WO2018120742A1 - 囊体材料、囊体、浮空器及囊体材料的制备方法 - Google Patents

囊体材料、囊体、浮空器及囊体材料的制备方法 Download PDF

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Publication number
WO2018120742A1
WO2018120742A1 PCT/CN2017/092062 CN2017092062W WO2018120742A1 WO 2018120742 A1 WO2018120742 A1 WO 2018120742A1 CN 2017092062 W CN2017092062 W CN 2017092062W WO 2018120742 A1 WO2018120742 A1 WO 2018120742A1
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Prior art keywords
layer
polyurethane
coating
capsule material
capsule
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PCT/CN2017/092062
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English (en)
French (fr)
Inventor
刘若鹏
栾琳
李同兵
钟招汉
苏亚军
沈华龙
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深圳光启空间技术有限公司
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Publication of WO2018120742A1 publication Critical patent/WO2018120742A1/zh

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64B—LIGHTER-THAN AIR AIRCRAFT
    • B64B1/00—Lighter-than-air aircraft
    • B64B1/58—Arrangements or construction of gas-bags; Filling arrangements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the present invention relates to the field of aerospace technology, and in particular to a method for preparing a capsule material, a capsule, an aerostat, and a capsule material. Background technique
  • the aerostat provides static lift by filling the air-light-filled gas inside, and can achieve air-stopping in the Earth's stratosphere and its airspace. It has military and civilian fields such as earth observation, missile warning, communication relay, and air travel. Wide application prospects.
  • the capsule material is usually composed of a weathering layer, a barrier layer and a bearing (fabric) layer. Its main performance indicators include strength, barrier properties, weather resistance, and processability. Among them, the helium barrier performance of the barrier layer directly determines the air space of the aerostat and the maintenance and use cost.
  • the gas barrier layer of the capsule material mainly has the following three types: First, a high barrier polymer film or coating, such as ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyester And a fluoropolymer film.
  • EVOH ethylene-vinyl alcohol copolymer
  • PVA polyvinyl alcohol
  • polyester a fluoropolymer film.
  • the best barrier property is EVOH
  • the ⁇ ⁇ coating is coated on the polyethylene film, and the transmittance can be as low as 20 mIJ (m2*atm*24h).
  • the barrier property of the polymer is sensitive to water vapor, and the barrier property rapidly decreases as the water absorption rate increases, so it is usually necessary to cover the water vapor barrier layer on both sides thereof.
  • Polyvinyl alcohol (PVA) barrier films also have the above problems.
  • the barrier property of polyester film is slightly worse than EVOH and PVA, but it is still excellent.
  • the polyester film with thickness greater than 16 ⁇ has good barrier property and the transmittance is 1800mL /(m2* a tm*24h)/(16 m). . Due to its excellent mechanical properties and environmental stability, it is widely used in capsule materials, especially in the lamination process.
  • the fluoropolymer is excellent in weather resistance and is generally used as a weather-resistant layer of a capsule material. Since it also has good gas barrier properties, it functions as an auxiliary gas barrier in the capsule material.
  • a polyvinyl fluoride film having a thickness of 25 ⁇ m has a transmittance of 2300 mIJ (m 2 * a tm * 24 h) / (25 m).
  • the second is an aluminized polymer film or aluminum foil, and the close metal accumulation gives it excellent gas barrier properties.
  • the third is a polymer blend; the gas barrier properties of the polymer are improved by blending the inorganic material with the polymer or polymer/polymer blending.
  • the aerostat capsule materials are made of aluminized material, aluminum foil or PET as a gas barrier layer.
  • the aluminized film or the aluminum foil has excellent gas barrier properties, it has two significant disadvantages: First, the slag resistance is poor, and the gas barrier property after the enthalpy is greatly attenuated; second, the aluminized film does not have The thermal welding performance, the preparation of the aerostats can only be achieved by gluing, which increases the complexity of the process; while the PET is a gas barrier layer, the capsule material is less flexible.
  • the requirement of the high barrier layer of the aerostat capsule material is to make the quality as small as possible while ensuring the barrier requirement, and the weathering performance and processing performance of the skin material are not affected.
  • the present invention is directed to a method for preparing a capsule material, a capsule, an aerostat, and a capsule material to solve the technical problem of poor gas barrier properties of the gas barrier layer in the prior art.
  • a capsule material comprises a gas barrier layer which is a coating or film prepared by dispersing a double hydroxide sheet material in a polymer.
  • the polymer is a thermoplastic polyurethane.
  • the double hydroxide sheet material accounts for 1 to 10% by weight of the gas barrier layer.
  • the capsule material includes a weather resistant layer, a gas barrier layer, a glue layer and a load-bearing layer which are laminated in this order from the outside to the inside.
  • the weathering layer has a mass percentage of 3 to 20%.
  • the weather resistant layer has a thickness of 20 to 35 micrometers.
  • the adhesive layer is a polyurethane hot melt adhesive or a two-component polyurethane adhesive.
  • the thickness of the glue layer is 10 to 25 microns.
  • the load bearing layer is a fabric.
  • the fabric is a polyester fiber or an aramid fiber.
  • the thickness of the bearing layer is 100 to 150 microns.
  • a capsule is provided.
  • the capsule is made of any of the above capsule materials.
  • an aerostat is provided.
  • the aerostat includes a balloon made of any of the above-described balloon materials.
  • a method of preparing a balloon material comprises the following steps: Sl, coating a glue layer on the front side of the load-bearing layer; S2, in N, N-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, butanone, acetone, toluene One or several kinds of mixed solvent, adding double hydroxide sheet material and dispersing agent, stirring and ultrasonically dispersing, then adding thermoplastic polyurethane, heating and stirring until the polyurethane is completely dissolved, obtaining a slurry, and coating the slurry on the rubber layer Upper, drying, removing the solvent to form a gas barrier layer; and S3, providing a weathering layer on the gas barrier layer.
  • the slurry is applied onto the adhesive layer by solution doctoring, and dried at 80 ° C or higher to remove the solvent.
  • the weather-resistant layer is coated on the surface of the gas barrier layer by solution coating, and the weather-resistant layer is a polyurethane containing 3% by mass of ZnO or a thermoplastic having a mass fraction of 5-20% TiO2.
  • a composite film or coating of polyurethane is a polyurethane containing 3% by mass of ZnO or a thermoplastic having a mass fraction of 5-20% TiO2.
  • the present invention improves the barrier property by blending and modifying the polymer with a double hydroxide sheet material to make it a capsule.
  • the barrier layer of the bulk material thereby producing a capsule material having good flexibility.
  • FIG. 1 is a schematic cross-sectional view showing a capsule material according to an embodiment of the present invention.
  • the present invention provides a method of preparing a capsule material, a capsule, an aerostat, and a capsule material.
  • a balloon material is provided.
  • the capsule material includes a gas barrier layer which is a coating or film prepared by dispersing a double hydroxide sheet material in a polymer.
