CN107286343B - 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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- CN107286343B CN107286343B CN201610206289.1A CN201610206289A CN107286343B CN 107286343 B CN107286343 B CN 107286343B CN 201610206289 A CN201610206289 A CN 201610206289A CN 107286343 B CN107286343 B CN 107286343B
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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
Abstract
The present invention discloses a kind of Halogen composite flame-proof Polyimide foams and preparation method thereof.The foamed material is made 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.It is reacted the preparation method is that aromatic dianhydride heats in polar solvent with fatty alcohol；Add deionized water, foam stabiliser and composite catalyst, Halogenless composite fire retardant obtains suspension；It is eventually adding that polyisocyanates is foamed and heating in vacuum solidification, finally obtains fire-retardant Polyimide foams.Foamed material obtained by the present invention has the characteristics that density is low, cell size distribution is uniform, mechanical property, heat resistance and flame retarding and smoke suppressing properties are excellent.It can satisfy the requirement of the high-end fields such as aerospace, 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 polyimides
Foamed material and preparation method thereof.
Background technique
Polyimides is while to be also resistant to pole so far in the highest polymer material of industrial circle application temperature classification
Low temperature has excellent mechanical property.The foam performance of polyimides is excellent, and density can design, radiation hardness, resistance to combustion, low hair
Smoke performance, no pernicious gas release.Polyimide foams be increasingly used in aerospace, transport by sea, national defence and
The critical materials such as the heat-insulated of the high-technology fields such as microelectronics, damping noise reduction and insulation.
The polyimide foam high comprehensive performance of powder foam method preparation, but preparation process is complicated, process route compared with
Long, the high requirements on the equipment, obtained froth pulp price costly, therefore limits it and is widely used.And isocyanates
The method of base polyimide foam simplifies production procedure, reduces production cost, but due to lower anti-between raw material
Speed and the lower extent of reaction are answered, the generation of a large amount of by-products (polyureas) is caused, reduces the flame retardant property of material.Chinese patent
The compound of hydrotalcite, inorganic mineral and organic liquid fire retardant is respectively adopted in (publication number CN103897395 and CN104497255)
As the fire retardant of isocyanate group Polyimide foams, flame retardant effect is excellent, since additive amount is larger, is easy to influence bubble
The structure and service performance of foam.Chinese patent (publication number CN104804190) is by answering polyimide foam and cellular material
Conjunction is prepared into honeycomb structure to improve its flame retardant property, but the method is limited to the flame retardant property raising of foam.
In view of not damaging product structure and service performance while improving Polyimide foams flame-retardancy requirements,
And the composite factors such as smoke when reducing product burning.The nothing that a kind of additive amount is few, nontoxic and pollution-free, flame retardant property is good need to be provided
Halogen fire retardant, to guarantee the structure and service performance of Polyimide foams.
Summary of the invention
It is an object of the present invention to provide a kind of Halogen composite flame-proof Polyimide foams.Foamed material tool
Have density is low, cell size distribution uniformly, mechanical property and the features such as excellent fireproof performance, overcome prior art system well
The problems such as structure and service performance are insufficient in standby polyimide.
It is another object of the present invention to provide a kind of preparation methods of Halogen composite flame-proof Polyimide foams.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of Halogen composite flame-proof Polyimide foams, the foamed material by following parts by weight raw material group
At:
Preferably, the Halogenless composite fire retardant is by graphene, graphite alkenyl phosphoric acid, graphene oxide, graphene oxide phosphorus
Acid, graphite phosphoric acid, graphite oxide phosphoric acid, graphite, graphite oxide, graphite, phosphorus type flame retardant, phosphorus pentoxide and it is elemental phosphorous in
Two or more compositions.
