant heat insulation composite cloth test At 20°C, in the atmosphere, a flame retardant heat insulation composite cloth of size 30cm ⁇ 30cm, with an outermost heat insulation layer of 1.0mm, was fixed with two metal clips and placed vertically on the safety table of the fume hood. The heat insulation performance was tested with a 1300°C flame for 3.0min, and 5 groups of parallel experiments were conducted. The corresponding data were obtained. When the 1200-1300°C butane spray gun flame was aimed at the front of the composite cloth and the surface fell on the outer flame area with the highest temperature of the flame, The coating foams when heated, and the foaming height is 30 times higher than the original coating. At the same time, a phase change occurs, and the coating is transformed into a porous carbonized layer.
  • the foaming process absorbs a lot of heat, and the final back temperature is only 84°C. After leaving the fire, the average afterburning time of the front side of the composite cloth is less than 0.1s, and the average smoldering time is less than 0.1s.
  • the specific experimental results are shown in Table 6.
  • flame retardant modified coating glue can be applied on the front and back of the composite cloth.
  • the thickness can be 1-2mm. After the coating is completely dry, it has high adhesion, will not fall off, will not crack, and has good flexibility.

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Abstract

本公开提供了一种改性阻燃化合物、改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法，属于阻燃剂技术领域，其中，改性阻燃化合物的结构如下：>式(I)；式(I)所示化合物为在式(II)所示化合物中引入Si-(OMe)3基团获得；其中，式(II)所示化合物的结构如下：式(II)；式(I)所示化合物中的P、Si元素具有良好的阻燃能力，与磷酸、铵盐、镁盐、三聚氰胺等共混剂共混后能够提高织物纤维的阻燃能力和结合牢度。

Description

改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法 技术领域
本公开属于阻燃剂技术领域，尤其涉及一种改性阻燃化合物、改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法。
背景技术
棉布，涤纶等纤维织物被广泛的应用到世界各地、各种行业中，例如服装、窗帘、布艺家具、以及商场、机场、娱乐场所、交通工具的内饰装修等领域里。纤维织物给人民生活带来便利的同时，由于其易燃性，也给人民带来了火灾隐患。当前使用的阻燃织物，如消防服尽管具备阻燃特性，但隔热性能较差，在火场中也不能较好的阻燃、隔热。
