CN107868210A - Polyurethane ferrite composite wave-absorbing fire proofing and preparation method thereof - Google Patents

Polyurethane ferrite composite wave-absorbing fire proofing and preparation method thereof Download PDF

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CN107868210A
CN107868210A CN201610854153.1A CN201610854153A CN107868210A CN 107868210 A CN107868210 A CN 107868210A CN 201610854153 A CN201610854153 A CN 201610854153A CN 107868210 A CN107868210 A CN 107868210A
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parts
absorbing
composite wave
fire proofing
ferrite composite
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王心超
程相林
温毓敏
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Henan Haina New Material Co Ltd
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Henan Haina New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing, wherein, it is obtained by the aggregated reaction of component of following mass parts：100 parts of PPG, 20~70 parts of toluene di-isocyanate(TDI), 0.2~1 part of Nano carbon white, 10~20 parts of deionized water, 5~20 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~30 parts of ferrite, 1~5 part of carborundum, 2~8 parts of Firebrake ZB, 0.02~0.4 part of stannous octoate, 0.03~0.6 part of triethylene diamine, 0.2~3 part of organic silicon surfactant, 1~10 part of sodium acid carbonate.Above-mentioned polyurethane ferrite composite wave-absorbing fire proofing provided by the invention has the characteristics that low cigarette, low toxicity, absorption frequency distribution that is fire retardant, absorbing ripple are wide.The present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing.

Description

Polyurethane ferrite composite wave-absorbing fire proofing and preparation method thereof
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of polyurethane ferrite composite wave-absorbing fire proofing and Its preparation method.
Background technology
Absorbing material, it is to refer to be projected onto the electromagnetic wave on its surface largely to absorb and change into the energy of other forms Amount and almost unreflected material.With the development of modern science and technology, influence of the electromagenetic wave radiation to environment increasingly increases. Airport, airplane flight are overdue because Electromagnetic Interference can not take off；In hospital, mobile phone can often disturb various electronic instrument for diagnosing and curing diseases The normal work of device.Other electromagnetic radiation causes wound directly or indirectly by fuel factor, non-thermal effect, cumulative effect to human body Evil.Therefore, electromagnetic pollution is administered, finds a kind of material that can be kept out and weaken electromagenetic wave radiation --- absorbing material, it has also become One big problem of material science.
Polyurethane foam has that porous, relative density is small, and heatproof, ageing-resistant, anti-organic solvent corrode, easily shaping The features such as processing, it is widely used in absorbing material.At present mainly by the way that wave absorbing agent is added into hard polyurethane foam system, It is re-introduced into mould and reacts foaming, or flexible polyurethane foams are cut into predetermined shape, impregnates wave absorbing agent solution to make Standby polyurethane foam composite wave-suction material, these materials have that complex manufacturing technology, function are single, inhale ripple auxiliary agent and be easy to come off, The defects of inflammable.
Chinese patent CN200910029840.X " foamed high resilience polyurethane wave-absorbing material and preparation method thereof " is open A kind of polyurethane wave-absorbing material prepared using the raw materials such as auxiliary agent, fire retardant are absorbed.But the material has that size is big, makes work The defects of skill complexity.It is to inhale ripple material that raising fire resistance, manufacture craft are simple while how improving absorbing property, reduce pollution Expect the key issue of development.
The content of the invention
In view of this, the present invention is it is necessory to provide a kind of polyurethane ferrite composite wave-absorbing fire proofing and its preparation side Method, to solve the above problems.
The present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing, and it is aggregated by the component of following mass parts Reaction obtains：100 parts of PPG, 20~70 parts of toluene di-isocyanate(TDI), 0.2~1 part of Nano carbon white, deionized water 10 ~20 parts, 5~20 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~30 parts of ferrite, 1~5 part of carborundum, boron Sour 2~8 parts of zinc, 0.02~0.4 part of stannous octoate, 0.03~0.6 part of triethylene diamine, organic silicon surfactant 0.2~3 Part, 1~10 part of sodium acid carbonate.
Wherein, the polyether polyol hydroxyl value is 30~60mgKOH/g.The isocyanates of the toluene di-isocyanate(TDI) Index is 0.60~1.15.