Preferably, the Halogenless composite fire retardant by the raw material of following portions by weight under vacuum or inert gas state with
The ball milling speed of 20~750rpm carries out 1~72h of ball milling and is prepared:
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: through graphite type material and phosphorus type flame retardant in mechanical milling process
Mutually removing, lamellar spacing is gradually thinning, and dispersion is highly uniform, is conducive to greatly improving for fire retardant performance；Stone
For black class material during removing, lamellar spacing are thinning, phosphorus type flame retardant also achieves nano-dispersed, meanwhile, active phosphorus is easy
It reacts with the edge of grapheme material after removing, generation graphite alkenyl phosphoric acid or phosphorylation graphite material, and graphite alkenyl phosphoric acid
Or phosphorylation graphite material all has efficient flame retardant property；In mechanical milling process, the presence of phosphorus type flame retardant facilitates graphite
The removing of class material, on the other hand, the dispersion that the graphene that grapheme material is removed is conducive to phosphorus type flame retardant is received
Rice grain, the nano-dispersed of phosphorus are 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, artificial graphite, expansion
Type graphite and more than one of all kinds of graphite oxides or a variety of.
Preferably, the phosphorus type flame retardant is selected from red phosphorus, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, polyphosphoric acid amine, phosphamidon, three
Hydroxyl phosphate, alkyl phosphate, aryl phosphate ester, annular phosphate, triphenyl phosphate, trimethyl phosphate, triethyl phosphate,
Tributyl phosphate, trioctyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, three monooctyl ester of phosphorous acid, Asia
Triphenyl phosphate, organophosphorated salt, phosphorous heterocylic compound, polymer phosphorus (phosphine) one of acid esters and organic metal phosphinate
Or it is a variety of.
It is highly preferred that the Halogenless composite fire retardant graphite-like raw material selection expanded graphites；Described is Phosphorus fire-retardant
Agent raw material selection red phosphorus.This is preferably made to further analyze physics, chemistry of the generation between raw material in mechanical milling process
With and ball milling after composite flame-retardant agent ingredient.For red phosphorus compared with other phosphorus type flame retardants, ingredient is single, and flame retarding efficiency is high, and
Intumescent and flaky graphite are the preferred raw materials that ball-milling method prepares graphene.
Preferably, the Halogenless composite fire retardant the preparation method comprises the following steps: raw graphite class material and phosphorus type flame retardant are put
It is placed in steel hermetically sealed can, vacuum or inert gas state is kept in hermetically sealed can, carry out 12~48h of ball milling, ball milling material and steel ball
Weight ratio is 1:20, and ball milling speed is 400~600rpm, and steel ball size is 4~8mm, and 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 is excessive or too small unfavorable
In raw material mutual shearing release effect and chemically react, steel sealing tank volume and steel ball size match is conducive to it is multiple
It closes the removing refinement of fire retardant and chemically reacts, the flame retardant property of composite flame-retardant agent can be effectively improved and reduce smoke
Amount.And even size distribution, specific surface area can be obtained using most suitable proportion of raw material, steel ball weight and steel ball size
Greatly, solubility is good and the most excellent composite flame-retardant agent of flame retarding efficiency and compared with low-smoke.In addition, ball milling speed and Ball-milling Time
The same physical and chemical performance for influencing composite flame-retardant agent prepares composite flame-retardant agent when ball milling speed is too big and Ball-milling Time is too long
When energy consumption and to equipment lose it is larger；Conversely, the physical and chemical properties of this composite flame-retardant agent obtained flame-retardant agent are poor.
In the formula of Halogen composite flame-proof Polyimide foams of the invention, conventional fire retardant is not selected,
But the new and effective Halogenless composite fire retardant developed after a large amount of creative works of the applicant is selected.According to this
It invents the formula limited and content selects the fire retardant to prepare Polyimide foams, isocyanate group can be met simultaneously
Structural behaviour and service performance in polyimide, the reason is as follows that:
Firstly, not only containing raw graphite and phosphorus type flame retardant in the composite flame-retardant agent, also contain because two raw materials are mutually shelled
From or occur chemical reaction and generate graphene, graphite alkenyl phosphoric acid, graphene oxide, graphite oxide alkenyl phosphoric acid, graphite phosphoric acid,
Elemental phosphorous etc., the substance that these reactions generate, with simple graphite-like material of graphite oxide phosphoric acid, phosphorus pentoxide and nano-dispersed
The simple mixed phase ratio of both material and phosphorus type flame retardant has more excellent flame retardant property, fire-retardant synergistic performance and suppression cigarette effect
Fruit, and in the superior dispersibility of the matrix such as resin, hot melt adhesive, coating or rubber and reinforcing effect, while rubber can be improved
Wearability and coating corrosion resistance.