  • the present invention improves the barrier property by blending and modifying the polymer with a double hydroxide sheet material to make it a capsule.
  • the barrier layer of the bulk material thereby producing a capsule material having good flexibility.
  • Double hydroxide is an anionic supramolecular layered material composed of bivalent and trivalent metal ions combined with a chemical formula of [Mx2+ M3+
  • the metal cation M may be Mg 2+ , A13+, Li+, Zn 2+, Cr+ or the like, and x is a molar ratio of M 2+ to M 3 + , and usually the x value is 2 to 4.
  • An- is an anionic compound which may be p-aminobenzoic acid (AB), terminal aminododecanoic acid (AL), sodium dodecyl sulfate (NaDBS), glycine, nitric acid, and the like.
  • LDH is that it can adjust its physicochemical properties by changing the metal cations and interlayer anions of the laminate, making LDH a multifunctional inorganic layered material, which is often used as a catalyst, catalyst carrier, drug carrier, magnetic carrier, polymer. Flame retardant, etc.
  • the present invention utilizes its lamellar properties to disperse it in a polymer and finds that it can significantly improve the gas barrier properties of the polymer.
  • the addition of LDH can also improve the UV resistance and thermal stability of the polymer.
  • the polymer is a thermoplastic polyurethane.
  • the polyurethane has good weather resistance, excellent flexibility, weldability and low temperature resistance, but the gas barrier property is relatively poor.
  • the present invention improves the barrier property by blending and modifying the double hydroxide sheet material of the polyurethane. As a barrier layer of the capsule material, a capsule material having good flexibility and heat welding is obtained.
  • the double hydroxide sheet material accounts for 1% to 10% by weight of the gas barrier layer.
  • the modified polyurethane has excellent overall properties.
  • the capsule material includes a weather resistant layer 10, a gas barrier layer 20, a glue layer 30, and a load bearing layer 40 which are laminated in this order from the outside to the inside.
  • the weathering layer has a mass percentage of 3 to 20%.
  • ZnO and Ti02 are excellent inorganic UV absorbers, which have high UV absorption efficiency and good light scattering effect on visible light, so they can provide UV and visible light protection for the inner layer.
  • the addition amount of the integrated ZnO or ruthenium 02 and the ultraviolet-visible light barrier property of the weather resistant coating layer are preferably 20 to 35 ⁇ m.
  • the adhesive layer is a polyurethane hot melt adhesive or a two-component polyurethane adhesive, the polyurethane adhesive provides excellent peel strength, and the same has excellent low temperature flexibility and Weatherability, therefore very suitable for interlayer bonding of the functional layers of the capsule material.
  • the thickness of the adhesive layer is from 10 to 25 microns.
  • the load-bearing layer is a fabric, preferably the fabric is a polyester fiber, an aramid fiber or other high-strength fiber.
  • the load bearing layer has a thickness of from 100 to 150 microns.
  • a capsule is provided.
  • the capsule is made of any of the above-described capsule materials.
  • an aerostat is provided.
  • the aerostat includes a balloon made of any of the above-described balloon materials.
  • a method of preparing a balloon material comprises the following steps: Sl, coating a glue layer on the front side of the load-bearing layer; S2, in N, N-dimethylacetamide, N, N-dimethylformamide, butanone, acetone, toluene One or several kinds of mixed solvent, adding double hydroxide sheet material and dispersing agent, stirring and ultrasonically dispersing, then adding thermoplastic polyurethane, heating and stirring until the polyurethane is completely dissolved, obtaining a slurry, and coating the slurry on the rubber layer Upper, drying, removing the solvent to form a gas barrier layer; and S3, providing a weathering layer on the gas barrier layer.
  • the slurry is coated on the adhesive layer by solution doctoring, and dried at 80 ° C or higher to remove the solvent.
  • a weather-resistant layer is coated on the surface of the gas barrier layer by solution coating, and the weather-resistant layer is a polyurethane containing 3% by mass of ZnO or a thermoplastic having a mass fraction of 5-20% TiO2.
  • Polyurethane complex Film or coating are not bonded together by a conventional adhesive, but the interlayer bonding is achieved by a solution or a hot melt coating process, and the bonding strength is high and the adhesive layer is omitted, thereby reducing the capsule body. Material surface density and reduced cost.
  • the balloon material of the present invention can be used for air ballooning, airships, tethered balloons, automotive airbags, and the like.
  • the embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer and a fabric layer from top to bottom; the weathering layer has a mass fraction of 3% ZnO thermoplastic polyether aliphatic polyurethane, thickness 20 microns; gas barrier layer is a double hydroxide layer (Mg2Al-AB) material with a mass fraction of 1% polyester aromatic polyurethane coating, thickness 40 Micron;
  • the adhesive layer material is a polyester polyurethane hot melt adhesive with a thickness of 10 ⁇ m, high and low temperature resistance; the fabric layer material is a polyarylate fiber, and the thickness is 110 micrometers.
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 Apply a 10 micron thick adhesive layer to the front side of the fabric layer having a thickness of 110 micrometers; the aramid fiber material of the fabric layer; and the polyurethane hot melt adhesive.
  • Step 2 using hydrazine, hydrazine-dimethylacetamide as a solvent, and adding a double hydroxide sheet material (Mg2)
  • thermoplastic polyether aliphatic polyurethane After ultrasonic stirring for 10 min, add thermoplastic polyether aliphatic polyurethane, stir until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution coating, and dried at 80 ° C or higher to remove the solvent;
  • the double hydroxide sheet filler in the barrier layer has a mass fraction of 2% and a coating thickness of 40 ⁇ m.
  • Step 3 coating a weatherable polyester aromatic polyurethane coating on the surface of the high barrier polyurethane coating by a melt coating method
  • the weatherable polyurethane coating contains 3% by mass of ZnO and has a thickness of 20 microns.
  • the embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer and a fabric layer from top to bottom; the weathering layer has a mass fraction of 10% ZnO thermoplastic polyether aliphatic polyurethane with a thickness of 25 ⁇ m; barrier layer is a thermoplastic polyether aromatic polyurethane coating containing 3% by weight of a double hydroxide (Mg2Al-AL) sheet filler, thickness 35 microns; rubber sheet
  • the material is a two-component polyurethane adhesive with a thickness of 20 ⁇ m; the fabric layer material is a polyarylate fiber having a thickness of 10 ⁇ m.
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 Apply a 25 micron thick adhesive layer to the front side of the fabric layer having a thickness of 110 micrometers; the fabric layer material is Kevlar fiber; and the adhesive layer material is a two-component polyurethane adhesive.
  • Step 2 using hydrazine, hydrazine-dimethylformamide as a solvent, adding a double hydroxide (Mg2Al-AL) sheet material, and a dispersing agent (ytterbium stearate), and stirring for 10 minutes after ultrasonic stirring.