Based on above-mentioned, the polyurethane ferrite composite wave-absorbing fire proofing by following mass parts the aggregated reaction of component Obtain：100 parts of PPG, 40~50 parts of toluene di-isocyanate(TDI), 0.4~0.8 part of Nano carbon white, deionized water 13~ 17 parts, 10~15 parts of methyl-phosphoric acid dimethyl ester, 4~6 parts of graphene oxide, 15~25 parts of ferrite, 2~4 parts of carborundum, boric acid 4~6 parts of zinc, 0.08~0.3 part of stannous octoate, 0.12~0.45 part of triethylene diamine, 1~2 part of organic silicon surfactant, carbon Sour 5~7 parts of hydrogen sodium.
The present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, and it includes following Step：
Raw material mixes：By PPG, methyl-phosphoric acid dimethyl ester, Nano carbon white, ferrite, carborundum, Firebrake ZB, octanoic acid Stannous, triethylene diamine, deionized water, organic silicon surfactant are stirred at room temperature uniformly, then handled through ultrasonic disperse Obtain first mixture；
Reaction foaming：Toluene di-isocyanate(TDI) is added into the first mixture and is stirred by ultrasonic 5~10 minutes, adds oxygen Graphite alkene and sodium acid carbonate, mould is then poured into rapidly and carries out room temperature foaming 30~90 minutes, obtains absorbing material gel；
Freeze-drying：The absorbing material gel be freeze-dried and produces the fire-retardant material of polyurethane ferrite composite wave-absorbing Material.
Included based on the step of above-mentioned, the reaction is foamed：In the presence of ultrasonic agitation, first by toluene di-isocyanate(TDI) 5~10 minutes in the first mixture is added under conditions of heating while stirring, graphene oxide and carbonic acid are added Hydrogen sodium；Then mould is poured into rapidly and carries out room temperature foaming 30~90 minutes, obtains the absorbing material gel.
Based on above-mentioned, in the step of raw material mixes, the ultrasonic disperse processing is carried out in a water bath.
Include based on above-mentioned, the step of the freeze-drying：First the absorbing material gel is freezed 10~70 hours, it is cold It is 5~50 DEG C below mixed solution freezing point temperature to freeze temperature；Then by the mixed solution after freezing further in -10~-100 DEG C low-temp low-pressure is dried 24~96 hours, and pressure is 0.1~1kPa；Finally by the dried mixed solution of low-temp low-pressure in 60~ 100 DEG C solidify 4~12 hours.
Compared with prior art, polyurethane ferrite composite wave-absorbing fire proofing provided by the invention uses methyl acid phosphate two Methyl esters is combined with Firebrake ZB, is allowed to play fire-retardant synergy so that the polyurethane ferrite composite wave-absorbing fire proofing There is low cigarette, low toxicity, fire retardant, and the fire resistance of the material reaches HF-1 levels；Sodium acid carbonate and graphene oxide Reaction produces bubble, while coordinates Freeze Drying Technique to remove the deionized water in the absorbing material gel so that preparation Polyurethane ferrite composite wave-absorbing fire proofing has loose structure, larger specific surface area, in addition, Nano carbon white and oxidation Graphene has larger adsorptivity, then coordinates with ferrite, carborundum so that the polyurethane ferrite composite wave-absorbing is fire-retardant Material has higher wave absorbing efficiency, and absorption frequency distribution is wide, suitable for wave-absorbing and camouflage field.The present invention uses chemical blowing skill Art and orientation Freeze Drying Technique are combined to prepare the polyurethane ferrite composite wave-absorbing fire proofing, preparation technology letter Single, small investment, production efficiency is high, environment-friendly.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment 1