因此，开发具有良好的阻燃且隔热的织物具有重要意义。
发明内容
本公开的一个方面提供了一种改性阻燃化合物，其具体结构如式(I)所示：
式(I)所示化合物为在式(II)所示化合物中引入Si-(OMe)3基团；
其中，式(II)所示化合物的结构如下：
作为本公开的第二个方面，提供了一种制备改性阻燃化合物中式(I)所示化合物的方法，包括：
A化合物与B化合物反应，得到式(I)所示化合物
作为本公开的第三个方面，提供了一种改性阻燃剂，包括：
式(I)所示化合物和式(II)所示化合物的混合物；以及
与混合物共混的共混剂，共混剂选自磷酸、铵盐、镁盐、三聚氰胺中一种或多种；
其中，式(I)与式(II)所示化合物的结构如下：
铵盐为氯化铵，镁盐选自氯化镁、硫酸镁中一种或多种。
作为本公开的第四个方面，提供了一种阻燃改性涂层胶，包括如下重量份数的各个组分：
其中，所有组分的重量份数之和为100，改性剂选自石墨、纤维、硅氧化物、钙氧化物、钛氧化物中一种或多种。
作为本公开的第五个方面，提供了一种阻燃改性涂层胶的制备方法，包括：
向含水性聚氨酯的反应器中加入稀释剂，搅拌直至液面中心出现旋涡；
向反应器内缓慢加入湿润剂、消泡剂、分散剂后，加入聚磷酸铵阻燃剂、成炭剂到反应器内并混合均匀；
再将改性剂加入至混合液中，再次分散搅拌均匀，得到阻燃改性涂层胶。
作为本公开的第六个方面，提供了一种阻燃隔热复合布的制备方法，包括：
在30-45℃下，将多片待处理织物浸泡于改性阻燃剂的水溶液中，浸泡处理后，在55-65℃下进行预烘，并在100-120℃下干燥，得到多片阻燃织物，其中改性阻燃剂与水的质量比为1∶10-30；
在每片阻燃织物两面涂敷阻燃改性涂层胶作为隔热层，得到阻燃隔热织物；
将多片阻燃隔热织物依次堆叠，利用阻燃改性涂层胶的粘性粘连在一起，干燥后得到阻燃隔热复合布；
其中，待处理织物包括棉布、无纺布、涤纶、维伦、纤维布中任意一种，且多个依次堆叠的阻燃隔热织物各不相同；
隔热层的厚度为0.1-3.5mm。
作为本公开的第七个方面，提供了一种阻燃隔热复合布，采用上述阻燃隔热复合布的制备方法制得。
基于上述技术方案，本公开提供的一种改性阻燃化合物、改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法至少包括以下有益效果之一：
(1)根据本公开的实施例，在式(II)所示化合物的基础上引入Si-(OMe)3，得到式(I)所示化合物，利用式(I)所示化合物中的P、Si元素具有良好的阻燃能力的特点，可以将其作为阻燃剂进行使用。
(2)根据本公开的实施例，利用式(I)与式(II)所示化合物中的P、Si元素都具有良好的阻燃能力，以及所选用的三聚氰胺和镁元素也都具有良好的阻燃性，将式(I)与式(II)与磷酸、铵盐、镁盐、三聚氰胺中至少一种共混剂进行混合，得到改性阻燃剂，所组成的改性阻燃剂提高织物的阻燃能力和阻燃剂与织物的结合牢度。
(3)根据本公开的实施例，通过将具有一定的耐高温能力、阻燃性的石墨、纤维等改性剂、和具有良好膨胀能力、隔热能力、粘连能力和兼容性较强的水性聚氨酯与聚磷酸铵阻燃剂、成炭剂、湿润剂、消泡剂等进行混合，所制备的阻燃改性涂层胶具有良好隔热能力的同时还具有良好的阻燃性。
(4)根据本公开的实施例，通过将多个待处理织物浸泡于改性阻燃剂中，并在含有改性阻燃剂织物的两面涂敷阻燃改性涂层胶，然后将多个织物依次堆叠进行组装，得到一系列组合的复合布。所形成的复合布在基本保持柔软的基础上具有阻燃特性，在火焰持续灼烧的情况下，在一定时间内复合布不会燃烧，且复合布离火后也没有阴燃。另一方面复合布中的改性涂层胶在火焰直接灼烧情况下，能够吸收大量热量发生相变，同时发泡膨胀，形成比原涂胶层厚数十倍的多孔碳化层，其在发泡过程中吸收大量的热量，使得所形成的多孔碳化层隔热性能较高，能够构成绝热屏障，从而使得该复合布具有阻燃性的同时还具有隔热能力，有望将其应用于阻燃隔热等场景中。
附图说明
图1为本公开实施例中改性阻燃化合物的红外光谱图；
图2为本公开实施例中改性阻燃剂的红外光谱图；
图3为本公开实施例中改性阻燃剂的热重-差热扫描曲线图；
图4为本公开实施例中阻燃改性涂层胶的红外光谱图；
图5为本公开实施例中阻燃改性涂层胶的热重-差热扫描曲线图；
图6为本公开实施例中垂直火焰喷烧阻燃隔热复合布的示意图；
图7为本公开实施例1中在1300℃火焰下复合布背面温度随时间变化图；
图8为本公开实施例1中锥形量热仪测试复合布质量随时间变化图；
