CN107286343A - A kind of Halogen composite flame-proof Polyimide foams and preparation method thereof - Google Patents
A kind of Halogen composite flame-proof Polyimide foams and preparation method thereof Download PDFInfo
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- CN107286343A CN107286343A CN201610206289.1A CN201610206289A CN107286343A CN 107286343 A CN107286343 A CN 107286343A CN 201610206289 A CN201610206289 A CN 201610206289A CN 107286343 A CN107286343 A CN 107286343A
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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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
- C08G2110/00—Foam properties
- C08G2110/0041—Foam properties having specified density
- C08G2110/005—< 50kg/m3
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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Abstract
The present invention discloses a kind of Halogen composite flame-proof Polyimide foams and preparation method thereof.The foamed material is made up of the raw material of following parts by weight：100 parts of aromatic dianhydride, 50~500 parts of polar solvent, 5~30 parts of fatty alcohol, 5~20 parts of deionized water, 15 parts of foam stabiliser, 5 parts of composite catalyst, 4~100 parts of Halogenless composite fire retardant, 100~500 parts of polyisocyanates.The preparation method is that aromatic dianhydride is heated and fatty alcohol reaction in polar solvent；Add deionized water, foam stabiliser and composite catalyst, Halogenless composite fire retardant and obtain suspension；It is eventually adding that polyisocyanates is foamed and heating in vacuum solidification, finally gives fire-retardant Polyimide foams.Foamed material obtained by the present invention has that density is low, cell size distribution uniform, mechanical property, heat resistance and the features such as excellent flame retarding and smoke suppressing properties.It disclosure satisfy that the requirement of the high-end field such as Aero-Space, navigation Polyimide foams.
Description
Technical field
The present invention relates to technical field of polymer materials, more particularly to a kind of low-density Halogen composite flame-proof
Polyimide foams and preparation method thereof.
Background technology
Polyimides is so far in industrial circle application temperature classification highest polymeric material, simultaneously
Also extremely low temperature is resistant to, with excellent mechanical property.The foam performance of polyimides is excellent, and density can
Design, radiation hardness, resistance to combustion, low smokiness energy, no pernicious gas release.Polyimide foams are got over
To be used for more the high-technology field such as Aero-Space, transport by sea, national defence and microelectronics it is heat-insulated,
The critical material such as damping noise reduction and insulation.
Polyimide foam high comprehensive performance prepared by powder foam method, but preparation technology is complicated, mistake
Journey circuit is longer, higher to equipment requirement, and obtained froth pulp price costly, therefore is limited
It is widely used.And the method for NCO polyimide foam simplifies production procedure, life is reduced
Cost is produced, but is due to the relatively low reaction speed and the relatively low extent of reaction between raw material, causes a large amount of pairs
The generation of product (polyureas), reduces the fire resistance of material.Chinese patent (publication number CN103897395
And CN104497255) the compound conduct of hydrotalcite, inorganic mineral and organic liquid fire retardant is respectively adopted
The fire retardant of NCO Polyimide foams, flame retardant effect is excellent, because addition is larger,
Easily influence the structure and performance of foam.Chinese patent (publication number CN104804190) is by inciting somebody to action
Polyimide foam and cellular material be compound to be prepared into alveolate texture to improve its fire resistance, but this
Method improves limited to the fire resistance of foam.
In view of while Polyimide foams flame-retardancy requirements being improved, product structure not being damaged and is made
With performance, and the composite factor such as smoke when reducing product burning.A kind of addition need to be provided few, nontoxic
The good halogen-free flame retardants of pollution-free, fire resistance, to ensure the structure of Polyimide foams with using
Performance.
The content of the invention
It is an object of the present invention to provide a kind of Halogen composite flame-proof Polyimide foams.The bubble
Foam material has that density is low, cell size distribution uniform, mechanical property and the features such as excellent fireproof performance,
The problems such as structure is with performance deficiency in the polyimide of prior art preparation is overcome well.
It is another object of the present invention to provide a kind of system of Halogen composite flame-proof Polyimide foams
Preparation Method.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of Halogen composite flame-proof Polyimide foams, the foamed material is by following parts by weight
Raw material is constituted：
Preferably, the Halogenless composite fire retardant is by graphene, graphite alkenyl phosphoric acid, graphene oxide, oxygen
Graphite alkenyl phosphoric acid, graphite phosphoric acid, graphite oxide phosphoric acid, graphite, graphite oxide, graphite, Phosphorus resistance
Fire agent, phosphorus pentoxide and it is elemental phosphorous in two or more composition.