The embodiment of the present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing, and it is by the component of following mass parts through poly- Reaction is closed to obtain：100 parts of PPG, 20 parts of toluene di-isocyanate(TDI), 0.2 part of Nano carbon white, 10 parts of deionized water, first 5 parts of base dimethyl phosphate, 2 parts of graphene oxide, 10 parts of ferrite, 1 part of carborundum, 2 parts of Firebrake ZB, 0.02 part of stannous octoate, 0.03 part of triethylene diamine, 0.2 part of organic silicon surfactant, 1 part of sodium acid carbonate.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, and it is wrapped Include following steps：
Raw material mixes：Above-mentioned mass parts, by PPG, methyl-phosphoric acid dimethyl ester, Nano carbon white, ferrite, carborundum, Firebrake ZB, stannous octoate, triethylene diamine, deionized water, organic silicon surfactant are stirred at room temperature uniformly, then through super Sound decentralized processing obtains first mixture；
Reaction foaming：In the presence of ultrasonic agitation, first toluene di-isocyanate(TDI) is added under conditions of heating while stirring Into the first mixture 5~10 minutes, graphene oxide and sodium acid carbonate are added；Then mould is poured into rapidly carries out room Temperature foaming 30 minutes, obtains absorbing material gel；
Freeze-drying：First the absorbing material gel is freezed 10 hours, cryogenic temperature is 5 below mixed solution freezing point temperature ℃；Then the mixed solution after freezing is further dried 24 hours in -10 DEG C of low-temp low-pressures, pressure is 0.1 kPa；Finally will The dried mixed solution of low-temp low-pressure solidifies 12 hours in 60 DEG C, obtains the above-mentioned fire-retardant material of polyurethane ferrite composite wave-absorbing Material.
Performance test
Absorbing property detection method：It is 3cm × 3cm that above-mentioned polyurethane ferrite composite wave-absorbing fire proofing is cut into area, Thickness is 4 mm rectangular patch sample, and the very smooth aluminium foil of layer of surface is sticked on a side surface, using digitlization The microwave reflection rate curve of vector network analyzer (8722ET types) test above-mentioned sample in 4~20 ghz bands.It will detect, Absorbing property is less than -32 db in 4GHz~20GHz frequency ranges.
Fire resistance detection method：According to GB/T 8332-2008 foamed plastics combustibility test method horizontal firing methods Detected to above-mentioned.After testing, the fire resistance of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing reaches HF-1 levels.
Embodiment 2
It is aggregated by the component of following mass parts that the embodiment of the present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing Reaction obtains：100 parts of PPG, 30 parts of toluene di-isocyanate(TDI), 0.4 part of Nano carbon white, 13 parts of deionized water, methyl 10 parts of dimethyl phosphate, 4 parts of graphene oxide, 15 parts of ferrite, 2 parts of carborundum, 4 parts of Firebrake ZB, 0.08 part of stannous octoate, three 0.12 part of ethylene diamine, 1 part of organic silicon surfactant, 5 parts of sodium acid carbonate.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, the system Preparation Method and the preparation method that embodiment 1 provides are essentially identical, and difference is：
Reaction foaming：Room temperature foamed time in the step is 60 minutes；
Freeze-drying：The step includes first freezing the absorbing material gel 30 hours, and cryogenic temperature solidifies for mixed solution 15 DEG C below point temperature；Then the mixed solution after freezing is further dried 48 hours in -30 DEG C of low-temp low-pressures, pressure is 0.3 kPa；Finally the dried mixed solution of low-temp low-pressure is solidified 10 hours in 70 DEG C, above-mentioned polyurethane ferrite is obtained and answers Close and inhale wave resistance combustible material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane ferrite composite wave-absorbing that above-described embodiment provides is hindered The absorption ripple performance and fire resistance of combustible material are detected, and testing result is：Absorbing property is in 4GHz~20GHz frequency ranges Interior to be less than -35 db, the fire resistance of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing reaches HF-1 levels.