图9A为本公开实施例1中复合布的阻燃改性涂层胶经喷烧厚碳化部分块状区域5微米尺度下的扫描电镜图；
图9B为本公开实施例1中复合布的阻燃改性涂层胶经喷烧厚碳化部分孔状区域5微米尺度下的扫描电镜图；
图9C为本公开实施例1中复合布的阻燃改性涂层胶经喷烧厚碳化部分层结构区域10微米尺度下的扫描电镜图。
具体实施方式
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本公开作进一步的详细说明。
针对现有织物不能同时实现较高的阻燃、隔热性能的问题，本公开提出了一种改性阻燃化合物、改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法，通过在原有的式(II)所示化合物的基础上引入Si-(OMe)3基团得到式(I)所示化合物，式(I)所示化合物中的P、Si元素具有良好的阻燃能力。将式(I)与式(II)所示化合物与磷酸、铵盐、镁盐、三聚氰胺等共混剂进行共混，得到改性阻燃剂。同时，利用发泡膨胀性、阻燃性和兼容性良好的水性聚氨酯与改性剂、聚磷酸铵阻燃剂、成炭剂、消泡剂等进行反应得到具有阻燃性能的改性涂层胶。最后，利用改性阻燃剂和阻燃改性涂层胶来处理待处理织物，使得织物同时具备阻燃性和隔热性。
具体地，本公开的第一个方面提供了一种改性阻燃化合物，其具体结构如式(I)所示：式(I)所示化合物为在式(II)所示化合物中引入Si-(OMe)3基团获得；其中，式(II)所示化合物的结构如下：
在本公开的实施例中，通过在式(II)所示化合物的基础上引入Si-(OMe)3，得到式(I)所示化合物，利用式(I)所示化合物中的P、Si元素具有良好的阻燃能力的特点，可以将其作为阻燃剂进行使用。
根据本公开的实施例，本公开第二个方面提供了一种制备改性阻燃剂中式(I)所示化合物的方法，包括：A化合物与B化合物反应，得到式(I)所示化合物
具体地，制备式(I)所示化合物的方法为：在有机溶剂和催化剂条件下，A化合物与B化合物混合形成阻燃混合液，向阻燃混合液中加pH调节剂，在预设温度下反应，得到式(I)所示化合物。其中，有机溶剂选自甲醇，催化剂选自氧化钙；A化合物与B化合物的摩尔比为1∶1～1∶1.2，如1∶1.02；预设反应温度为50-70℃，如60℃；pH调节剂调节阻燃混合液的pH为中性，pH为6-7。
例如：将A化合物(91.7mL，1mol)与CaO(16.8g，0.3mol)置于反应器内进行搅拌。然后，加入甲醇溶剂300mL，并在安装冷凝管、温度计后放入水浴中，预先加热到50℃，随后将B化合物(242mL，1.02mol)滴加到反应器内，在滴加过程中将反应温度控制在65℃，反应30min后结束停止反应；经过滤、甲醇洗涤，得到式(I)所示化合物，式(I)所示化合物的红外光谱图如图1所示；其中，得到式(I)所示化合物的具体反应式如下：
本公开的第三个方面提供了一种改性阻燃剂，包括：式(I)所示化合物与(II)所示化合物的混合物；以及与该混合物共混的共混剂，其中共混剂选自磷酸、铵盐、镁盐、三聚氰胺中一种或多种；铵盐为氯化铵，镁盐选自氯化镁、硫酸镁中一种或多种，其中式(I)所示化合物与式(II)所示化合物的结构分别如下：
根据本公开的实施例，式(I)与式(II)所示化合物中的Si、P元素都具有良好的阻燃能力，所选用的三聚氰胺和镁元素也都具有良好的阻燃性，将式(I)与式(II)所示化合物与磷酸、铵盐、镁盐、三聚氰胺中至少一种共混剂进行混合，得到改性阻燃剂，所组成的改性阻燃剂提高织物的阻燃能力的同时利用磷酸、氯化铵、硫酸镁等共混剂与式(I)与式(II)所示化合物之间的溶解性，提高了阻燃剂与织物的结合牢度。
根据本公开的实施例，共混剂与混合物(包括式(I)与式(II)所示化合物)的共混质量比为1∶20-50，式(I)所示化合物与式(II)所示化合物的质量比为1∶1-3，在此比例范围内所组成的改性阻燃剂具有良好的阻燃性，其中，共混质量比可选为1∶20、1∶30、1∶40、1∶50等，式(I)与式(II)所示化合物的质量比可以为1∶1、1∶2、1∶3等。
图2为本公开实施例中改性阻燃剂的红外光谱图，图3为本公开实施例中改性阻燃剂的热重-差热扫描曲线图。
从图3中可以看到在温度逐渐升高的过程中，伴随一定的质量损失，同时有1个明显吸热峰，可以说明改性阻燃剂具有一定的吸热能力。