  • a double hydroxide Mg2Al-AL
  • a dispersing agent ytterbium stearate
  • thermoplastic polyether aliphatic polyurethane heat and stir until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution doctoring, and dried at 80 ° C or higher to remove the solvent;
  • the mass fraction of the double hydroxide sheet filler in the barrier layer was 3%, and the thickness of the coating layer was 35 ⁇ m.
  • Step 3 coating a weatherable polyether aromatic polyurethane coating on the surface of the high barrier polyurethane coating by a melt coating method
  • the weatherable polyurethane coating contains a mass fraction of 10% of ZnO and a thickness of 25 microns.
  • This embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer, and a fabric layer from top to bottom; the weathering layer has a mass fraction of 20% ZnO thermoplastic polyether aliphatic polyurethane coating, thickness 25 microns; barrier layer is a double hydroxide layer ( ⁇ 2 ⁇ 1- ⁇ L) filler content of 5% polyester aromatic polyurethane composite film The thickness of the adhesive layer is 20 ⁇ , the high-low temperature resistant polyester polyurethane hot melt adhesive; the fabric layer material is aramid fiber, and the thickness is 110 microns.
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 Applying a 20 ⁇ m thick adhesive layer to the front side of the fabric layer having a thickness of 110 ⁇ m; the material of the fabric layer is aramid fiber; and the adhesive layer material is a polyurethane hot melt adhesive.
  • Step 2 adding a mixture of hydrazine, hydrazine-dimethylacetamide and methyl ethyl ketone in a mass ratio of 1:1 as a solvent, adding a double hydroxide (Zn2Al-AL) sheet material, and a dispersing agent thereto After stirring, ultrasonically disperse lOmin, add thermoplastic polyester aromatic polyurethane, heat and stir until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution scraping, and dried at 80 ° C or higher to remove the solvent;
  • the barrier layer has a double hydroxide sheet filler mass fraction of 5% and a coating thickness of 25 micrometers.
  • Step 3 coating a weatherable polyether aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by solution knife coating;
  • the weatherable polyurethane coating contains 20% ZnO mass fraction and a thickness of 25 microns.
  • the embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer, and a fabric layer from top to bottom;
  • the weathering layer has a mass fraction of 15% Ti02 thermoplastic polyester aliphatic polyurethane coating with a thickness of 30 microns;
  • barrier layer is a polyether aliphatic polyurethane composite film with a mass fraction of 7% containing double hydroxide (Zn2Al-DS), with a thickness of 30 ⁇ m;
  • the adhesive layer material is a two-component polyurethane adhesive with a thickness of 20 ⁇ m;
  • the fabric layer material is Kevlar fiber and has a thickness of 120 ⁇ m.
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 coating a 10 ⁇ m thick adhesive layer on the front side of the 120 ⁇ m thick fabric layer; the fabric layer material is Kevlar fiber; and the adhesive layer material is a two component polyurethane adhesive.
  • Step 2 using a mixture of ruthenium, osmium-dimethylformamide and acetone in a mass ratio of 3:1 as a solvent, adding a double hydroxide (Zn2Al-DS) sheet material thereto, and a dispersant ( BYK-160), after ultrasonic stirring for 10 min, add thermoplastic polyester aliphatic polyurethane, stir until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution doctoring, and dried at 80 ° C or higher to remove the solvent;
  • the double hydroxide (Zn2Al-DS) sheet filler in the barrier layer has a mass fraction of 7% and a coating thickness of 30 ⁇ m.
  • Step 3 coating a weatherable polyether aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by solution knife coating;
  • the weatherable polyurethane coating contains 15% by mass of Ti02 and has a thickness of 30 microns.
  • This embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer, and a fabric layer from top to bottom; the weathering layer has a mass fraction of 15 % ⁇ 02 thermoplastic polyurethane coating, thickness 30 microns; barrier layer is a thermoplastic polyether aromatic polyurethane coating with a mass fraction of 8% containing a double hydroxide (Mg2Al-DS), thickness 25 microns; Layer material is thickness 25 ⁇ , high temperature resistant polyurethane hot melt adhesive; fabric layer material is aramid fiber, thickness is 110 microns.
  • a double hydroxide Mg2Al-DS
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 coating a 10 ⁇ m thick glue layer on the front side of the fabric layer having a thickness of 110 ⁇ m; the material of the fabric layer is an aramid dimension; and the glue layer material is a polyurethane hot melt adhesive.
  • Step 2 adding a double hydroxide layer (Mg2Al-DS) material and a dispersing agent (BYK) with a mixture of ruthenium, dimethyl acetamide and toluene in a mass ratio of 5:1. -170), after ultrasonic stirring for 10 min, adding thermoplastic polyurethane, stirring, until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution coating, and dried at 80 ° C or higher to remove the solvent;
  • the barrier layer has a double hydroxide layer filler mass fraction of 8% and a coating thickness of 25 micrometers.
  • Step 3 coating a weatherable polyester aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by a melt coating method
  • the weatherable polyurethane coating contains 15% by mass of Ti02 and has a thickness of 30 microns.
  • the embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer and a fabric layer from top to bottom; the weathering layer has a mass fraction of 20% TiO2 thermoplastic polyether aliphatic polyurethane coating with a thickness of 35 microns; the barrier layer is a thermoplastic polyester aromatic polyurethane coating containing 10% by mass of the double hydroxide layer (Mg2Al-D S) filler.
  • the thickness of the adhesive layer is a two-component polyurethane adhesive with a thickness of 15 ⁇ m; the fabric layer material is aramid fiber with a thickness of 10 ⁇ m.
  • the method for preparing the above capsule material comprises the following steps:
  • Step 1 Coating a 15 ⁇ m thick adhesive layer on the front side of the fabric layer having a thickness of 110 ⁇ m; the fabric layer material is aramid fiber; and the adhesive layer material is a two-component polyurethane adhesive.
  • Step 2 using butanone as a solvent, adding a double hydroxide (Mg2Al-DS) sheet material, and a dispersing agent (calcium stearate), stirring and ultrasonic dispersion for 10 min, adding thermoplastic polyester aromatic Polyurethane
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution doctoring, and dried at 80 ° C or higher to remove the solvent;
  • the double hydroxide (Mg2Al-DS) sheet filler in the barrier layer has a mass fraction of 10% and a coating thickness of 15 micrometers.
  • Step 3 coating a weatherable polyether aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by solution knife coating;
  • the weatherable polyurethane coating contains 20% by mass of Ti02 and a thickness of 35 microns.
  • This embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer, and a fabric layer from top to bottom; the weathering layer is a quality containing Ti02.
  • a thermoplastic polyester aliphatic polyurethane having a fraction of 5% and a thickness of 25 ⁇ m; a barrier layer of a polyether aliphatic polyurethane coating containing a double hydroxide layer (Mg2Al-N03) having a mass fraction of 10% and having a thickness of 15 Micron;
  • the adhesive layer material is a two-component polyurethane adhesive with a thickness of 10 microns;
  • the fabric layer material is aramid fiber with a thickness of 110 microns.