Embodiment 3
The embodiment of the present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing, and it is by the component of following mass parts through poly- Reaction is closed to obtain：100 parts of PPG, 40 parts of toluene di-isocyanate(TDI), 0.6 part of Nano carbon white, 15 parts of deionized water, first 13 parts of base dimethyl phosphate, 5 parts of graphene oxide, 20 parts of ferrite, 3 parts of carborundum, 5 parts of Firebrake ZB, 0.2 part of stannous octoate, 0.3 part of triethylene diamine, 1.6 parts of organic silicon surfactant, 6 parts of sodium acid carbonate.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, the system Preparation Method and the preparation method that embodiment 1 provides are essentially identical, and difference is：
Reaction foaming：Room temperature foamed time in the step is 60 minutes；
Freeze-drying：The step includes first freezing the absorbing material gel 40 hours, and cryogenic temperature solidifies for mixed solution 30 DEG C below point temperature；Then the mixed solution after freezing is further dried 60 hours in -50 DEG C of low-temp low-pressures, pressure is 0.6 kPa；Finally the dried mixed solution of low-temp low-pressure is solidified 8 hours in 80 DEG C, above-mentioned polyurethane ferrite is obtained and answers Close and inhale wave resistance combustible material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane ferrite composite wave-absorbing that above-described embodiment provides is hindered The absorption ripple performance and fire resistance of combustible material are detected, and testing result is：Absorbing property is in 4GHz~20GHz frequency ranges Interior to be less than -39 db, the fire resistance of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing reaches HF-1 levels.
Embodiment 4
It is aggregated by the component of following mass parts that the embodiment of the present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing Reaction obtains：100 parts of PPG, 50 parts of toluene di-isocyanate(TDI), 0.8 part of Nano carbon white, 17 parts of deionized water, methyl 15 parts of dimethyl phosphate, 6 parts of graphene oxide, 25 parts of ferrite, 4 parts of carborundum, 6 parts of Firebrake ZB, 0.3 part of stannous octoate, three 0.45 part of ethylene diamine, 2 parts of organic silicon surfactant, 7 parts of sodium acid carbonate.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, the system Preparation Method and the preparation method that embodiment 1 provides are essentially identical, and difference is：
Reaction foaming：Room temperature foamed time in the step is 90 minutes；
Freeze-drying：The step includes first freezing the absorbing material gel 60 hours, and cryogenic temperature solidifies for mixed solution 40 DEG C below point temperature；Then the mixed solution after freezing is further dried 72 hours in -80 DEG C of low-temp low-pressures, pressure is 0.8 kPa；Finally the dried mixed solution of low-temp low-pressure is solidified 6 hours in 90 DEG C, above-mentioned polyurethane ferrite is obtained and answers Close and inhale wave resistance combustible material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane ferrite composite wave-absorbing that above-described embodiment provides is hindered The absorption ripple performance and fire resistance of combustible material are detected, and testing result is：Absorbing property is in 4GHz~20GHz frequency ranges Interior to be less than -39 db, the fire resistance of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing reaches HF-1 levels.
Embodiment 5
The embodiment of the present invention provides a kind of polyurethane ferrite composite wave-absorbing fire proofing, and it is by the component of following mass parts through poly- Reaction is closed to obtain：100 parts of PPG, 70 parts of toluene di-isocyanate(TDI), 1 part of Nano carbon white, 20 parts of deionized water, methyl 20 parts of dimethyl phosphate, 8 parts of graphene oxide, 30 parts of ferrite, 5 parts of carborundum, 8 parts of Firebrake ZB, 0.4 part of stannous octoate, three 0.6 part of ethylene diamine, 3 parts of organic silicon surfactant, 10 parts of sodium acid carbonate.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing, the system Preparation Method and the preparation method that embodiment 1 provides are essentially identical, and difference is：
Reaction foaming：Room temperature foamed time in the step is 90 minutes；
Freeze-drying：The step includes first freezing the absorbing material gel 70 hours, and cryogenic temperature solidifies for mixed solution 50 DEG C below point temperature；Then the mixed solution after freezing is further dried 96 hours in -100 DEG C of low-temp low-pressures, pressure 1 kPa；Finally the dried mixed solution of low-temp low-pressure is solidified 4 hours in 100 DEG C, obtains the above-mentioned compound suction of polyurethane ferrite Wave resistance combustible material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane ferrite composite wave-absorbing that above-described embodiment provides is hindered The absorption ripple performance and fire resistance of combustible material are detected, and testing result is：Absorbing property is in 4GHz~20GHz frequency ranges Interior to be less than -37 db, the fire resistance of above-mentioned polyurethane ferrite composite wave-absorbing fire proofing reaches HF-1 levels.