根据本公开的实施例，本公开的第四个方面提供了一种阻燃改性涂层胶，包括如下重量份数的各个组分：改性剂1-10份、水性聚氨酯20-50份、聚磷酸铵阻燃剂20-50份、成炭剂10-30份、湿润剂0.1-0.5份、消泡剂0.1-0.5份、分散剂0.1-0.5份、防沉降剂0.1-0.5份、稀释剂10-30份；其中，所有组分的重量份数之和为100，改性剂选自石墨、纤维、硅氧化物、钙氧化物、钛氧化物中至少一种；所获得的阻燃改性涂层胶的红外光谱图如图4所示。
在本公开的实施例中，利用所选用的水性聚氨酯在反应过程中容易发生膨胀、隔热、粘连和对式(I)、式(II)所示化合物及其他组分具有良好的兼容性的特点，所选用的改性剂具有多孔结构、耐高温和阻燃的特点以及聚磷酸铵阻燃剂具有良好的阻燃性且能够与改性剂、水性聚氨酯混匀的特点，将水性聚氨酯与改性剂、聚磷酸铵阻燃剂、成炭剂等进行掺杂，从而制备得到阻燃改性涂层胶，该阻燃改性涂层胶具有阻燃性的同时还具有隔热性且涂层胶中各个组分均匀分散。
根据本公开的实施例，润湿剂为BYK-306、BYK-S706、BYK-361、BYK-359、SN-4727A中的一种或多种的组合；消泡剂为SN-6710、有机硅消泡剂、矿物油、聚醚中的一种或多种的组合；成炭剂为葡萄糖、淀粉、蔗糖、环糊精、季戊四醇、双季戊四醇中的一种或多种的组合；分散剂为BYK-2150、BYK-330、BYK-341、BYK-307、BYK-2155、BYK-104S、SN-1728A、SN-1728、SN-1729、SN-1776、SN-1760、SN-1790A、SN-1791、SN-1790、SN-1792、SN-1798中的一种或多种的组合；防沉降剂为聚酰胺蜡、膨润土、聚乙烯蜡中的一种或多种的组合；稀释剂为汽油、水、甲醇、二甲苯、异丙醇、乙醇、乙酸乙酯、丙二醇二甲醚中的一种或多种的组合。
图5为本公开实施例中阻燃改性涂层胶的热重-差热扫描曲线图。
从图5中可以看到在温度逐渐升高的过程中，有一定的质量损失，同时有3个明显吸热峰，可以说明阻燃改性涂层胶具有较强的吸热能力。
根据本公开的实施例，本公开的第五个方面，提供了一种阻燃改性涂层胶的制备方法，包括：向含水性聚氨酯的反应器中加入稀释剂，搅拌直至液面中心出现旋涡，以使水性聚氨酯充分溶解；向反应器内缓慢加入湿润剂、消泡剂、分散剂后，以使加入的湿润剂、消泡剂、分散剂混合均匀；加入聚磷酸铵阻燃剂、成炭剂到反应器内并混合均匀；再将改性剂加入至混合液中，再次分散搅拌均匀，得到阻燃改性涂层胶。通过上述添加顺序，能够使水性聚氨酯、改性剂、聚磷酸铵阻燃剂、成炭剂、消泡剂等均匀分散，有助于获得粘性适中、阻燃剂分散均匀的阻燃改性涂层胶。
根据本公开的实施例，本公开第六个方面，提供了一种阻燃隔热复合布的制备方法，包括：在30-45℃下，将多片待处理织物浸泡于上述实施例中的改性阻燃剂的水溶液中，浸泡处理后，在55-65℃下进行预烘，并在100-120℃下干燥，得到多片阻燃织物；在每片阻燃织物两面涂敷上述实施例中的阻燃改性涂层胶，作为隔热层，得到阻燃隔热织物；然后，将多片阻燃隔热织物依次叠放，利用阻燃改性涂层胶的粘性将多片阻燃隔热织物相互连接在一起，干燥后得到阻燃隔热复合布，其中浸泡处理时间为10-40min，预烘时间为20-60min，干燥时间为10-40min，改性阻燃剂与水的质量比为1∶10-30。
根据本公开的实施例，隔热层的厚度为0.1-3.5mm，优选隔热层的厚度为0.1-2mm，使得复合布具有较高的隔热性和透气性，同时维持复合布的柔软性。
根据本公开的实施例，待处理织物包括棉布、无纺布、涤纶、维伦、纤维布中任意一种，且多个依次堆叠的阻燃隔热织物各不相同。例如，以棉布、无纺布、涤纶依次堆叠得到阻燃隔热复合布，或者以棉布、维伦、涤纶依次堆叠得到的阻燃隔热复合布。
在本公开的实施例中，在30-45℃下将多片待处理织物浸泡有助于织物浸湿，使改性阻燃剂均匀分散于待处理织物上；然后在55-65℃下进行预烘，有助于改性阻燃剂浸润到待处理织物中；最后，在100-120℃下进行干燥，去除待处理织物上多余的水分。
根据本公开的实施例，本公开第七个方面，提供了一种阻燃隔热复合布，该阻燃隔热复合布由上述实施例中的隔热复合布的制备方法获得。
在本公开的实施例中，通过将改性阻燃剂和阻燃改性涂层胶协同使用，再将不同待处理织物进行组装，得到一系列不同的阻燃隔热复合布。所形成的阻燃隔热复合布在基本保持柔软的基础上具有阻燃特性，在火焰持续灼烧的情况下，在一段时间内复合布不会燃烧且复合布离火后也没有阴燃，表明该复合布具有良好的阻燃性能。另外，该复合布在火焰直接灼烧的情况下，能够吸收大量热量发生相变，同时发泡膨胀，形成比原阻燃改性涂层胶厚数十倍的多孔碳化层，利用碳化层的多孔结构使其隔热性能提高，构成了隔热屏障。通过上述阻燃改性涂层胶、阻燃改性剂处理后的织物，有效降低了由织物引发火灾的可能，同时将该复合布做成消防服，具有良好的隔热性，以保障消防人员安全。