  • the above method for preparing a capsule material comprises the following steps:
  • Step 1 coating a 10 ⁇ m thick adhesive layer on the front side of the fabric layer having a thickness of 110 ⁇ m; the material of the fabric layer is an aramid dimension; and the adhesive layer material is a two-component polyurethane adhesive.
  • Step two using hydrazine, hydrazine-dimethylacetamide as a solvent, adding a double hydroxide (Mg2Al-DS) sheet material, and a dispersing agent (BYK-160), stirring and ultrasonic dispersion for 10 min, Add thermoplastic polyester aromatic polyurethane and stir until the polyurethane is completely dissolved.
  • the polyurethane solution is coated on the surface of the woven fabric coated with the adhesive by solution coating, and dried at 80 ° C or higher to remove the solvent;
  • the barrier layer has a double hydroxide sheet filler mass fraction of 10% and a coating thickness of 15 micrometers.
  • Step 3 coating a weatherable polyether aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by solution knife coating;
  • the weatherable polyurethane coating contains ⁇ 02 in a mass fraction of 5% and a thickness of 25 microns.
  • This embodiment provides a capsule material, which is composed of a four-layer structure, which is a weathering layer, a gas barrier layer, a rubber layer, and a fabric layer from top to bottom;
  • the weathering layer is a quality containing Ti02. 5% thermoplastic polyester aliphatic polyurethane with a thickness of 25 ⁇ m;
  • barrier layer is a pure polyether aliphatic polyurethane coating with a thickness of 25 ⁇ m;
  • adhesive layer is a two-component polyurethane adhesive with a thickness of 10 ⁇ m
  • the fabric layer material is aramid fiber with a thickness of 110 microns;
  • the method for preparing the above capsule material comprises the following steps: [0104] Step 1: Coating a 10 ⁇ m thick adhesive layer on the front side of the fabric layer having a thickness of 110 ⁇ m; the material of the fabric layer is aramid mesh; and the adhesive layer material is a two-component polyurethane adhesive.
  • Step 2 Using hydrazine, hydrazine-dimethylacetamide as a solvent, adding a thermoplastic polyester aromatic polyurethane, and stirring until the polyurethane is completely dissolved.
  • the polyurethane solution was coated on the surface of the woven fabric coated with the adhesive by solution doctoring, and dried at 80 ° C or higher to remove the solvent; the coating thickness was 125 ⁇ m.
  • Step 3 coating a weatherable polyether aliphatic polyurethane coating on the surface of the high barrier polyurethane coating by solution knife coating;
  • the weatherable polyurethane coating contains 5%02 in a mass fraction of 5% and a thickness of 25 microns.
  • Table 1 shows the helium permeability (ml/24 h.atm.m2) of the comparative examples and examples after untwisting and enthalpy.
  • the gas barrier layer of the capsule material of the embodiment of the invention may be a thermoplastic polyurethane, which is softer than ordinary skin material, has significantly improved folding pressure and smash resistance, and is subjected to folding and shear fatigue loads. The back barrier performance is always maintained at a high level, and the damage resistance is good;
  • the outermost layer (weathering layer) of the capsule material of the embodiment of the invention is made of thermoplastic polyurethane as a matrix resin, has heat weldability, and simplifies the manufacturing process of the aerostat;