Preferably, the Halogenless composite fire retardant by the raw material of following portions by weight in vacuum or inert gas
1~72h of ball milling is carried out under state with 20~750rpm ball milling speed to prepare：
100 parts of graphite type material；
50~600 parts of phosphorus type flame retardant.
The fire retardant mechanism of the Halogenless composite fire retardant is as follows：By graphite type material and phosphorus type flame retardant in ball
Mutually peeled off during mill, lamellar spacing is gradually thinning, and it is scattered highly uniform, be conducive to fire retardant
Fire resistance is greatly improved；Graphite type material is during stripping, lamellar spacing are thinning, Phosphorus resistance
Combustion agent also achieves nano-dispersed, meanwhile, active phosphorus easily occurs anti-with the edge of grapheme material after stripping
Should, generation graphite alkenyl phosphoric acid or phosphorylation graphite material, and graphite alkenyl phosphoric acid or phosphorylation graphite material are all
Possesses efficient fire resistance；In mechanical milling process, the presence of phosphorus type flame retardant contributes to graphite type material
Stripping, on the other hand, grapheme material peels off obtained graphene and is conducive to the scattered of phosphorus type flame retardant
Nano particle is obtained, the nano-dispersed of phosphorus is more conducive to the raising of composite flame-retardant agent performance.
Preferably, the graphite type material is selected from flaky graphite, blocky graphite, amorphous graphite, people
Make the one or more in graphite, expanded graphites and all kinds of graphite oxides of the above.
Preferably, the phosphorus type flame retardant is selected from red phosphorus, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, polyphosphoric acid
Amine, phosphamidon, trihydroxy phosphate, alkyl phosphate, aryl phosphate ester, annular phosphate, tricresyl phosphate
Phenyl ester, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, Trimethyl phosphite,
Triethyl phosphite, tributyl phosphite, the monooctyl ester of phosphorous acid three, triphenyl phosphite, organophosphorated salt,
One or more in phosphorous heterocylic compound, polymer phosphorus (phosphine) acid esters and organic metal phosphinate.
It is highly preferred that the Halogenless composite fire retardant graphite-like raw material selection expanded graphites；Described
Phosphorus type flame retardant raw material selection red phosphorus.Preferably should occur to further analyze in mechanical milling process in raw material
Between physics, after chemical action and ball milling composite flame-retardant agent composition.Red phosphorus with it is other Phosphorus fire-retardant
Agent is compared, and composition is single, and flame retarding efficiency is high, and to be ball-milling method prepare graphite for intumescent and flaky graphite
The preferred feedstock of alkene.
Preferably, the preparation method of the Halogenless composite fire retardant is：By raw graphite class material and Phosphorus
Fire retardant is positioned in steel hermetically sealed can, holding vacuum or inert gas state in hermetically sealed can, and progress ball milling 12~
48h, ball milling material and steel ball weight ratio are 1：20, ball milling speed is 400~600rpm, steel ball size
For 4~8mm, the volume of steel hermetically sealed can is 0.05~5L.
In the preparation process of the Halogenless composite fire retardant, the volume of steel ball size or steel hermetically sealed can it is excessive or
The too small mutual shearing release effect for being unfavorable for raw material and chemically react, steel sealing tank volume and steel
Bulb diameter, which matches, is conducive to the stripping of composite flame-retardant agent to refine and chemically react, and can effectively improve
The fire resistance and reduction smoke amount of composite flame-retardant agent.And using most suitable proportion of raw material, steel ball
Weight and steel ball size can obtain that even size distribution, specific surface area be big, solubility is good and fire-retardant effect
Rate most excellent composite flame-retardant agent and compared with low-smoke.In addition, ball milling speed and Ball-milling Time equally influence
The physical and chemical performance of composite flame-retardant agent, ball milling speed is too big and during long Ball-milling Time, prepares compound hinders
Fire agent when energy consumption and to equipment lose it is larger；Conversely, the physics of this composite flame-retardant agent obtained flame-retardant agent and
Chemical property is poor.