实施例1
棉布-纤维布-无纺布阻燃隔热复合布制备过程如下：
(1)实际改性阻燃剂在应用时需要与一定比例的水进行复配，改性阻燃剂与水的质量比为1∶10-30。将棉布置于改性阻燃剂水溶液中浸泡20min，将浸泡温度控制在30℃，待浸泡处理结束后，于60℃预烘20min，然后在100℃烘箱中干燥15min；纤维布置于改性阻燃剂溶液中浸泡40min，将浸泡温度控制在45℃，待浸泡处理结束后，于60℃预烘60min，然后 在120℃烘箱中干燥30min；无纺布布置于改性阻燃剂溶液中浸泡10min，将浸泡温度控制在30℃，待浸泡处理结束后，于60℃预烘20min，然后在100℃烘箱干燥10min，得到由三种不同阻燃织物。其中，该改性阻燃剂水溶液包括：式(I)所示化合物5重量份、式(II)所示化合物10重量份、磷酸0.04重量份、三聚氰胺0.1重量份、水200重量份。
(2)将相应的阻燃织物进行隔热处理的步骤如下：将含有改性阻燃剂的棉布、纤维布以及无纺布的双面涂覆0.1-1.0mm厚的阻燃改性涂层胶。其中，该阻燃改性涂层胶，由如下重量份数的原料配制而成：改性剂(膨胀石墨)7重量份、水性聚氨酯乳液(江苏兴丰化学科技有限公司的E11(商品型号))45重量份、多聚磷酸铵23重量份、成炭剂(季戊四醇)12重量份、润湿剂(德国毕克品牌的BYK-S706(商品型号))0.8重量份、消泡剂(矿物油)0.3重量份、分散剂(德国毕克品牌的BYK-2150(商品型号))0.4重量份、防沉降剂(膨润土)0.5重量份、和稀释剂(水)11重量份。同时利用阻燃改性涂层胶的粘连性，按照棉布-纤维布-无纺布的顺序粘连在一起，即得到棉布-纤维布-无纺布阻燃隔热复合布。
为了进一步提升其隔热性能，可以继续在复合布的正反面涂覆阻燃改性涂层胶，厚度可以涂覆1-2mm，待涂层完全干燥后，该复合布的附着力高，不会脱落，不会开裂同时具有很好的柔韧性。
对实施例1制得的阻燃隔热复合布进行阻燃隔热性能测试，具体过程如下：
首先，以垂直法直接测定实施例中步骤(1)制得的阻燃织物，其中，垂直火焰喷烧阻燃隔热复合布的示意图如图6所示。
棉布阻燃测试：在20℃下，大气氛围中，将大小为300cm×80cm的棉布放入垂直燃烧测试仪中，点火，测试续燃时间、阴燃时间以及碳化长度，进行5组平行实验，具体实验结果如表1。
表1.棉布阻燃织物垂直燃烧测试
由表1可知，棉布阻燃织物的续燃平均时间小于0.1s、阴燃平均时间为0.8s以及碳化平均长度为3.0mm。
纤维布阻燃测试：在20℃下，大气氛围中，将大小为300cm×80cm的纤维布放入垂直燃烧测试仪中，点火，测试续燃时间、阴燃时间以及损毁长度，进行5组平行实验，具体实验结果见表2。
表2.纤维布阻燃织物垂直燃烧测试
由表2可知，纤维布阻燃织物的续燃平均时间小于0.1s、阴燃平均时间小于0.1s以及碳化平均长度为1mm。
无纺布阻燃测试：在20℃下，大气氛围中，将大小为300cm×80cm的棉纤维放入垂直燃烧测试仪中，点火，测试续燃时间、阴燃时间以及损毁长度，进行5组平行实验，具体实验结果见表3。
表3.无纺布阻燃织物垂直燃烧测试
由表3可知，无纺布阻燃织物的续燃平均时间小于0.1s、阴燃平均时间为1.0s以及碳化平均长度为4.0mm。
阻燃隔热复合布测试：在20℃下，大气氛围中，将大小为30cm×30cm的阻燃隔热复合布，其最外层隔热层为1.0mm。两个金属夹固定复合布，垂直放置于通风橱安全台面上。采用1300℃火焰测试其隔热性能，测试时间5.0min，进行5组平行实验。得到相应数据。当1200-1300℃丁烷喷枪火焰对准复合布正面的喷烧，表面落在火焰的最高温度的外焰区域，涂层受热发泡，发泡高度比原涂层高出30倍，同时发生相变，涂层转化成多孔碳化层，发泡过程吸收大量的热量，最终背面温度仅有55℃，燃烧过程中复合布背面温度变化情况如图7。复合布离火后，复合布正面续燃时间平均小于0.1s、阴燃平均时间小于0.1s，具体实验结果见表4。
表4.阻燃复合布燃烧测试
进一步地，利用锥形量热仪测量复合布质量损失，具体步骤为：在25℃下，大气氛围中，将大小为12cm×12cm的阻燃隔热复合布在50kw/m2辐射强度下测试15min，质量损失1.5g，单位面积质量损失速率为0.116g/m2/s，具体实验结果如图8所示。