Secondly, the pattern of the composite flame-retardant agent is the mixing of two-dimensional sheet structure and particulate matter, two-dimensional sheet structure stone
Black alkenes lamella size 50nm~50 μm, phosphorus fire retardant particle size is 10nm~1 μm, specific surface area is 20~200m2/g；Institute
Stating the solubility of composite flame-retardant agent in deionized water is 0.15~0.9mg/mL；The composite flame-retardant agent is in dimethylformamide
In solubility be 0.2~1.2mg/mL；Solubility of the composite flame-retardant agent in chloroform is 0.05~0.85mg/mL；Institute
Stating solubility of the composite flame-retardant agent in tetrahydrofuran is 0.05~0.80mg/mL；The composite flame-retardant agent is in dimethylbenzene
Solubility is 0.02~0.75mg/mL, and the superiority of the composite flame-retardant agent is embodied in bigger specific surface area, phosphorus type flame retardant
Nano-dispersed, dispersibility excellent in polarity and nonpolar solvent.
In addition, added composite flame-retardant agent is in the preparation process of Polyimide foams between meeting and high molecular material
Synergistic effect is generated, polyisocynate monomer and the oxygen-containing functional group on graphite alkenyl phosphoric acid surface are easy to happen chemical reaction, favorably
In the dispersion of fire retardant and the raising of foam mechanics and heat resistance.
Preferably, the foamed material is made of the raw material of following parts by weight:
This preferred raw material form can get density is lower, foam structure uniformly, mechanical property, heat resistance and fire-retardant suppression
The excellent Polyimide foams of smoke performance.
Preferably, the aromatic dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether, four acid anhydrides (ODPA), 3,3 ', 4,4 '-xenyls
Tetracarboxylic dianhydride (BPDA), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (BTDA), pyromellitic acid dianhydride (PMDA), 2,2- bis-
[4- (3,4- Phenoxyphenyl)] propane dianhydride (two acid dianhydride of bisphenol A-type) (BPADA), 3,3 ', 4,4 '-xenyl sulfone tetracarboxylics
Dianhydride (DSDA), 2,3,3 ', 4 '-xenyl tetracarboxylic dianhydrides (α-BPDA), bicyclic [2.2.1] heptane -2,3,5,6- tetracid two
Acid anhydride (BHDA), 2,2- bis- [4- (bis- sections of flag benzene vanadium of 3,4- are difficult) benzene] hexafluoropropane dianhydrides (BFDA), pentamethylene tetracid dianhydride
(CPDA) 3,3 ', 4,4 '-diphenylsulfone acid's dianhydrides (DSDA), in 4,4 '-hexafluoroisopropyli,enes-phthalic anhydride (6FDA)
It is one or more.As above preferred aromatic dianhydride reactivity is high, is easier to foam, obtains ideal foamed material.
Preferably, the polar solvent is selected from n,N-Dimethylformamide, n,N-dimethylacetamide, N- crassitude
Ketone or dimethyl sulfoxide.It is highly preferred that the polar solvent is that as above preferably polar solvent has for n,N-Dimethylformamide selection
It is better dispersed conducive to monomer and auxiliary agent.
Preferably, the fatty alcohol is methanol or ethyl alcohol.Preferred fat alcohol can shorten the reaction time, reduce the preparation of foam
Cost.
Preferably, the foam stabiliser is non-hydrolytic type water soluble polyether siloxanes and polyvinyl alcohol with the weight of 1:0~2
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 600) is with the mixing of 1:1 weight ratio.
This preferably not only contributes to obtain structure equably foamed material, is more advantageous to obtaining excellent in mechanical performance foamed material.