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Abstract

一种囊体材料、囊体、浮空器及囊体材料的制备方法。其中该囊体材料包括气体阻隔层（20），气体阻隔层（20）为双氢氧化物片层材料分散于聚合物之中所制备的涂层或薄膜。由于聚合物本身通常具有较好的柔韧性，但气体阻隔性能比较差，通过对聚合物进行双氢氧化物片层材料共混改性，提高其阻隔性，使其作为囊体材料的阻隔层，从而制得具有良好柔韧性的囊体材料。

Description

说明书 发明名称：囊体材料、 囊体、 浮空器及囊体材料的制备方法 技术领域
[0001] 本发明涉及航空航天技术领域， 具体而言， 涉及一种囊体材料、 囊体、 浮空器 及囊体材料的制备方法。 背景技术
[0002] 浮空器通过内部充满轻于空气的气体提供静升力， 可在地球平流层及其以下空 域实现驻空停留， 在对地观测、 导弹预警、 通信中继、 航空旅游等军民领域具 有广泛的应用前景。 囊体材料作为浮空器的主体结构材料， 通常由耐候层、 阻 隔层、 承力 （织物） 层复合而成， 其主要性能指标包括强度、 阻隔性、 耐候性 、 可加工性能等。 其中， 阻隔层的氦气阻隔性能直接决定了浮空器的驻空吋间 以及维护使用成本。
[0003] 目前， 囊体材料的气体阻隔层主要有以下三类： 一是高阻隔性聚合物薄膜或涂 层， 如乙烯-乙烯醇共聚物 （EVOH) 、 聚乙烯醇 （PVA) 、 聚酯以及含氟聚合 物薄膜。 其中， 阻隔性最好的是 EVOH, 将 Ιμηι ΕνθΗ涂层涂覆在聚乙烯薄膜上 ， 透氦率就可以低至 20mIJ(m2*atm*24h)。 但该聚合物的阻隔性对水汽敏感， 阻 隔性随吸水率增加而迅速降低， 因此通常需要在其两侧覆盖水汽阻隔层。 聚乙 烯醇 （PVA) 阻隔性薄膜也存在上述问题。 聚酯薄膜的阻隔性相比 EVOH和 PVA 稍差但仍算优异， 厚度大于 16μηι的聚酯薄膜自身阻隔性较好， 透氦率为 1800mL /(m2*atm*24h)/(16 m)。 同吋由于其优异的力学性能和环境稳定性， 使其广泛应 用于囊体材料， 尤其是层压复合工艺制造的囊体材料。 含氟聚合物耐候性极佳 ， 通常作为囊体材料的耐候层， 由于其也具有不错的气体阻隔性， 在囊体材料 中起到辅助的气体阻隔作用。 如厚度 25μηι的聚氟乙烯薄膜其透氦率为 2300mIJ( m2*atm*24h)/(25 m)。 二是镀铝聚合物薄膜或铝箔， 紧密的金属堆积赋予其优异 的气体阻隔性。 三是聚合物共混物； 通过无机材料与聚合物共混或聚合物 /聚合 物共混， 提高聚合物的气体阻隔性。
技术问题 [0004] 目前， 浮空器囊体材料大多采用镀铝材料、 铝箔或 PET为气体阻隔层。 虽然镀 铝膜或铝箔具有优异的气体阻隔性， 但其具有两个显著的缺点： 其一， 耐揉搓 性较差， 经揉搓后的气体阻隔性衰减较大； 其二， 镀铝膜不具有热焊接性能， 制备浮空器吋只能通过涂胶粘接， 增加了工艺的复杂性； 而 PET为气体阻隔层的 囊体材料柔性较差。
[0005] 浮空器囊体材料对高阻隔层的要求是在保证阻隔要求的情况下使质量尽量小， 同吋不影响蒙皮材料耐候性能和加工性能。
问题的解决方案
技术解决方案
[0006] 本发明旨在提供一种囊体材料、 囊体、 浮空器及囊体材料的制备方法， 以解决 现有技术中气体阻隔层耐揉搓性较差的技术问题。
[0007] 为了实现上述目的， 根据本发明的一个方面， 提供了一种囊体材料。 该囊体材 料包括气体阻隔层， 气体阻隔层为双氢氧化物片层材料分散于聚合物之中所制 备的涂层或薄膜。
[0008] 进一步地， 聚合物为热塑性聚氨酯。
[0009] 进一步地， 双氢氧化物片层材料占气体阻隔层的重量百分比为 1~10%。
[0010] 进一步地， 囊体材料包括由外向内依次层叠设置的耐候层、 气体阻隔层、 胶层 和承重层。
[0011] 进一步地， 耐候层为含质量百分数为 3~20%
ZnO的聚氨酯或含质量分数为 5~20%TiO2的热塑性聚氨酯的复合膜或涂层。
[0012] 进一步地， 耐候层的厚度为 20~35微米。
[0013] 进一步地， 胶层为聚氨酯热熔胶或双组份聚氨酯胶黏剂。
[0014] 进一步地， 胶层的厚度为 10~25微米。
[0015] 进一步地， 承重层为织物。
[0016] 进一步地， 织物为涤纶纤维或芳纶纤维。
[0017] 进一步地， 承重层的厚度为 100~150微米。
[0018] 根据本发明的另一个方面， 提供了一种囊体。 该囊体由上述任一种囊体材料制 成。 [0019] 根据本发明的再一个方面， 提供了一种浮空器。 该浮空器包括囊体， 囊体由上 述任一种囊体材料制成。
[0020] 根据本发明的又一个方面， 提供了一种囊体材料的制备方法。 该制备方法包括 以下步骤： Sl， 在承重层的正面涂覆胶层； S2， 以 N， N-二甲基乙酰胺、 Ν,Ν-二 甲基甲酰胺、 丁酮、 丙酮、 甲苯中的一种或几种混合为溶剂， 加入双氢氧化物 片层材料以及分散剂， 搅拌后超声分散， 然后加入热塑性聚氨酯， 加热搅拌至 聚氨酯完全溶解， 得到浆料， 将浆料涂覆在胶层上， 干燥， 除去溶剂形成气体 阻隔层； 以及 S3， 在气体阻隔层上设置耐候层。
[0021] 进一步地， S2中， 通过溶液刮涂法在将浆料涂覆在胶层上， 在 80°C以上干燥， 除去溶剂。
[0022] 进一步地， S3中， 通过溶液刮涂法在气体阻隔层表面涂布耐候层， 耐候层为含 质量百分数为 3~20% ZnO的聚氨酯或含质量分数为 5~20%TiO2的热塑性聚氨酯的 复合膜或涂层。
[0023] 根据本发明的再一个方面， 提供一种囊体材料在探空气球、 飞艇、 系留气球、 汽车气囊方面的应用。
发明的有益效果
有益效果
[0024] 由于聚合物本身通常具有较好的柔韧性， 但气体阻隔性能比较差， 本发明通过 对聚合物进行双氢氧化物片层材料共混改性， 提高其阻隔性， 使其作为囊体材 料的阻隔层， 从而制得具有良好柔韧性的囊体材料。
对附图的简要说明
附图说明
[0025] 构成本申请的一部分的说明书附图用来提供对本发明的进一步理解， 本发明的 示意性实施例及其说明用于解释本发明， 并不构成对本发明的不当限定。 在附 图中：
[0026] 图 1示出了根据本发明一实施方式的囊体材料剖面结构示意图。 本发明的实施方式
[0027] 需要说明的是， 在不冲突的情况下， 本申请中的实施例及实施例中的特征可以 相互组合。 下面将参考附图并结合实施例来详细说明本发明。
[0028] 针对现有技术中存在的问题， 本发明提供一种囊体材料、 囊体、 浮空器及囊体 材料的制备方法。
[0029] 根据本发明一种典型的实施方式， 提供一种囊体材料。 该囊体材料包括气体阻 隔层， 气体阻隔层为双氢氧化物片层材料分散于聚合物之中所制备的涂层或薄 膜。
[0030] 由于聚合物本身通常具有较好的柔韧性， 但气体阻隔性能比较差， 本发明通过 对聚合物进行双氢氧化物片层材料共混改性， 提高其阻隔性， 使其作为囊体材 料的阻隔层， 从而制得具有良好柔韧性的囊体材料。
[0031] 双氢氧化物 （LDH) 是一种阴离子型超分子层状材料， 层板间由二价和三价金 属离子结合组成， 其化学通式为 [Mx2+ M3+
(ΟΗ)2χ+2]+·(Αη- l/n)«mH20 , 其中 An-是指层间阴离子。 金属阳离子 M可以是 Mg 2+、 A13+、 Li+、 Zn2+、 Cr+等， x为 M2+和 M3+的摩尔比， 通常 x值为 2~4。 An- 为阴离子化合物， 可以是对氨基苯甲酸 （AB) 、 端氨基十二烷基酸 (AL)、 十二 烷基磺酸钠 （NaDBS) 、 氨基乙酸、 硝酸等。 LDH的优点在于可以通过改变层 板金属阳离子及层间阴离子来调节其物理化学性能， 使 LDH成为一种多功能的 无机层状材料， 常用作催化剂、 催化剂载体、 药物载体、 磁性载体、 聚合物阻 燃剂等。 本发明利用其层状特性， 将其分散在聚合物中， 发现其可显著提高聚 合物的气体阻隔性能， 此外 LDH的加入还可提高聚合物的耐紫外性能和热稳定 性。