In the formula of the Halogen composite flame-proof Polyimide foams of the present invention, routine is selected
Fire retardant, but have selected the new and effective nothing developed after a large amount of creative works of the applicant
Halogen composite flame-retardant agent.The formula and content limited according to the present invention selects the fire retardant to prepare polyimides
Foamed material, the structural behaviour and performance in NCO polyimide can be met simultaneously,
Reason is as follows：
First, raw graphite and phosphorus type flame retardant are not only contained in the composite flame-retardant agent, also containing because of two originals
Graphene, graphite alkenyl phosphoric acid, graphene oxide, oxygen that material is mutually peeled off or occurs chemical reaction and generate
Graphite alkenyl phosphoric acid, graphite phosphoric acid, graphite oxide phosphoric acid, phosphorus pentoxide and nano-dispersed it is elemental phosphorous
Deng, these reaction generation material, simply mixed with both simple graphite type material and phosphorus type flame retardant
Compare, with more excellent fire resistance, fire-retardant synergistic performance and smoke suppressing effect, and resin,
The matrix such as PUR, coating or rubber more excellent dispersiveness and enhancing effect, while rubber can be improved
The corrosion resistance of wearability and coating.
Secondly, the pattern of the composite flame-retardant agent is the mixing of two-dimensional sheet structure and particulate matter, two-dimensional slice
Shape structure graphite alkenes lamella size 50nm~50 μm, phosphorus fire retardant particle size be 10nm~1 μm,
Specific surface area is 20~200m2/g；The solubility of the composite flame-retardant agent in deionized water be 0.15~
0.9mg/mL；Solubility of the composite flame-retardant agent in dimethylformamide is 0.2~1.2mg/mL；
Solubility of the composite flame-retardant agent in chloroform is 0.05~0.85mg/mL；The composite flame-retardant agent exists
Solubility in tetrahydrofuran is 0.05~0.80mg/mL；The composite flame-retardant agent is molten in dimethylbenzene
Xie Du is 0.02~0.75mg/mL, the superiority of the composite flame-retardant agent be embodied in bigger specific surface area,
The nano-dispersed of phosphorus type flame retardant, dispersiveness excellent in polarity and non-polar solven.
In addition, the composite flame-retardant agent added meeting and high score in the preparation process of Polyimide foams
Sub- storeroom produces synergy, and polyisocynate monomer and the oxygen-containing functional group on graphite alkenyl phosphoric acid surface hold
Easily chemically react, be conducive to the raising of scattered and foam mechanics and the heat resistance of fire retardant.
Preferably, the foamed material is made up of the raw material of following parts by weight：
This preferred feedstock composition can obtain that density is relatively low, foam structure uniform, mechanical property, heat resistance
And the excellent Polyimide foams of flame retarding and smoke suppressing properties.
Preferably, the aromatic dianhydride is selected from 3,3 ', 4, the acid anhydrides of 4 '-diphenyl ether four (ODPA), 3,3 ', 4,4 '-connection
Phenyl tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic acid
Dianhydride (PMDA), 2,2- bis- [4- (3,4- Phenoxyphenyls)] propane dianhydride (acid dianhydride of bisphenol A-type two)
(BPADA), 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride (DSDA), 2,3,3 ', 4 '-xenyl tetracarboxylic
Dianhydride (α-BPDA), bicyclic [2.2.1] heptane -2,3,5,6- tetracarboxylic dianhydrides (BHDA), the double [4- (3,4- of 2,2-
Two sections of flag benzene vanadium are difficult) benzene] hexafluoropropane dianhydride (BFDA), pentamethylene tetracarboxylic dianhydride (CPDA) 3,3 ', 4,4 '
In-diphenylsulfone acid dianhydride (DSDA), 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride (6FDA)
One or more.As above preferred aromatic dianhydride reactivity is high, is more easy to foaming, obtains preferably bubble
Foam material.
Preferably, the polar solvent is selected from DMF, DMA, N-
Methyl pyrrolidone or dimethyl sulfoxide (DMSO).It is highly preferred that the polar solvent is DMF
As above preferred polar solvent is conducive to monomer and auxiliary agent preferably to disperse for selection.
Preferably, the fatty alcohol is methanol or ethanol.Preferred fat alcohol can shorten the reaction time, reduction bubble
The preparation cost of foam.