通过实验结果对比，利用改性阻燃剂和阻燃改性涂层胶对棉布、无纺布、涤纶、维伦以及纤维布改性所制备的复合布，具有很好的阻燃隔热的能力。复合布的表面遇火后会立即相变吸热，同时形成碳化层(如图9A，图9B、图9C)，这些碳化层具有非常好的隔热性能。如果将其推广应用到织物纤维相关邻域，可以有效防止火灾的发生与蔓延，显著降低由植物纤维引起的火灾发生率以及火灾所造成的损失；与此同时，利用其良好的吸热、隔热能力可应用于防护器材和消防救援设备的原材料，尤其是防火隔热消防服的生产制备。该复合布柔韧性强，重量轻，内层无纺布舒适；受热时，其外表面可以发泡隔绝大部分热量，为消防员救援作业提供一个相对绝热体系，最大限度保障消防员的生命安全。
实施例2
涤纶-维伦-纤维布阻燃隔热复合布制备步骤如下：
(1)将涤纶置于改性阻燃剂水溶液中浸泡30min，将浸泡温度控制在35℃，待浸泡处理结束后，于60℃预烘25min，然后在100℃烘箱干燥20min；将维伦置于改性阻燃剂溶液中浸泡15min，温度控制在40℃，待浸泡处理结束后，于60℃预烘25min，然后在100℃烘箱干燥25min；将纤维布置于改性阻燃剂溶液中浸泡40min，温度控制在45℃，待浸泡处理结束后，于60℃预烘60min，然后在120℃烘箱干燥30min。得到三种不同阻燃织物纤维。其中，该改性阻燃剂包括：式(I)所示化合物5重量份、式(II)所示化合物10重量份、磷酸0.04重量份、三聚氰胺0.1重量份、水200重量份。
(2)将相应的阻燃织物进行隔热处理的步骤如下：将涤纶、维伦以及纤维布的双面涂覆0.1-1.0mm厚的阻燃改性涂层胶。其中，该阻燃改性涂层胶，由如下重量份数的原料配制而成：改性剂(膨胀石墨)7重量份、水性聚氨酯乳液(江苏兴丰化学科技有限公司的E11(商品型号))45重量份、多聚磷酸铵23重量份、成炭剂(季戊四醇)12重量份、润湿剂(德国毕克品牌的BYK-S706(商品型号))0.8重量份、消泡剂(矿物油)0.3重量份、分散剂(德国毕克品牌的BYK-2150(商品型号))0.4重量份、防沉降剂(膨润土)0.5重量份、和稀释剂(水)11重量份。同时利用阻燃改性涂层胶的粘连性，按照涤纶-维伦-纤维布的顺序粘连在一起，即得到涤纶-维伦-纤维阻燃隔热复合布。
阻燃隔热复合布测试：在20℃下，大气氛围中，将大小为30cm×30cm的阻燃隔热复合布，其最外层隔热层为1.0mm。两个金属夹固定复合布，垂直放置于通风橱安全台面上。采用1300℃火焰测试其隔热性能，测试时间5.0min，进行5组平行实验。得到相应数据。当 1200-1300℃丁烷喷枪火焰对准复合布正面的喷烧，表面落在火焰的最高温度的外焰区域，涂层受热发泡，发泡高度比原涂层高出30倍，同时发生相变，涂层转化成多孔碳化层，发泡过程吸收大量的热量，最终背面温度仅有67℃。复合布离火后，复合布正面续燃时间平均小于0.1s、阴燃平均时间小于0.1s，具体实验结果见表5。
表5.阻燃复合布燃烧测试
为了进一步提升其隔热性能，可以继续在复合布的正反面涂覆阻燃改性涂层胶，厚度可以涂覆1-2mm，待涂层完全干燥后，附着力高，不会脱落，不会开裂同时具有很好的柔韧性。
实施例3
(1)将棉布置于改性阻燃剂水溶液中浸泡20min，将浸泡温度控制在30℃，待浸泡处理结束后，于60℃预烘20min，然后在100℃烘箱干燥15min；将维伦置于改性阻燃剂溶液浸泡15min，将浸泡温度控制在40℃，待浸泡处理结束后，于60℃预烘25min，然后在100℃烘箱干燥25min；将涤纶置于改性阻燃剂溶液中浸泡30min，将浸泡温度控制在35℃，待浸泡处理结束后，于60℃预烘25min，然后在100℃烘箱干燥20min。得到三种不同阻燃织物纤维。其中，该改性阻燃剂包括：式(I)所示化合物5重量份、式(II)所示化合物10重量份、磷酸0.04重量份、三聚氰胺0.1重量份、水200重量份。
(2)将相应的阻燃织物进行隔热处理的步骤如下：将棉布、维伦以及涤纶的双面涂覆0.1-1.0mm厚的阻燃改性涂层胶；同时利用阻燃改性涂层胶的粘连性，按照棉布-维伦-涤纶的顺序粘连在一起，即得到棉布-维伦-涤纶阻燃隔热复合布。其中，该阻燃改性涂层胶，由如下重量份数的原料配制而成：改性剂(膨胀石墨)7重量份、水性聚氨酯乳液(江苏兴丰化学科技有限公司的E11(商品型号))45重量份、多聚磷酸铵23重量份、成炭剂(季戊四醇)12重量份、润湿剂(德国毕克品牌的BYK-S706(商品型号))0.8重量份、消泡剂(矿物油)0.3重量份、分散剂(德国毕克品牌的BYK-2150(商品型号))0.4重量份、防沉降剂(膨润土)0.5重量份、和稀释剂(水)11重量份。
