CN107857987A - Polyurethane composite flame-retardant absorbing material and preparation method thereof - Google Patents
Polyurethane composite flame-retardant absorbing material and preparation method thereof Download PDFInfo
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- 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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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
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- 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
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- C08K5/00—Use of organic ingredients
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
Abstract
The invention provides a kind of polyurethane composite flame-retardant absorbing material, it is characterised in that it is obtained by the aggregated reaction of component of following mass parts：100 parts of PPG, 30~70 parts of toluene di-isocyanate(TDI), 0.01~0.5 part of nano carbon sol, 10~20 parts of deionized water, 5~30 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~20 parts of ferrite, 2~6 parts of zirconium oxide, 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 composite flame-retardant absorbing material 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 composite flame-retardant absorbing material.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of polyurethane composite flame-retardant absorbing material 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, it is of the invention it is necessory to provide a kind of polyurethane composite flame-retardant absorbing material and preparation method thereof, with
Solve the above problems.
The present invention provides a kind of polyurethane composite flame-retardant absorbing material, and it aggregated is reacted by the component of following mass parts
Arrive：100 parts of PPG, 30~70 parts of toluene di-isocyanate(TDI), 0.01~0.5 part of nano carbon sol, deionized water 10~
20 parts, 5~30 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~20 parts of ferrite, 2~6 parts of zirconium oxide, boric acid
1~10 part of zinc, 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.
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 composite flame-retardant absorbing material is obtained by the aggregated reaction of component of following mass parts：
100 parts of PPG, 40~60 parts of toluene di-isocyanate(TDI), 0.1~0.3 part of nano carbon sol, 13~17 parts of deionized water,
12~23 parts of methyl-phosphoric acid dimethyl ester, 4~6 parts of graphene oxide, 13~17 parts of ferrite, 3~5 parts of zirconium oxide, Firebrake ZB 4~
7 parts, 0.08~0.3 part of stannous octoate, 0.12~0.45 part of triethylene diamine, 1~2 part of organic silicon surfactant, bicarbonate
5~7 parts of sodium.
The present invention also provides a kind of preparation method of above-mentioned polyurethane composite flame-retardant absorbing material, and it comprises the following steps：
Raw material mixes：By PPG, methyl-phosphoric acid dimethyl ester, nano carbon sol, ferrite, zirconium oxide, 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 polyurethane composite flame-retardant 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 composite flame-retardant absorbing material provided by the invention using methyl-phosphoric acid dimethyl ester with
Firebrake ZB is combined, and is allowed to play fire-retardant synergy so that the polyurethane composite flame-retardant absorbing material has low cigarette, low
The features such as malicious, fire retardant, and the fire resistance of the material reaches HF-1 levels；Sodium acid carbonate and graphene oxide react generation
Bubble, while coordinate Freeze Drying Technique to remove the deionized water in the absorbing material gel so that the polyurethane of preparation is answered
Closing flame-retarding wave-absorbing material has a loose structure, larger specific surface area, in addition, nano carbon sol and graphene oxide have it is larger
Adsorptivity and electric conductivity, then with ferrite, zirconium oxide coordinate so that the polyurethane composite flame-retardant absorbing material have it is higher
Wave absorbing efficiency, absorption frequency distribution is wide, suitable for wave-absorbing and camouflage field.Further, since nano carbon sol and graphene have
Preferable electric conductivity, and be evenly dispersed in polyurethane matrix and form good conductive network, prepare gained polyurethane
The electric property of composite improves and stably, excess effusion value is low.The present invention is using chemical foaming technology and orientation freeze-drying skill
Art is combined to prepare the polyurethane composite flame-retardant absorbing material, and preparation technology is simple, small investment, and production efficiency is high, environment
It is 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 composite flame-retardant absorbing material, its by following mass parts the aggregated reaction of component
Obtain：100 parts of PPG, 30 parts of toluene di-isocyanate(TDI), 0.02 part of nano carbon sol, 10 parts of deionized water, methyl phosphorus
5 parts of dimethyl phthalate, 2 parts of graphene oxide, 10 parts of ferrite, 2 parts of zirconium oxide, 2 parts of Firebrake ZB, 0.02 part of stannous octoate, three second
0.03 part of alkene diamines, 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 composite flame-retardant absorbing material, and it includes following
Step：
Raw material mixes：Above-mentioned mass parts, by PPG, methyl-phosphoric acid dimethyl ester, nano carbon sol, ferrite, zirconium oxide,
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 above-mentioned polyurethane composite flame-retardant absorbing material.