Preferably, the foam stabiliser be non-hydrolytic type water soluble polyether siloxanes and polyvinyl alcohol with
1:0~2 weight is than mixing.This preferred foams stabilizer is conducive to preparation structure equably foamed material.
In a specific embodiment, the non-hydrolytic type water soluble polyether siloxanes can for DC193,
AK8805 or L580.
In a specific embodiment, the molecular weight of the polyvinyl alcohol is 100~1000.
It is highly preferred that the foam stabiliser is DC193, polyvinyl alcohol (molecular weight is 600) is with 1:1
Weight is than mixing.This preferably not only contributes to obtaining even structure foamed material, is more beneficial for obtaining power
Learn excellent performance ground foamed material.
Preferably, the composite catalyst is isoquinolin, triethanolamine, triethylenediamine, stannous octoate
With the one or more in dibutyl tin laurate.It is highly preferred that the composite catalyst be isoquinolin,
Any two in triethanolamine and dibutyl tin laurate are with 1:1 weight is than mixing.This is preferably combined and urged
Agent can improve the time needed for the degree and shortening imidizate of foamed material imidizate.
Preferably, the polyisocyanates is polyphenyl polymethylene polyisocyanates (PAPI), diphenyl
Methane diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI) and hexamethylene diisocyanate (HDI)
In one or more.This preferably polyisocynate monomer activity is big, is conducive to the progress of foaming process
And the generation of foam.
Present invention also offers a kind of preparation method of Halogen composite flame-proof Polyimide foams.
A kind of preparation method of Halogen composite flame-proof Polyimide foams as described above, including it is as follows
Step：
1) aromatic dianhydride and polar solvent are heated to 70~100 DEG C and are uniformly dispersed, add fatty alcohol
0.2~1h of esterification is carried out in 60~80 DEG C of backflows, solution A is obtained；
2) deionized water, foam stabiliser and composite catalyst are disperseed in solution A in 50~70 DEG C
Uniformly, Halogenless composite fire retardant is then added, well mixed suspension B is obtained；
3) it is rapidly added in suspension B by polyisocyanates and stirs 4~15s obtain compound, will
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
4) foam intermediate first passes through 140~200 DEG C of 1~2h of heating in vacuum, then by 250~
300 DEG C of heat, which are dried, carries out 0.5~2h of sub- amidatioon, finally gives Halogen composite flame-proof polyimide foam material
Material.
The present invention preparating mechanism be：Aromatic dianhydride is heated in polar solvent reacts with fatty alcohol, obtains
The solution of aromatic diacid diester；By deionized water, foam stabiliser and composite catalyst in aromatic diacid two
It is uniformly dispersed in ester solution；Halogenless composite fire retardant is added in above-mentioned solution, and uniformly hanged
Supernatant liquid；Polyisocyanates is rapidly added in suspension and high-speed stirred is uniform, compound is quickly fallen
Enter free foaming in mould and obtain foam intermediate；Foam intermediate solidifies by heating in vacuum, final
To fire-retardant Polyimide foams.
Preferably, step 1) in, aromatic dianhydride is heated to 80~100 DEG C and scattered equal with polar solvent
It is even, add fatty alcohol backflow and carry out 0.5~1h of esterification.This preferable temperature is conducive to the equal of aromatic dianhydride
It is even scattered, the too low bad dispersibility of temperature, the volatile dereaction activity of the too high aromatic dianhydride of temperature；Preferably return
The stream time ensures that esterification is fully completed.
Preferably, step 2) in solution A after addition Halogenless composite fire retardant, in 1000~20000rpm
Rotating speed under stirring 0.5~2h be well mixed.Halogen can be combined by this preferred mixing speed and time
Fire retardant is dispersed in solution A.
Preferably, step 3) in suspension B be maintained between -20~30 DEG C of scopes, then with many isocyanides
Free foaming after being stirred after acid esters mixing under 1000~20000rpm rotating speed.This preferred ground temperature
Degree ensure that monomer and auxiliary agent be fully mixed it is even before do not chemically react, it is ensured that foaming structure is more
Uniformly；Preferably mixing speed ensure that monomer and auxiliary agent are well mixed within a short period of time.
Preferably, step 4) in foam intermediate first pass through 150~180 DEG C progress vacuum heating treatments,
And initial temperature is 15~35 DEG C, heating rate is 1~10 DEG C/min.This preferred initial temperature and liter
Warm speed ensure that Polyimide foams are fully chemically reacted and ensure that foam structure is not sent out
Life is collapsed.