阻燃隔热复合布测试：在20℃下，大气氛围中，将大小为30cm×30cm的阻燃隔热复合布，其最外层隔热层为1.0mm。两个金属夹固定复合布，垂直放置于通风橱安全台面上。采用1300℃火焰测试其隔热性能，测试时间3.0min，进行5组平行实验。得到相应数据。当1200-1300℃丁烷喷枪火焰对准复合布正面的喷烧，表面落在火焰的最高温度的外焰区域， 涂层受热发泡，发泡高度比原涂层高出30倍，同时发生相变，涂层转化成多孔碳化层，发泡过程吸收大量的热量，最终背面温度仅有84℃。离火后，复合布正面续燃时间平均小于0.1s、阴燃平均时间小于0.1s，具体实验结果见表6。
表6.阻燃复合布燃烧测试
为了进一步提升其隔热性能，可以继续在复合布的正反面涂覆阻燃改性涂层胶，厚度可以涂覆1-2mm，待涂层完全干燥后，附着力高，不会脱落，不会开裂同时具有很好的柔韧性。
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步详细说明，应理解的是，以上所述仅为本公开的具体实施例而已，并不用于限制本公开，凡在本公开的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。

Claims (11)

  1. 一种改性阻燃化合物，其具体结构如式(I)所示：
    式(I)所示化合物为在式(II)所示化合物中引入Si-(OMe)3基团获得；
    其中，式(II)所示化合物的结构如下：
  2. 一种制备权利要求1中所述式(I)所示化合物的方法，包括：
    A化合物与B化合物反应，得到式(I)所示化合物
  3. 根据权利要求2所述的方法，其中，所述方法包括：
    在有机溶剂和催化剂条件下，A化合物与B化合物混合形成阻燃混合液，向所述阻燃混合液中加pH调节剂，在预设温度下反应，得到式(I)所示化合物；
    其中：
    所述有机溶剂选自甲醇，催化剂选自氧化钙；
    所述A化合物与B化合物的摩尔比为1∶1～1∶1.2；
    预设反应温度为50-70℃；
    所述pH调节剂调节所述阻燃混合液的pH为中性，pH为6-7。
  4. 一种改性阻燃剂，包括：
    式(I)所示化合物和式(II)所示化合物的混合物；以及
    与所述混合物共混的共混剂，所述共混剂选自磷酸、铵盐、镁盐、三聚氰胺中一种或多种；
    其中，所述式(I)与式(II)所示化合物的结构如下：
    所述铵盐为氯化铵，所述镁盐选自氯化镁、硫酸镁中一种或多种。
  5. 根据权利要求4所述的改性阻燃剂，其中，所述共混剂与所述混合物的共混质量比为1∶20-50，式(I)所示化合物与式(II)所示化合物的质量比为1∶1-3。
  6. 一种阻燃改性涂层胶，包括如下重量份数的各个组分：
    其中，所有组分的重量份数之和为100，所述改性剂选自石墨、纤维、硅氧化物、钙氧化物、钛氧化物中一种或多种。
  7. 根据权利要求6所述的阻燃改性涂层胶，其中：
    所述润湿剂为BYK-306、BYK-S706、BYK-361、BYK-359、SN-4727A中的一种或多种的组合；
    所述消泡剂为SN-6710、有机硅消泡剂、矿物油、聚醚中的一种或多种的组合；
    所述成炭剂为葡萄糖、淀粉、蔗糖、环糊精、季戊四醇、双季戊四醇中的一种或多种的组合；
    所述分散剂为BYK-2150、BYK-330、BYK-341、BYK-307、BYK-2155、BYK-104S、SN-1728A、SN-1728、SN-1729、SN-1776、SN-1760、SN-1790A、SN-1791、SN-1790、SN-1792、SN-1798中的一种或多种的组合；
    所述防沉降剂为聚酰胺蜡、膨润土、聚乙烯蜡中的一种或多种的组合；
    所述稀释剂为汽油、水、甲醇、二甲苯、异丙醇、乙醇、乙酸乙酯、丙二醇二甲醚中的一种或多种的组合。
  8. 一种制备权利要求6-7中任一项所述的阻燃改性涂层胶的方法，包括：
    向含水性聚氨酯的反应器中加入稀释剂，搅拌直至液面中心出现旋涡；
    向所述反应器内缓慢加入湿润剂、消泡剂、分散剂后，加入聚磷酸铵阻燃剂、成炭剂到所述反应器内并混合均匀；
    再将改性剂加入至混合液中，再次分散搅拌均匀，得到所述阻燃改性涂层胶。
  9. 一种阻燃隔热复合布的制备方法，包括：
    在30-45℃下，将多片待处理织物浸泡于权利要求4-5中任一项所述的改性阻燃剂的水溶液中，浸泡处理后，在55-65℃下进行预烘，并在100-120℃下干燥，得到多片阻燃织物，其中改性阻燃剂与水的质量比为1∶10-30；
    在每片所述阻燃织物两面涂敷权利要求6-7中任一项所述的阻燃改性涂层胶作为隔热层，得到阻燃隔热织物；