Performance test
Absorbing property detection method：It is 3cm × 3cm that above-mentioned polyurethane composite flame-retardant absorbing material is cut into area, thickness 4
Mm rectangular patch sample, and the very smooth aluminium foil of layer of surface is sticked on a side surface, using digital vector network
The microwave reflection rate curve of analyzer (8722ET types) test above-mentioned sample in 4~20 ghz bands.It will detect, absorbing property
It is less than -39 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 composite flame-retardant absorbing material reaches HF-1 levels.
Embodiment 2
The embodiment of the present invention provides a kind of polyurethane composite flame-retardant absorbing material and aggregated reacted by the component of following mass parts
Arrive：100 parts of PPG, 40 parts of toluene di-isocyanate(TDI), 0.1 part of nano carbon sol, 13 parts of deionized water, methyl acid phosphate two
12 parts of methyl esters, 4 parts of graphene oxide, 13 parts of ferrite, 3 parts of zirconium oxide, 4 parts of Firebrake ZB, 0.08 part of stannous octoate, triethylene two
0.12 part of amine, 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 composite flame-retardant absorbing material, the preparation method
The preparation method provided with embodiment 1 is 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, obtains above-mentioned polyurethane composite flame-retardant
Absorbing material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane composite flame-retardant absorbing material provided above-described embodiment
Absorption ripple performance and fire resistance detected, testing result is：Absorbing property is small in 4GHz~20GHz frequency ranges
In -43 db, the fire resistance of above-mentioned polyurethane composite flame-retardant absorbing material reaches HF-1 levels.
Embodiment 3
The embodiment of the present invention provides a kind of polyurethane composite flame-retardant absorbing material, its by following mass parts the aggregated reaction of component
Obtain：100 parts of PPG, 50 parts of toluene di-isocyanate(TDI), 0.2 part of nano carbon sol, 15 parts of deionized water, methyl acid phosphate
18 parts of dimethyl ester, 5 parts of graphene oxide, 15 parts of ferrite, 4 parts of zirconium oxide, 5 parts of Firebrake ZB, 0.2 part of stannous octoate, triethylene
0.3 part of diamines, 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 composite flame-retardant absorbing material, the preparation method
The preparation method provided with embodiment 1 is 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, obtains above-mentioned polyurethane composite flame-retardant
Absorbing material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane composite flame-retardant absorbing material provided above-described embodiment
Absorption ripple performance and fire resistance detected, testing result is：Absorbing property is small in 4GHz~20GHz frequency ranges
In -48 db, the fire resistance of above-mentioned polyurethane composite flame-retardant absorbing material reaches HF-1 levels.
Embodiment 4
The embodiment of the present invention provides a kind of polyurethane composite flame-retardant absorbing material and aggregated reacted by the component of following mass parts
Arrive：100 parts of PPG, 60 parts of toluene di-isocyanate(TDI), 0.3 part of nano carbon sol, 17 parts of deionized water, methyl acid phosphate two
23 parts of methyl esters, 6 parts of graphene oxide, 17 parts of ferrite, 5 parts of zirconium oxide, 7 parts of Firebrake ZB, 0.3 part of stannous octoate, triethylene two
0.45 part of amine, 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 composite flame-retardant absorbing material, the preparation method
The preparation method provided with embodiment 1 is 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, obtains above-mentioned polyurethane composite flame-retardant
Absorbing material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane composite flame-retardant absorbing material provided above-described embodiment
Absorption ripple performance and fire resistance detected, testing result is：Absorbing property is small in 4GHz~20GHz frequency ranges
In -45 db, the fire resistance of above-mentioned polyurethane composite flame-retardant absorbing material reaches HF-1 levels.