The formula and preparation method of Polyimide foams provided by the present invention, compared with prior art,
By adding the efficient halogen-free composite flame-retardant agent prepared by grapheme material and Phosphorus fire proofing, Ke Yishi
Show significantly improving for flame retarding efficiency；The excellent gas barrier property of graphite alkenes material and heat conductivility can
The foaming capacity of polyimides is improved, further the density of reduction foamed material；In addition, graphite alkenes material
Material can play humidification to high polymer material, improve the mechanical mechanics property of foamed material.Overcome
The shortcoming of conventional flame retardant filler increase foam density, destruction foaming structure and performance.
Therefore, the foamed material obtained by the present invention has that density is low, cell size distribution uniform, mechanical property
The features such as energy and excellent fireproof performance.It disclosure satisfy that the high-end fields such as Aero-Space, navigation are steeped with polyimides
The fire safety demands of foam material.
Beneficial effects of the present invention are as follows：
The inventive method, which prepares Polyimide foams, has that cost is low, density is low, foam structure
Uniformly, the advantages of mechanical property, heat resistance and more excellent flame retarding and smoke suppressing properties, overcome well
Structure and the problems such as not enough performance in polyimide prepared by prior art, disclosure satisfy that boat
The requirement of the high-end field such as empty space flight, navigation Polyimide foams.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the scanning of Halogen composite flame-proof Polyimide foams prepared by the embodiment of the present invention 2
Electron microscope.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done into one with reference to preferred embodiments and drawings
The explanation of step.Similar part is indicated with identical reference in accompanying drawing.Those skilled in the art
It should be appreciated that following specifically described content is illustrative and be not restrictive, it should not be limited with this
Protection scope of the present invention.
The Halogenless composite fire retardant that product of the present invention is used is to be prepared by grapheme material and Phosphorus fire proofing
Efficient halogen-free composite flame-retardant agent.Polyimide foam monomer selects BTDA and PAPI；Polar solvent is selected
Select N,N-dimethylformamide (DMF)；Foam stabiliser selects DC193 and PEG-600 with 1:1 weight
Amount is than mixing；Composite catalyst selects isoquinolin and dibutyl tin laurate with 1:1 weight is than mixing.Bubble
High-speed stirred speed used in foam material preparation process is 8000rpm.
Embodiment 1：
(1) graphite compares 1 with red phosphorus with weight:0.5 prepares Halogenless composite fire retardant；Specific preparation process
It is as follows：
The steel ball of 6.67g expanded graphites, 3.33g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100
It in mL steel hermetically sealed can, will be vacuumized in hermetically sealed can, ball milling 48h carried out with 480rpm ball milling speed
Afterwards, the black powder obtained as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, added
15 parts of methanol carry out esterification 0.5h in 70 DEG C of backflows, obtain settled solution A；
(3) by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 5 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 200 parts of PAPI are rapidly added in the suspension B of step (3) and high-speed stirred 10s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 0.5h is carried out by 280 DEG C of oven heats, fire-retardant Polyimide foams are finally given.Should
The scanning electron microscope (SEM) photograph of Halogen composite flame-proof Polyimide foams is as shown in Figure 1；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94 test.Measure result and be listed in table 1
In.