[0032] 优选的， 聚合物为热塑性聚氨酯。 聚氨酯具有良好的耐候性、 优异的柔韧性、 可焊接性和耐低温性能， 但是气体阻隔性能比较差， 本发明通过对聚氨酯进行 双氢氧化物片层材料共混改性， 提高其阻隔性， 作为囊体材料的阻隔层， 从而 制得具有良好柔韧性和可热焊接的囊体材料。
[0033] 优选的， 双氢氧化物片层材料占气体阻隔层的重量百分比为 1~10%。 在此范围 内， 改性的聚氨酯整体性能优良。 [0034] 根据本发明一种典型的实施方式， 如图 1所示， 囊体材料包括由外向内依次层 叠设置的耐候层 10、 气体阻隔层 20、 胶层 30和承重层 40。
[0035] 优选的， 耐候层为含质量百分数为 3~20%
ZnO的聚氨酯或含质量分数为 5~20%TiO2的热塑性聚氨酯的复合膜或涂层。 ZnO 与 Ti02是优良的无机紫外吸收剂， 对紫外线吸收效率高， 同吋对可见光具有很 强的光散射效应， 因此可对内层材料提供紫外与可见光防护功能。 优选的， 综 合 ZnO或 Ή02的添加量以及耐候涂层的紫外-可见光阻隔性， 耐候层的厚度优选 为 20~35微米。
[0036] 根据本发明一种典型的实施方式， 胶层为聚氨酯热熔胶或双组份聚氨酯胶黏剂 ， 聚氨酯类胶黏剂可提供优异的剥离强度， 同吋具有优异的低温柔韧性和耐候 性， 因此非常适合用于囊体材料各功能层的层间胶合。 优选的， 胶层的厚度为 1 0~25微米。
[0037] 根据本发明一种典型的实施方式， 承重层为织物， 优选的， 织物为涤纶纤维、 芳纶纤维或其他高强纤维。 优选的， 承重层的厚度为 100~150微米。
[0038] 根据本发明一种典型的实施方式， 提供一种囊体。 该囊体由上述任一种囊体材 料制成。
[0039] 根据本发明一种典型的实施方式， 提供一种浮空器。 该浮空器包括囊体， 囊体 由上述任一种囊体材料制成。
[0040] 根据本发明一种典型的实施方式， 提供一种囊体材料的制备方法。 该制备方法 包括以下步骤： Sl， 在承重层的正面涂覆胶层； S2， 以 N， N-二甲基乙酰胺、 N, N-二甲基甲酰胺、 丁酮、 丙酮、 甲苯中的一种或几种混合为溶剂， 加入双氢氧 化物片层材料以及分散剂， 搅拌后超声分散， 然后加入热塑性聚氨酯， 加热搅 拌至聚氨酯完全溶解， 得到浆料， 将浆料涂覆在胶层上， 干燥， 除去溶剂形成 气体阻隔层； 以及 S3， 在气体阻隔层上设置耐候层。
[0041] 优选的， S2中， 通过溶液刮涂法在将浆料涂覆在胶层上， 在 80°C以上干燥， 除 去溶剂。
[0042] 优选的， S3中， 通过溶液刮涂法在气体阻隔层表面涂布耐候层， 耐候层为含质 量百分数为 3~20% ZnO的聚氨酯或含质量分数为 5~20%TiO2的热塑性聚氨酯的复 合膜或涂层。 气体阻隔层和耐候层间不使用常规的胶黏剂贴合， 而是通过溶液 或热融涂布工艺实现层间贴合， 粘接强度高并省掉了胶黏剂层， 从而降低囊体 材料面密度并降低了成本。
[0043] 本发明的囊体材料可以用于探空气球、 飞艇、 系留气球、 汽车气囊等方面。
[0044] 下面将结合实施例进一步说明本发明的有益效果。
[0045] 实施例 1
[0046] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数为 3%ZnO的热塑性聚 醚脂肪族聚氨酯， 厚度为 20微米； 气体阻隔层为含双氢氧化物片层 （Mg2Al-AB ) 材料质量分数为 1%的聚酯芳香族聚氨酯涂层， 厚度为 40微米； 胶层材料为厚 度 10μηι， 耐高低温的聚酯型聚氨酯热熔胶， ； 织物层材料为聚芳酯纤维， 厚度 为 110微米。
[0047] 上述囊体材料的制备方法， 包含以下步骤：
[0048] 步骤一： 在厚度为 110微米的织物层的正面涂覆 10微米厚的胶层； 织物层的材 料为芳纶纤维； 胶层材料为聚氨酯热熔胶。
[0049] 步骤二： 以 Ν,Ν-二甲基乙酰胺为溶剂， 向其中加入双氢氧化物片层材料 （Mg2
A1-AB) ， 以及分散剂 （硬脂酸钙） ， 搅拌后超声分散 10min， 加入热塑性聚醚 脂肪族聚氨酯， 搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在涂有胶黏剂的织 布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂；
[0050] 阻隔层中双氢氧化物片层填料质量分数为 2%， 涂层厚度为 40微米。
[0051] 步骤三： 通过熔融涂覆法在高阻隔聚氨酯涂层表面涂布耐候聚酯芳香族聚氨酯 涂层；
[0052] 耐候聚氨酯涂层含质量分数 3%的 ZnO， 厚度为 20微米。
[0053] 实施例 2.
[0054] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数为 10%ZnO的热塑性聚 醚型脂肪族聚氨酯， 厚度为 25微米； 阻隔层为含双氢氧化物 （Mg2Al-AL) 片层 填料质量分数为 3%的热塑性聚醚型芳香族聚氨酯涂层， 厚度为 35微米； 胶层材 料为双组份聚氨酯胶黏剂， 厚度为 20微米； 织物层材料为聚芳酯纤维， 厚度为 1 10微米。
[0055] 上述的囊体材料的制备方法， 包含以下步骤：
[0056] 步骤一： 在厚度为 110微米的织物层的正面涂覆 25微米厚的胶层； 织物层的材 料为凯夫拉纤维； 胶层材料为双组份聚氨酯胶黏剂。
[0057] 步骤二： 以 Ν,Ν-二甲基甲酰胺为溶剂， 向其中加入双氢氧化物 （Mg2Al-AL) 片层材料， 以及分散剂 （硬脂酸钡） ， 搅拌后超声分散 10min， 加入热塑性聚醚 脂肪族聚氨酯， 加热搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在涂有胶黏剂 的织布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂；
[0058] 阻隔层中双氢氧化物片层填料质量分数为 3%， 涂层厚度为 35微米。
[0059] 步骤三： 通过熔融涂覆法在高阻隔聚氨酯涂层表面涂布耐候聚醚性芳香族聚氨 酯涂层；
[0060] 耐候聚氨酯涂层含质量分数含 ZnO质量分数 10%的， 厚度为 25微米。
[0061] 实施例 3.
[0062] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数为 20%ZnO的热塑性聚 醚型脂肪族聚氨酯涂层， 厚度为 25微米； 阻隔层为含双氢氧化物片层 （Ζη2Α1-Α L) 填料质量分数为 5%的聚酯型芳香族聚氨酯复合膜， 厚度为 25微米； 胶层材 料为厚度 20μηι， 耐高低温的聚酯型聚氨酯热熔胶； 织物层材料为芳纶纤维， 厚 度为 110微米。
[0063] 上述的囊体材料的制备方法， 包含以下步骤：
[0064] 步骤一： 在厚度为 110微米的织物层的正面涂覆 20微米厚的胶层； 织物层的材 料为芳纶纤维； 所述胶层材料为聚氨酯热熔胶。
[0065] 步骤二： 以 Ν,Ν-二甲基乙酰胺与丁酮质量分数比为 1:1的混合物为溶剂， 向其 中加入双氢氧化物 （Zn2Al-AL) 片层材料， 以及分散剂， 搅拌后超声分散 lOmin ， 加入热塑性聚酯芳香族聚氨酯， 加热搅拌， 至聚氨酯完全溶解。 通过溶液刮 涂法在涂有胶黏剂的织布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂；
[0066] 所述阻隔层中双氢氧化物片层填料质量分数为 5%， 涂层厚度为 25微米。 [0067] 步骤三： 通过溶液刮涂法在高阻隔聚氨酯涂层表面涂布耐候聚醚脂肪族聚氨酯 涂层；
[0068] 耐候聚氨酯涂层含 ZnO质量分数为 20%， 厚度为 25微米。
[0069] 实施例 4.