Preferably, the composite catalyst is isoquinolin, triethanolamine, triethylenediamine, stannous octoate and two laurels
One of sour dibutyl tin is a variety of.It is highly preferred that the composite catalyst is isoquinolin, triethanolamine and tin dilaurate two
Any two in butyl tin are with the mixing of 1:1 weight ratio.Preferably foamed material imidizate can be improved in composite catalyst for this
Time needed for degree and shortening imidizate.
Preferably, the polyisocyanates is that polyphenyl polymethylene polyisocyanates (PAPI), diphenyl methane two are different
One of cyanate (MDI), toluene di-isocyanate(TDI) (TDI) and hexamethylene diisocyanate (HDI) are a variety of.This is preferably
Ground polyisocynate monomer activity is big, is conducive to the progress of foaming process and the generation of foam.
The present invention also provides a kind of preparation methods of Halogen composite flame-proof Polyimide foams.
A kind of preparation method of Halogen composite flame-proof Polyimide foams as described above, includes the following steps:
1) aromatic dianhydride is heated to 70~100 DEG C with polar solvent and be uniformly dispersed, add fatty alcohol 60~80
DEG C reflux carry out 0.2~1h of esterification, obtain solution A；
2) deionized water, foam stabiliser and composite catalyst are uniformly dispersed in solution A in 50~70 DEG C, are then added
Add Halogenless composite fire retardant, obtains uniformly mixed suspension B；
3) polyisocyanates is rapidly added in suspension B and stirs 4~15s to obtain mixture, mixture is quick
It pours into free foaming in mold and obtains foam intermediate；
4) foam intermediate first passes through 140~200 DEG C of 1~2h of heating in vacuum, then dries and carries out by 250~300 DEG C of heat
Sub- 0.5~2h of amidation finally obtains Halogen composite flame-proof Polyimide foams.
Preparating mechanism of the invention are as follows: aromatic dianhydride heats in polar solvent reacts with fatty alcohol, obtains aromatic diacid
The solution of diester；Deionized water, foam stabiliser and composite catalyst are uniformly dispersed in two ester solution of aromatic diacid；By nothing
Halogen composite flame-retardant agent is added in above-mentioned solution, and obtains uniform suspension；Polyisocyanates is rapidly added to suspension
In and high-speed stirred it is uniform, mixture is quickly poured into free foaming in mold and obtains foam intermediate；Foam intermediate is passed through
Heating in vacuum solidification, finally obtains fire-retardant Polyimide foams.
Preferably, in step 1), aromatic dianhydride is heated to 80~100 DEG C with polar solvent and is uniformly dispersed, and fat is added
Alcohol reflux carries out 0.5~1h of esterification.This preferable temperature is conducive to the evenly dispersed of aromatic dianhydride, the too low dispersibility of temperature
Difference, the volatile dereaction activity of the excessively high aromatic dianhydride of temperature；Preferred return time guarantees that esterification is sufficiently completed.
Preferably, it after adding Halogenless composite fire retardant in solution A in step 2), is stirred under the revolving speed of 1000~20000rpm
0.5~2h is mixed to be uniformly mixed.Halogenless composite fire retardant can be dispersed in solution A by this preferred mixing speed and time
In.
Preferably, suspension B is maintained between -20~30 DEG C of ranges in step 3), after then mixing with polyisocyanates
The free foaming after mixing evenly under the revolving speed of 1000~20000rpm.Preferably temperature can guarantee that monomer and auxiliary agent fill for this
Point be mixed it is even before do not chemically react, guarantee that foaming structure is more uniform；Preferably mixing speed can guarantee monomer and help
Agent is uniformly mixed within a short period of time.
Preferably, foam intermediate first passes through 150~180 DEG C of progress vacuum heating treatments, and initial temperature in step 4)
It is 15~35 DEG C, heating rate is 1~10 DEG C/min.This preferred initial temperature and heating rate can guarantee polyimide foam
Material is sufficiently chemically reacted and guarantees that foam structure does not collapse.