Embodiment 2：
(1) graphite compares 1 with red phosphorus with weight:1 prepares Halogenless composite fire retardant；Specific preparation process is such as
Under：
The steel ball of 5g expanded graphites, 5g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100mL's
It in steel hermetically sealed can, will be vacuumized in hermetically sealed can, carried out after ball milling 48h, obtained with 480rpm ball milling speed
The black powder arrived as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, added
15 parts of methanol carry out esterification 0.5h in 70 DEG C of backflows, obtain settled solution A；
(3) by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 5 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 200 parts of PAPI are rapidly added in the suspension B of step (3) and high-speed stirred 12s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 0.8h is carried out by 280 DEG C of oven heats, fire-retardant Polyimide foams are finally given.Should
The scanning electron microscope (SEM) photograph of Halogen composite flame-proof Polyimide foams is as shown in Figure 1；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 3：
(1) graphite compares 1 with red phosphorus with weight:1.5 prepare Halogenless composite fire retardant；Specific preparation process
It is as follows：
The steel ball of 4g expanded graphites, 6g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100mL's
It in steel hermetically sealed can, will be vacuumized in hermetically sealed can, carried out after ball milling 48h, obtained with 480rpm ball milling speed
The black powder arrived as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 90 DEG C with 200 parts of DMF and be uniformly dispersed, add 15
Part methanol carries out esterification 0.5h in 70 DEG C of backflows, obtains settled solution A；
(3) by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 6 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 150 parts of PAPI are rapidly added in step (3) suspension B and high-speed stirred 5s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 2h is carried out by 280 DEG C of oven heats, fire-retardant Polyimide foams are finally given；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 4：
(1) graphite compares 1 with red phosphorus with weight:4 prepare Halogenless composite fire retardant；Specific preparation process is such as
Under：
The steel ball of 2g expanded graphites, 8g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100mL's
It in steel hermetically sealed can, will be vacuumized in hermetically sealed can, carried out after ball milling 48h, obtained with 480rpm ball milling speed
The brown powder arrived as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 90 DEG C with 100 parts of DMF and be uniformly dispersed, add 15
Part methanol carries out esterification 1h in 70 DEG C of backflows, obtains settled solution A；
(3) by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 7 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 250 parts of PAPI are rapidly added in step (3) suspension B and high-speed stirred 8s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 1h, then
Sub- amidatioon 0.5h is carried out by 250 DEG C of oven heats, fire-retardant Polyimide foams are finally given；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 5：
(1) graphite compares 1 with red phosphorus with weight:6 prepare Halogenless composite fire retardant；Specific preparation process is such as
Under：
The steel ball of 1.43g expanded graphites, 8.57g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100
It in mL steel hermetically sealed can, will be vacuumized in hermetically sealed can, ball milling 48h carried out with 480rpm ball milling speed
Afterwards, the Red-brown powder obtained as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 90 DEG C with 150 parts of DMF and be uniformly dispersed, add 20
Part methanol carries out esterification 0.3h in 80 DEG C of backflows, obtains settled solution A；
(3) by 12 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 70 DEG C, then add 10 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 200PAPI is rapidly added in step (3) suspension B and high-speed stirred 10s, will
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 150 DEG C of heating in vacuum 1.5h, so
Sub- amidatioon 1h is carried out by 280 DEG C of oven heats afterwards, fire-retardant Polyimide foams are finally given；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 6：
(1) graphite compares 1 with red phosphorus with weight:10 prepare Halogenless composite fire retardant；Specific preparation process is such as
Under：
The steel ball of 0.91g expanded graphites, 9.09g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100
It in mL steel hermetically sealed can, will be vacuumized in hermetically sealed can, ball milling 48h carried out with 480rpm ball milling speed
Afterwards, the Red-brown powder obtained as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 180 parts of DMF and be uniformly dispersed, added
18 parts of methanol carry out esterification 0.8h in 75 DEG C of backflows, obtain settled solution A；
(3) by 8 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 15 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 220 parts of PAPI are rapidly added in step (3) suspension B and high-speed stirred 15s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 170 DEG C of heating in vacuum 1.5h, so
Sub- amidatioon 1.5h is carried out by 260 DEG C of oven heats afterwards, fire-retardant Polyimide foams are finally given；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 7：
(1) graphite compares 1 with red phosphorus with weight:5 prepare Halogenless composite fire retardant；Specific preparation process is such as
Under：
The steel ball of 1.67g expanded graphites, 8.33g simple substance red phosphorus and a diameter of 6mm of 200g is put into 100
It in mL steel hermetically sealed can, will be vacuumized in hermetically sealed can, ball milling 48h carried out with 480rpm ball milling speed
Afterwards, the black powder obtained as Halogenless composite fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 120 parts of DMF and be uniformly dispersed, added
18 parts of methanol carry out esterification 0.4h in 70 DEG C of backflows, obtain settled solution A；
(3) by 8 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 65 DEG C, then add 8 parts of Halogenless composite fire retardants, obtain
Uniform suspension B；
(4) 200 parts of PAPI are rapidly added in step (3) suspension B and high-speed stirred 8s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 160 DEG C of heating in vacuum 2h, then
Sub- amidatioon 0.5h is carried out by 290 DEG C of oven heats, fire-retardant Polyimide foams are finally given；
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Comparative example 1：
(1) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, added
15 parts of methanol carry out esterification 0.5h in 70 DEG C of backflows, obtain settled solution A；
(2) by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (1)
In settled solution A in be uniformly dispersed in 60 DEG C, obtain uniform suspension B；
(3) 200 parts of PAPI are rapidly added in step (2) suspension B and high-speed stirred 10s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(4) foam intermediate obtained in step (3) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 0.5h is carried out by 280 DEG C of oven heats, pure Polyimide foams are obtained.