[0070] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数为 15%Ti02的热塑性 聚酯脂肪族聚氨酯涂层， 厚度为 30微米； 阻隔层为含双氢氧化物 （Zn2Al-DS) 片层填料质量分数为 7%的聚醚脂肪族聚氨酯复合膜， 厚度为 30微米； 胶层材料 为双组份聚氨酯胶黏剂， 厚度为 20微米； 织物层材料为凯夫拉纤维， 厚度为 120 微米。
[0071] 上述的囊体材料的制备方法， 包含以下步骤：
[0072] 步骤一： 在厚度为 120微米的织物层的正面涂覆 10微米厚的胶层； 织物层的材 料为凯夫拉纤维； 所述胶层材料为双组份聚氨酯胶黏剂。
[0073] 步骤二： 以 Ν,Ν-二甲基甲酰胺与丙酮质量分数比为 3:1的混合物为溶剂， 向其 中加入双氢氧化物 （Zn2Al-DS) 片层材料， 以及分散剂 （BYK-160) ， 搅拌后 超声分散 10min， 加入热塑性聚酯脂肪族聚氨酯， 搅拌， 至聚氨酯完全溶解。 通 过溶液刮涂法在涂有胶黏剂的织布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶 剂；
[0074] 所述阻隔层中双氢氧化物 （Zn2Al-DS) 片层填料质量分数为 7%， 涂层厚度为 3 0微米。
[0075] 步骤三： 通过溶液刮涂法在高阻隔聚氨酯涂层表面涂布耐候聚醚脂肪族聚氨酯 涂层；
[0076] 耐候聚氨酯涂层含质量分数 15%的 Ti02， 厚度为 30微米。
[0077] 实施例 5.
[0078] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数 15% Ή02的热塑性聚 氨酯涂层， 厚度为 30微米； 阻隔层为含双氢氧化物 （Mg2Al-DS) 片层填料质量 分数为 8%的热塑性聚醚芳香族聚氨酯涂层， 厚度为 25微米； 胶层材料为厚度 25 μηι， 耐高低温的聚氨酯热熔胶； 织物层材料为芳纶纤维， 厚度为 110微米。
[0079] 上述的囊体材料的制备方法， 包含以下步骤：
[0080] 步骤一： 在厚度为 110微米的织物层的正面涂覆 10微米厚的胶层； 织物层的材 料为芳纶维； 所述胶层材料为聚氨酯热熔胶。
[0081] 步骤二： 以 Ν,Ν-二甲基乙酰胺与甲苯质量分数比为 5:1混合物为溶剂， 向其中 加入双氢氧化物片层 （Mg2Al-DS) 材料， 以及分散剂 (BYK-170), 搅拌后超声 分散 10min， 加入热塑性聚氨酯， 搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在 涂有胶黏剂的织布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂；
[0082] 所述阻隔层中双氢氧化物片层填料质量分数为 8%， 涂层厚度为 25微米。
[0083] 步骤三： 通过熔融涂覆法在高阻隔聚氨酯涂层表面涂布耐候聚酯脂肪族聚氨酯 涂层；
[0084] 耐候聚氨酯涂层含质量分数 15%的 Ti02， 厚度为 30微米。
[0085] 实施例 6.
[0086] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含质量分数为 20%TiO2的热塑性 聚醚脂肪族聚氨酯涂层， 厚度为 35微米； 阻隔层为含双氢氧化物片层 （Mg2Al-D S) 填料质量分数为 10%的热塑性聚酯芳香族聚氨酯涂层， 厚度为 15微米； 胶层 材料为双组份聚氨酯胶黏剂， 厚度为 15微米； 织物层材料为芳纶纤维， 厚度为 1 10微米。
[0087] 上述的囊体材料的制备方法， 包含以下步骤：
[0088] 步骤一： 在厚度为 110微米的织物层的正面涂覆 15微米厚的胶层； 织物层的材 料为芳纶纤维； 所述胶层材料为双组份聚氨酯胶黏剂。
[0089] 步骤二： 以丁酮为溶剂， 向其中加入双氢氧化物 （Mg2Al-DS) 片层材料， 以 及分散剂 （硬脂酸钙） ， 搅拌后超声分散 10min， 加入热塑性聚酯芳香族聚氨酯
， 搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在涂有胶黏剂的织布面涂覆聚氨 酯溶液， 在 80°C以上干燥， 除去溶剂；
[0090] 所述阻隔层中双氢氧化物 （Mg2Al-DS) 片层填料质量分数为 10%， 涂层厚度 为 15微米。 [0091] 步骤三： 通过溶液刮涂法在高阻隔聚氨酯涂层表面涂布耐候聚醚脂肪族聚氨酯 涂层；
[0092] 耐候聚氨酯涂层含质量分数 20%的 Ti02， 厚度为 35微米。
[0093] 实施例 7.