    将多片所述阻燃隔热织物依次堆叠，利用所述阻燃改性涂层胶的粘性粘连在一起，干燥后得到所述阻燃隔热复合布；
    其中，所述待处理织物包括棉布、无纺布、涤纶、维伦、纤维布中任意一种，且多个依次堆叠的所述阻燃隔热织物各不相同；
    所述隔热层的厚度为0.1-3.5mm。
  10. 根据权利要求9所述的方法，其中，所述隔热层的厚度为0.1-2mm。
  11. 一种阻燃隔热复合布，其中，所述阻燃隔热复合布采用权利要求9-10中任一项所述的方法制得。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6343964A (ja) * 1986-08-11 1988-02-25 Daihachi Kagaku Kogyosho:Kk 表面改質無機粉体およびそれを含有する樹脂組成物
CN102060873A (zh) * 2010-09-16 2011-05-18 中国科学技术大学 N-羟甲基-3-(二甲氧基磷酰基)丙酰胺的制备方法
CN103608505A (zh) * 2011-06-22 2014-02-26 株式会社钟化 仿麂皮风格阻燃性交织织物
CN109652984A (zh) * 2018-12-12 2019-04-19 上海雅运新材料有限公司 一种织物阻燃涂层整理剂组合物及其制备方法
US20190153663A1 (en) * 2017-11-22 2019-05-23 Ten Cate Protect B.V. Method for Producing a Flame-Resistant Textile Article
CN114958139A (zh) * 2022-05-20 2022-08-30 中国科学技术大学先进技术研究院 一种阻燃剂、制法、含上述阻燃剂的涂层及含阻燃涂层的防爆电池箱
CN116854729A (zh) * 2023-06-30 2023-10-10 中国科学技术大学 改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6343964A (ja) * 1986-08-11 1988-02-25 Daihachi Kagaku Kogyosho:Kk 表面改質無機粉体およびそれを含有する樹脂組成物
CN102060873A (zh) * 2010-09-16 2011-05-18 中国科学技术大学 N-羟甲基-3-(二甲氧基磷酰基)丙酰胺的制备方法
CN103608505A (zh) * 2011-06-22 2014-02-26 株式会社钟化 仿麂皮风格阻燃性交织织物
US20190153663A1 (en) * 2017-11-22 2019-05-23 Ten Cate Protect B.V. Method for Producing a Flame-Resistant Textile Article
CN109652984A (zh) * 2018-12-12 2019-04-19 上海雅运新材料有限公司 一种织物阻燃涂层整理剂组合物及其制备方法
CN114958139A (zh) * 2022-05-20 2022-08-30 中国科学技术大学先进技术研究院 一种阻燃剂、制法、含上述阻燃剂的涂层及含阻燃涂层的防爆电池箱
CN116854729A (zh) * 2023-06-30 2023-10-10 中国科学技术大学 改性阻燃剂、阻燃改性涂层胶、复合布及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BIRNBAUM JEROME C., BUSCHE BRAD, LIN YUEHE, SHAW WENDY J., FRYXELL GLEN E.: "Synthesis of carbamoylphosphonate silanes for the selective sequestration of actinides", CHEMICAL COMMUNICATIONS, ROYAL SOCIETY OF CHEMISTRY, UK, no. 13, 19 June 2002 (2002-06-19), UK , pages 1374 - 1375, XP093252578, ISSN: 1359-7345, DOI: 10.1039/b200186c *

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