(5) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Comparative example 2：
(1) pure graphite is prepared into fire retardant according to the ball milling condition ball milling of embodiment 1；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, added
15 parts of methanol carry out esterification 0.5h in 70 DEG C of backflows, obtain settled solution A；
(3) by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 100 parts of fire retardants, obtain uniform
Suspension B；
(4) 200 parts of PAPI are rapidly added in the suspension B of step (3) and high-speed stirred 10s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 1h is carried out by 280 DEG C of oven heats, fire-retardant Polyimide foams are finally given.
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Comparative example 3：
(1) pure red phosphorus is prepared into fire retardant according to the ball milling condition ball milling of embodiment 1；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, added
15 parts of methanol carry out esterification 0.5h in 70 DEG C of backflows, obtain settled solution A；
(3) by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In settled solution A in be uniformly dispersed in 60 DEG C, then add 10 parts of fire retardants, uniformly hanged
Supernatant liquid B；
(4) 200 parts of PAPI are rapidly added in step (3) component A solution and high-speed stirred 10s,
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, then
Sub- amidatioon 2h is carried out by 280 DEG C of oven heats, fire-retardant Polyimide foams are finally given.
(6) to density, compressive strength, HRR, limited oxygen index and the water of obtained foamed material
Flat vertical combustion is tested, and establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM
D7309, limited oxygen index GB/T 2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Table 1
It can be drawn from upper table：It is close that the addition of Halogenless composite fire retardant not only contributes to polyimide foam
The reduction of degree and the raising of compressive strength, and foam HRR substantially reduce and foam pole
Limited oxygen index, which has, significantly to be improved.Illustrate the proportioning according to component in inventive formulation and content, pass through
The flame-retardant smoke inhibition effect added Halogenless composite fire retardant and prepare obtained polyimide foam is very excellent,
Not only there is excellent structural behaviour, also with excellent performance, existing skill can be overcome well
The problems such as structure is with performance deficiency in polyimide prepared by art.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
It can also be made other changes in different forms on the basis of described above, here can not be to all
Embodiment be exhaustive, it is every to belong to the obvious change that technical scheme is extended out
Change or change the row still in protection scope of the present invention.
Claims (10)
1. a kind of Halogen composite flame-proof Polyimide foams, it is characterised in that the foamed material by
The raw material composition of following parts by weight：
2. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, its feature
It is：The Halogenless composite fire retardant is by graphene, graphite alkenyl phosphoric acid, graphene oxide, graphite oxide
Alkenyl phosphoric acid, graphite phosphoric acid, graphite oxide phosphoric acid, graphite oxide, graphite, phosphorus type flame retardant, five oxidations
Two phosphorus and it is elemental phosphorous in two or more composition.
3. a kind of Halogen composite flame-proof Polyimide foams according to claim 1 or 2, its
It is characterised by, the Halogenless composite fire retardant is by the raw material of following portions by weight in vacuum or inert gas shape
1~72h of ball milling is carried out under state with 20~750rpm ball milling speed to prepare：
100 parts of graphite type material；
50~600 parts of phosphorus type flame retardant.
4. a kind of Halogen composite flame-proof Polyimide foams according to claim 3, its feature
It is：The graphite type material be selected from flaky graphite, blocky graphite, amorphous graphite, Delanium,
One or more in expanded graphites and all kinds of graphite oxides of the above；The phosphorus type flame retardant is selected from
Red phosphorus, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, polyphosphoric acid amine, phosphamidon, trihydroxy phosphate, alkyl phosphorus
Acid esters, aryl phosphate ester, annular phosphate, triphenyl phosphate, trimethyl phosphate, triethyl phosphate,
Tributyl phosphate, trioctyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite,
The monooctyl ester of phosphorous acid three, triphenyl phosphite, organophosphorated salt, phosphorous heterocylic compound, polymer phosphorus (phosphine)
One or more in acid esters and organic metal phosphinate.