[0094] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含 Ti02的质量分数为 5%的热塑性 聚酯脂肪族聚氨酯， 厚度为 25微米； 阻隔层为含双氢氧化物片层 （Mg2Al-N03 ) 填料质量分数为 10%的聚醚脂肪族聚氨酯涂层， 厚度为 15微米； 胶层材料为 双组份聚氨酯胶黏剂， 厚度为 10微米； 织物层材料为芳纶纤维， 厚度为 110微米
[0095] 上述的囊体材料的制备方法， 包含以下步骤：
[0096] 步骤一： 在厚度为 110微米的织物层的正面涂覆 10微米厚的胶层； 织物层的材 料为芳纶维； 所述胶层材料为双组份聚氨酯胶黏剂。
[0097] 步骤二： 以 Ν,Ν-二甲基乙酰胺为溶剂， 向其中加入双氢氧化物 （Mg2Al-DS) 片层材料， 以及分散剂 （BYK-160) ， 搅拌后超声分散 10min， 加入热塑性聚酯 芳香族聚氨酯， 搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在涂有胶黏剂的织 布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂；
[0098] 所述阻隔层中双氢氧化物片层填料质量分数为 10%， 涂层厚度为 15微米。
[0099] 步骤三： 通过溶液刮涂法在高阻隔聚氨酯涂层表面涂布耐候聚醚脂肪族聚氨酯 涂层；
[0100] 耐候聚氨酯涂层含 Ή02的质量分数为 5%， 厚度为 25微米。
[0101] 对比例
[0102] 本实施例提供一种囊体材料， 该囊体材料由四层结构组成， 从上至下顺次为耐 候层、 气体阻隔层、 胶层、 织物层； 耐候层为含 Ti02的质量分数为 5%的热塑性 聚酯脂肪族聚氨酯， 厚度为 25微米； 阻隔层为纯聚醚脂肪族聚氨酯涂层， 厚度 为 25微米； 胶层材料为双组份聚氨酯胶黏剂， 厚度为 10微米； 织物层材料为芳 纶纤维， 厚度为 110微米；
[0103] 上述的囊体材料的制备方法， 包含以下步骤： [0104] 步骤一： 在厚度为 110微米的织物层的正面涂覆 10微米厚的胶层； 织物层的材 料为芳纶维； 所述胶层材料为双组份聚氨酯胶黏剂。
[0105] 步骤二： 以 Ν,Ν-二甲基乙酰胺为溶剂， 加入热塑性聚酯芳香族聚氨酯， 搅拌， 至聚氨酯完全溶解。 通过溶液刮涂法在涂有胶黏剂的织布面涂覆聚氨酯溶液， 在 80°C以上干燥， 除去溶剂； 涂层厚度为 125微米。
[0106] 步骤三： 通过溶液刮涂法在高阻隔聚氨酯涂层表面涂布耐候聚醚脂肪族聚氨酯 涂层；
[0107] 耐候聚氨酯涂层含 Ή02的质量分数为 5%， 厚度为 25微米。
[0108] 下表 1为对比例和实施例在未揉搓和揉搓后的氦气渗透率 （ml/24h.atm.m2) 。
Figure imgf000013_0001
[0109] 从以上的描述中， 可以看出， 本发明上述的实施例实现了如下技术效果： [0110] 1) 通过向聚氨酯树脂中添加双氢氧化物片层材料， 其阻隔效果得到显著提升
[0111] 2) 本发明实施例的囊体材料的气体阻隔层可以为热塑性聚氨酯， 与普通蒙皮 材料相比更加柔软， 耐折压、 耐揉搓性能显著提高， 经受折压和剪切疲劳载荷 后阻隔性能始终保持在较高水平， 耐损伤性能较好；
[0112] 3) 本发明实施例的囊体材料的气体阻隔层和耐候层间不使用常规的胶黏剂贴 合， 而是通过溶液或热融涂布工艺实现层间贴合， 粘接强度高并省掉了胶黏剂 层， 从而降低囊体材料面密度并降低了成本；
[0113] 4) 本发明实施例的囊体材料的最外层 （耐候层） 以热塑性聚氨酯为基体树脂 ， 具有可热焊接性， 简化了浮空器制造工艺；
[0114] 5) 制备工艺简单， 采用涂覆工艺， 不必在多种工艺设备上进行材料加工。 以上所述仅为本发明的优选实施例而已， 并不用于限制本发明， 对于本领域的 技术人员来说， 本发明可以有各种更改和变化。 凡在本发明的精神和原则之内 ， 所作的任何修改、 等同替换、 改进等， 均应包含在本发明的保护范围之内。

Claims

权利要求书
[权利要求 1] 一种囊体材料， 其特征在于， 所述囊体材料包括气体阻隔层， 所述气 体阻隔层为双氢氧化物片层材料分散于聚合物之中所制备的涂层或薄 膜。
[权利要求 2] 根据权利要求 1所述的囊体材料， 其特征在于， 所述聚合物为热塑性 聚氨酯。
[权利要求 3] 根据权利要求 1所述的囊体材料， 其特征在于， 所述双氢氧化物片层 材料占所述气体阻隔层的重量百分比为 1~10%。
[权利要求 4] 根据权利要求 1所述的囊体材料， 其特征在于， 所述囊体材料包括由 外向内依次层叠设置的耐候层、 气体阻隔层、 胶层和承重层。
[权利要求 5] 根据权利要求 4所述的囊体材料， 其特征在于， 所述耐候层为含质量 百分数为 3~20% ZnO的聚氨酯或含质量分数为 5~20%TiO 2的热塑性聚 氨酯的复合膜或涂层。
[权利要求 6] 根据权利要求 5所述的囊体材料 ， 其特征在于 所述耐候层的厚度为 2
0~35微米。
[权利要求 7] 根据权利要求 4所述的囊体材料 ， 其特征在于 所述胶层为聚氨酯热 熔胶或双组份聚氨酯胶黏剂。
[权利要求 8] 根据权利要求 7所述的囊体材料 ， 其特征在于 所述胶层的厚度为 10~
25微米。
[权利要求 9] 根据权利要求 4所述的囊体材料 ， 其特征在于 所述承重层为织物。
[权利要求 10] 根据权利要求 9所述的囊体材料， 其特征在于 所述织物为涤纶纤维 或芳纶纤维。
[权利要求 11] 根据权利要求 4所述的囊体材料 ， 其特征在于 所述承重层的厚度为 1
00 150微米。
[权利要求 12] —种囊体， 其特征在于， 所述囊体由权利要求 1至 11中任一项所述的 囊体材料制成。
[权利要求 13] —种浮空器， 包括囊体， 其特征在于， 所述囊体由权利要求 1至 11中 任一项所述的囊体材料制成。
[权利要求 14] 一种囊体材料的制备方法， 其特征在于， 包括以下步骤： Sl， 在承重层的正面涂覆胶层；
S2， 以 N， N-二甲基乙酰胺、 Ν,Ν-二甲基甲酰胺、 丁酮、 丙酮、 甲苯 中的一种或几种混合为溶剂， 加入双氢氧化物片层材料以及分散剂， 搅拌后超声分散， 然后加入热塑性聚氨酯， 加热搅拌至所述聚氨酯完 全溶解， 得到浆料， 将所述浆料涂覆在所述胶层上， 干燥， 除去溶剂 形成气体阻隔层； 以及
S3 , 在所述气体阻隔层上设置耐候层。
[权利要求 15] 根据权利要求 14所述的方法， 其特征在于， 所述 S2中， 通过溶液刮涂 法在将所述浆料涂覆在所述胶层上， 在 80°C以上干燥， 除去溶剂。
[权利要求 16] 根据权利要求 14所述的方法， 其特征在于， 所述 S3中， 通过溶液刮涂 法在所述气体阻隔层表面涂布耐候层， 所述耐候层为含质量百分数为 3-20% ZnO的聚氨酯或含质量分数为 5~20%TiO 2的热塑性聚氨酯的复 合膜或涂层。
[权利要求 17] 如权利要求 1至 11中任一项所述的囊体材料在探空气球、 飞艇、 系留 气球、 汽车气囊方面的应用。
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