The formula and preparation method of Polyimide foams provided by the present invention, compared with prior art, by adding
Add by the efficient halogen-free composite flame-retardant agent of grapheme material and the preparation of Phosphorus fire proofing, significantly mentioning for flame retarding efficiency may be implemented
It is high；The excellent gas barrier property of graphite alkenes material and heating conduction can be improved the foaming capacity of polyimides, further
Reduce the density of foamed material；In addition, graphite alkenes material can play humidification to high molecular material, foamed material is improved
Mechanical mechanics property.Conventional flame retardant filler is overcome to increase foam density, destroy the shortcomings that foaming structure and service performance.
Therefore, the foamed material obtained by the present invention have density is low, cell size distribution uniformly, mechanical property and fire-retardant
The features such as haveing excellent performance.The fire safety that can satisfy the high-end fields such as aerospace, navigation Polyimide foams is wanted
It asks.
Beneficial effects of the present invention are as follows:
Polyimide foams are prepared at low cost, density is low, foam structure is uniform, mechanics in the method for the present invention
The advantages that performance, more excellent heat resistance and flame retarding and smoke suppressing properties, the polyamides for overcoming prior art preparation well are sub-
The problems such as structure and service performance are insufficient in amine product, can satisfy the high-end fields such as aerospace, navigation and is steeped with polyimides
The requirement of foam material.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the scanning electron microscope (SEM) photograph of the Halogen composite flame-proof Polyimide foams of the preparation of the embodiment of the present invention 2.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
The Halogenless composite fire retardant that product of the present invention uses is efficient to be prepared by grapheme material with Phosphorus fire proofing
Halogenless composite fire retardant.Polyimide foam monomer selects BTDA and PAPI；Polar solvent selects N,N-dimethylformamide
(DMF)；Foam stabiliser selects DC193 and PEG-600 with the mixing of 1:1 weight ratio；Composite catalyst selects isoquinolin and February
Dilaurylate is with the mixing of 1:1 weight ratio.High-speed stirred rate used in foamed material preparation process is 8000rpm.
Embodiment 1:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:0.5；Specific preparation process is as follows:
6.67g expanded graphites, 3.33g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL
In, it will be vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained black powder is that Halogen is multiple
Close fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, 15 parts of methanol are added and flow back at 70 DEG C
Esterification 0.5h is carried out, clear solution A is obtained；
(3) the clear solution A by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 to in the suspension B of step (3) simultaneously high-speed stirred 10s, mixture is quick
It pours into free foaming in mold and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 0.5h, finally obtains fire-retardant Polyimide foams.The Halogen composite flame-proof polyimide foam material
The scanning electron microscope (SEM) photograph of material is as shown in Figure 1；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94 test.Measure that the results are shown in Table 1.
Embodiment 2:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:1；Specific preparation process is as follows:
5g expanded graphites, 5g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL, will
It is vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained black powder is Halogen composite flame-proof
Agent；
(2) 100 parts of BTDA are heated to 100 DEG C with 100 parts of DMF and be uniformly dispersed, 15 parts of methanol are added and flow back at 70 DEG C
Esterification 0.5h is carried out, clear solution A is obtained；
(3) the clear solution A by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 to in the suspension B of step (3) simultaneously high-speed stirred 12s, mixture is quick
It pours into free foaming in mold and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 0.8h, finally obtains fire-retardant Polyimide foams.The Halogen composite flame-proof polyimide foam material
The scanning electron microscope (SEM) photograph of material is as shown in Figure 1；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 3:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:1.5；Specific preparation process is as follows:
4g expanded graphites, 6g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL, will
It is vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained black powder is Halogen composite flame-proof
Agent；
(2) 100 parts of BTDA are heated to 90 DEG C with 200 parts of DMF and be uniformly dispersed, 15 parts of methanol are added and are flowed back at 70 DEG C