Finally it should be noted that：The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof；To the greatest extent The present invention is described in detail with reference to preferred embodiments for pipe, those of ordinary skills in the art should understand that：Still The embodiment of the present invention can be modified or equivalent substitution is carried out to some technical characteristics；Without departing from this hair The spirit of bright technical scheme, it all should cover among the claimed technical scheme scope of the present invention.

Claims (6)

1. a kind of polyurethane ferrite composite wave-absorbing fire proofing, it is characterised in that it is aggregated by the component of following mass parts Reaction obtains：100 parts of PPG, 20~70 parts of toluene di-isocyanate(TDI), 0.2~1 part of Nano carbon white, deionized water 10 ~20 parts, 5~20 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~30 parts of ferrite, 1~5 part of carborundum, boron Sour 2~8 parts of zinc, 0.02~0.4 part of stannous octoate, 0.03~0.6 part of triethylene diamine, organic silicon surfactant 0.2~3 Part, 1~10 part of sodium acid carbonate, wherein, the polyether polyol hydroxyl value is 30~60mgKOH/g, the toluene di-isocyanate(TDI) Isocyanates index be 0.60~1.15.
2. polyurethane ferrite composite wave-absorbing fire proofing according to claim 1, it is characterised in that it is by following quality The aggregated reaction of component of part obtains：100 parts of PPG, 40~50 parts of toluene di-isocyanate(TDI), Nano carbon white 0.4~ 0.8 part, 13~17 parts of deionized water, 10~16 parts of methyl-phosphoric acid dimethyl ester, 4~6 parts of graphene oxide, ferrite 15~25 Part, 2~4 parts of carborundum, 4~6 parts of Firebrake ZB, 0.08~0.3 part of stannous octoate, 0.12~0.45 part of triethylene diamine are organic 1~2 part of silicon surface active agent, 5~7 parts of sodium acid carbonate.
3. a kind of preparation method of the polyurethane ferrite composite wave-absorbing fire proofing described in claim 1 or 2, it includes following Step：
Raw material mixes：By PPG, methyl-phosphoric acid dimethyl ester, Nano carbon white, ferrite, carborundum, Firebrake ZB, octanoic acid Stannous, triethylene diamine, deionized water, organic silicon surfactant are stirred at room temperature uniformly, then handled through ultrasonic disperse Obtain first mixture；
Reaction foaming：Toluene di-isocyanate(TDI) is added into the first mixture and is stirred by ultrasonic 5~10 minutes, adds oxygen Graphite alkene and sodium acid carbonate, mould is then poured into rapidly and carries out room temperature foaming 30~90 minutes, obtains absorbing material gel；
Freeze-drying：The absorbing material gel be freeze-dried and produces the fire-retardant material of polyurethane ferrite composite wave-absorbing Material.
4. the preparation method of polyurethane ferrite composite wave-absorbing fire proofing according to claim 3, it is characterised in that institute The step of stating reaction foaming includes：In the presence of ultrasonic agitation, first by toluene di-isocyanate(TDI) in the bar to heat while stirring It is added under part in the first mixture 5~10 minutes, adds graphene oxide and sodium acid carbonate；Then mould is poured into rapidly Tool carries out room temperature and foamed 30~90 minutes, obtains the absorbing material gel.
5. the preparation method of polyurethane ferrite composite wave-absorbing fire proofing according to claim 4, it is characterised in that In the step of raw material mixing, the ultrasonic disperse processing is carried out in a water bath.
6. the preparation method of the polyurethane ferrite composite wave-absorbing fire proofing according to claim 3 or 4 or 5 any one, Characterized in that, the step of freeze-drying, includes：First the absorbing material gel is freezed 10~70 hours, cryogenic temperature For 5~50 DEG C below mixed solution freezing point temperature；Then by the mixed solution after freezing further in -10~-100 DEG C of low temperature Low pressure is dried 24~96 hours, and pressure is 0.1~1kPa；Finally by the dried mixed solution of low-temp low-pressure in 60~100 DEG C Solidification 4~12 hours.
CN201610854153.1A 2016-09-23 2016-09-23 Polyurethane ferrite composite wave-absorbing fire proofing and preparation method thereof Withdrawn CN107868210A (en)

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