5. a kind of Halogen composite flame-proof Polyimide foams according to claim 3, its feature
It is：The preparation method of the Halogenless composite fire retardant is：By raw graphite class material and phosphorus type flame retardant
It is positioned in steel hermetically sealed can, vacuum or inert gas state is kept in hermetically sealed can, carries out 12~48h of ball milling,
Ball milling material and steel ball weight ratio are 1：20, ball milling speed be 400~600rpm, steel ball size be 4~
8mm, the volume of steel hermetically sealed can is 0.05~5L.
6. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, its feature
It is, the foamed material is made up of the raw material of following parts by weight：
7. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, its feature
It is：The aromatic dianhydride be selected from the acid anhydrides of 3,3 ', 4,4 '-diphenyl ether four, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride,
3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,2- bis- [4- (3,4- Phenoxyphenyls)] propane
Dianhydride (acid dianhydride of bisphenol A-type two), 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, 2,3,3 ', 4 '-xenyl four
Double [the 4- of carboxyl dianhydride, bicyclic [2.2.1] heptane -2,3,5,6- tetracarboxylic dianhydrides, 2,2- (bis- sections of flag benzene vanadium of 3,4- are difficult)
Benzene] hexafluoropropane dianhydride, pentamethylene tetracarboxylic dianhydride, 3,3 ', 4,4 '-diphenylsulfone acid dianhydride, 4,4 '-hexafluoro be sub-
One or more in isopropyl-phthalic anhydride；The polar solvent be selected from N,N-dimethylformamide,
DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE or dimethyl sulfoxide (DMSO)；The fatty alcohol is methanol or ethanol；
The foam stabiliser is non-hydrolytic type water soluble polyether siloxanes and polyvinyl alcohol with 1:0~2 weight is than mixed
Close；The composite catalyst is isoquinolin, triethanolamine, triethylenediamine, stannous octoate and two bays
One or more in sour dibutyl tin；The polyisocyanates be polyphenyl polymethylene polyisocyanates,
One kind or many in methyl diphenylene diisocyanate, toluene di-isocyanate(TDI) and hexamethylene diisocyanate
Kind.
8. a kind of preparation method of Halogen composite flame-proof Polyimide foams as claimed in claim 1,
It is characterised in that it includes following steps：
1) aromatic dianhydride and polar solvent are heated to 70~100 DEG C and are uniformly dispersed, add fatty alcohol
0.2~1h of esterification is carried out in 60~80 DEG C of backflows, solution A is obtained；
2) deionized water, foam stabiliser and composite catalyst are disperseed in solution A in 50~70 DEG C
Uniformly, Halogenless composite fire retardant is then added, well mixed suspension B is obtained；
3) it is rapidly added in suspension B by polyisocyanates and stirs 4~15s obtain compound, will
Compound is quickly poured into free foaming in mould and obtains foam intermediate；
4) foam intermediate first passes through 140~200 DEG C of 1~2h of heating in vacuum, then by 250~
300 DEG C of heat, which are dried, carries out 0.5~2h of sub- amidatioon, finally gives Halogen composite flame-proof polyimide foam material
Material.
9. a kind of preparation side of Halogen composite flame-proof Polyimide foams according to claim 8
Method, it is characterised in that：Step 1) in, aromatic dianhydride is heated to 80~100 DEG C with polar solvent and divided
Dissipate uniform, add fatty alcohol backflow and carry out 0.5~1h of esterification；Preferably, step 2) in solution A
After middle addition Halogenless composite fire retardant, 0.5~2h mixing is stirred under 1000~20000rpm rotating speed
Uniformly.
10. a kind of preparation of Halogen composite flame-proof Polyimide foams according to claim 8
Method, it is characterised in that：Step 3) in suspension B be maintained between -20~30 DEG C of scopes, Ran Houyu
Free foaming after being stirred after polyisocyanates mixing under 1000~20000rpm rotating speed；It is preferred that
Ground, step 4) in foam intermediate first pass through 150~180 DEG C of progress vacuum heating treatments, and initial temperature
Spend for 15~35 DEG C, heating rate is 1~10 DEG C/min.
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| CN113185752A (en) * | 2021-06-09 | 2021-07-30 | 北京理工大学 | Method for preparing flame retardant by adopting red phosphorus stripped graphite |
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