Row esterification 0.5h, obtains clear solution A；
(3) the clear solution A by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 simultaneously high-speed stirred 5s, mixture is quickly poured into
Free foaming obtains foam intermediate in mold；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 2h, finally obtains fire-retardant Polyimide foams；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 4:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:4；Specific preparation process is as follows:
2g expanded graphites, 8g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL, will
It is vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained brown powder is Halogen composite flame-proof
Agent；
(2) 100 parts of BTDA are heated to 90 DEG C with 100 parts of DMF and be uniformly dispersed, 15 parts of methanol are added and are flowed back at 70 DEG C
Row esterification 1h, obtains clear solution A；
(3) the clear solution A by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 simultaneously high-speed stirred 8s, mixture is quickly poured into
Free foaming obtains foam intermediate in mold；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 1h, is then dried by 250 DEG C of heat
Case carries out sub- amidation 0.5h, finally obtains fire-retardant Polyimide foams；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 5:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:6；Specific preparation process is as follows:
1.43g expanded graphites, 8.57g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL
In, it will be vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained Red-brown powder is Halogen
Composite flame-retardant agent；
(2) 100 parts of BTDA are heated to 90 DEG C with 150 parts of DMF and be uniformly dispersed, 20 parts of methanol are added and are flowed back at 80 DEG C
Row esterification 0.3h, obtains clear solution A；
(3) the clear solution A by 12 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 simultaneously high-speed stirred 10s, mixture is quickly poured into
Free foaming obtains foam intermediate in mold；
(5) foam intermediate obtained in step (4) is first passed through into 150 DEG C of heating in vacuum 1.5h, then passes through 280 DEG C of heat
Baking oven carries out sub- amidation 1h, finally obtains fire-retardant Polyimide foams；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 6:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:10；Specific preparation process is as follows:
0.91g expanded graphites, 9.09g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL
In, it will be vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained Red-brown powder is Halogen
Composite flame-retardant agent；
(2) 100 parts of BTDA are heated to 100 DEG C with 180 parts of DMF and be uniformly dispersed, 18 parts of methanol are added and flow back at 75 DEG C
Esterification 0.8h is carried out, clear solution A is obtained；
(3) the clear solution A by 8 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 simultaneously high-speed stirred 15s, mixture is quickly fallen
Enter free foaming in mold 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, then passes through 260 DEG C of heat
Baking oven carries out sub- amidation 1.5h, finally obtains fire-retardant Polyimide foams；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Embodiment 7:
(1) graphite and red phosphorus prepare Halogenless composite fire retardant with weight ratio 1:5；Specific preparation process is as follows:
1.67g expanded graphites, 8.33g simple substance red phosphorus and 200g diameter are that the steel ball of 6mm is put into the steel hermetically sealed can of 100mL
In, it will be vacuumized in hermetically sealed can, after carrying out ball milling 48h with the ball milling speed of 480rpm, obtained black powder is that Halogen is multiple
Close fire retardant；
(2) 100 parts of BTDA are heated to 100 DEG C with 120 parts of DMF and be uniformly dispersed, 18 parts of methanol are added and flow back at 70 DEG C
Esterification 0.4h is carried out, clear solution A is obtained；
(3) the clear solution A by 8 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 simultaneously high-speed stirred 8s, mixture is quickly poured into
Free foaming obtains foam intermediate in mold；
(5) foam intermediate obtained in step (4) is first passed through into 160 DEG C of heating in vacuum 2h, is then dried by 290 DEG C of heat
Case carries out sub- amidation 0.5h, finally obtains fire-retardant Polyimide foams；
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit 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, 15 parts of methanol are added and flow back at 70 DEG C
Esterification 0.5h is carried out, clear solution A is obtained；
(2) the clear solution A by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (1)
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 simultaneously high-speed stirred 10s, mixture is quickly fallen
Enter free foaming in mold and obtains foam intermediate；
(4) foam intermediate obtained in step (3) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 0.5h, obtains pure Polyimide foams.