Embodiment 5
The embodiment of the present invention provides a kind of polyurethane composite flame-retardant absorbing material, its by following mass parts the aggregated reaction of component
Obtain：100 parts of PPG, 70 parts of toluene di-isocyanate(TDI), 0.5 part of nano carbon sol, 20 parts of deionized water, methyl acid phosphate
30 parts of dimethyl ester, 8 parts of graphene oxide, 20 parts of ferrite, 6 parts of zirconium oxide, 8 parts of Firebrake ZB, 0.4 part of stannous octoate, triethylene
0.6 part of diamines, 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 composite flame-retardant absorbing material, the preparation method
The preparation method provided with embodiment 1 is 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, above-mentioned polyurethane composite flame-retardant is obtained and inhales ripple
Material.
Performance test
Using the identical method with being provided in embodiment 1, the polyurethane composite flame-retardant absorbing material provided above-described embodiment
Absorption ripple performance and fire resistance detected, testing result is：Absorbing property is small in 4GHz~20GHz frequency ranges
In -44 db, the fire resistance of above-mentioned polyurethane composite flame-retardant absorbing material 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 composite flame-retardant absorbing material, it is characterised in that it aggregated is reacted by the component of following mass parts
Arrive：100 parts of PPG, 30~70 parts of toluene di-isocyanate(TDI), 0.01~0.5 part of nano carbon sol, deionized water 10~
20 parts, 5~30 parts of methyl-phosphoric acid dimethyl ester, 2~8 parts of graphene oxide, 10~20 parts of ferrite, 2~6 parts of zirconium oxide, boric acid
2~8 parts of zinc, 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, wherein, the polyether polyol hydroxyl value is 30~60mgKOH/g, the toluene di-isocyanate(TDI) it is different
The index of cyanate is 0.60~1.15.
2. polyurethane composite flame-retardant absorbing material according to claim 1, it is characterised in that it by following mass parts group
Lease making polymerisation obtains：100 parts of PPG, 40~60 parts of toluene di-isocyanate(TDI), 0.1~0.3 part of nano carbon sol,
13~17 parts of deionized water, 12~23 parts of methyl-phosphoric acid dimethyl ester, 4~6 parts of graphene oxide, 13~17 parts of ferrite, oxidation
3~5 parts of zirconium, 4~7 parts of Firebrake ZB, 0.08~0.3 part of stannous octoate, 0.12~0.45 part of triethylene diamine, organosilyl surface are lived
1~2 part of agent of property, 5~7 parts of sodium acid carbonate.
3. a kind of preparation method of the polyurethane composite flame-retardant absorbing material described in claim 1 or 2, it comprises the following steps：
Raw material mixes：By PPG, methyl-phosphoric acid dimethyl ester, nano carbon sol, ferrite, zirconium oxide, 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 polyurethane composite flame-retardant absorbing material.
4. the preparation method of polyurethane composite flame-retardant absorbing material according to claim 3, it is characterised in that the reaction
The step of foaming, includes：In the presence of ultrasonic agitation, first toluene di-isocyanate(TDI) is added under conditions of heating while stirring
Enter into the first mixture 5~10 minutes, add graphene oxide and sodium acid carbonate；Then mould progress is poured into rapidly
Room temperature foams 30~90 minutes, obtains the absorbing material gel.
5. the preparation method of polyurethane composite flame-retardant absorbing material according to claim 4, it is characterised in that in the original
In the step of material mixing, the ultrasonic disperse processing is carried out in a water bath.
6. the preparation method of the polyurethane composite flame-retardant absorbing material according to claim 3 or 4 or 5 any one, its feature
It is, includes the step of the freeze-drying：First the absorbing material gel is freezed 10~70 hours, cryogenic temperature is mixing
5~50 DEG C below solution freezing point temperature；Then the mixed solution after freezing is further done in -10~-100 DEG C of low-temp low-pressures
Dry 24~96 hours, pressure was 0.1~1kPa；Finally by the dried mixed solution of low-temp low-pressure in 60~100 DEG C solidify 4~
12 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111704706A (en) * | 2019-04-22 | 2020-09-25 | 朱晶晶 | Processing technology of polyurethane foam for fireproof insulation board |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111704706A (en) * | 2019-04-22 | 2020-09-25 | 朱晶晶 | Processing technology of polyurethane foam for fireproof insulation board |
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