(5) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit 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, 15 parts of methanol are added and flow back at 70 DEG C
Esterification 0.5h is carried out, clear solution A is obtained；
(3) the clear solution A by 15 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
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 to in the suspension B of step (3) simultaneously high-speed stirred 10s, mixture is quick
It pours into free foaming in mold and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 1h, finally obtains fire-retardant Polyimide foams.
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit 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, 15 parts of methanol are added and flow back at 70 DEG C
Esterification 0.5h is carried out, clear solution A is obtained；
(3) the clear solution A by 10 parts of deionized waters, 15 parts of foam stabilisers and 5 parts of composite catalysts in step (2)
In be uniformly dispersed in 60 DEG C, then add 10 parts of fire retardants, obtain uniform suspension B；
(4) 200 parts of PAPI are rapidly added in step (3) component A solution simultaneously high-speed stirred 10s, mixture is quick
It pours into free foaming in mold and obtains foam intermediate；
(5) foam intermediate obtained in step (4) is first passed through into 180 DEG C of heating in vacuum 2h, is then dried by 280 DEG C of heat
Case carries out sub- amidation 2h, finally obtains fire-retardant Polyimide foams.
(6) it burns to the density of obtained foamed material, compressive strength, heat release rate, limit oxygen index and horizontal vertical
It is tested, establishing criteria is compression GB/T 8813-2008, miniature calorimeter ASTM D7309, limit oxygen index GB/T
2406-93, vertical combustion UL94.Measure that the results are shown in Table 1.
Table 1
It follows that the addition of Halogenless composite fire retardant not only contributes to the reduction of polyimide foam density from upper table
It is substantially reduced with the heat release rate of the raising of compressive strength, and foam and the limit oxygen index of foam has and significantly improves
?.Illustrate the proportion according to component in inventive formulation and content, is prepared by addition Halogenless composite fire retardant poly-
The flame-retardant smoke inhibition effect of acid imide foam is very excellent, not only has excellent structural behaviour, also has excellent service performance,
The problems such as structure and service performance are insufficient in the polyimide of prior art preparation can be overcome well.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (11)
1. a kind of Halogen composite flame-proof Polyimide foams, which is characterized in that the foamed material is by following parts by weight
Raw material composition:
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 Halogenless composite fire retardant is by the raw material of following portions by weight with 20~750 rpm under vacuum or inert gas state
Ball milling speed carry out 1~72 h of ball milling be prepared:
100 parts of graphite type material；
50~600 parts of phosphorus type flame retardant.
2. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, it is characterised in that: the Halogen
Composite flame-retardant agent is by graphene, graphite alkenyl phosphoric acid, graphene oxide, graphite oxide alkenyl phosphoric acid, graphite phosphoric acid, graphite oxide phosphorus
Two or more compositions in acid, graphite oxide, graphite and phosphorus type flame retardant.
3. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, it is characterised in that: the graphite
Class material be selected from flaky graphite, blocky graphite, amorphous graphite, artificial graphite, expanded graphites and more than all kinds of graphite
One of oxide is a variety of；The phosphorus type flame retardant is selected from red phosphorus, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium polyphosphate, phosphorus
Amine, trihydroxy phosphate, alkyl phosphate, aryl phosphate ester, annular phosphate, triphenyl phosphate, trimethyl phosphate, tricresyl phosphate
Ethyl ester, tributyl phosphate, trioctyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, phosphorous acid three are pungent
Ester, triphenyl phosphite, organophosphorated salt, phosphorous heterocylic compound, polymeric phosphoric acid ester, polymer phosphine acid esters and organophosphinic acids
One of metal salt is a variety of.
4. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, it is characterised in that: the Halogen
Composite flame-retardant agent the preparation method comprises the following steps: raw graphite class material and phosphorus type flame retardant are placed in steel hermetically sealed can, in hermetically sealed can
Vacuum or inert gas state are kept, carries out 12~48 h of ball milling, ball milling material and steel ball weight ratio are 1:20, and ball milling speed is
400~600 rpm, steel ball size are 4~8 mm, and the volume of steel hermetically sealed can is 0.05 ~ 5 L.
5. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, which is characterized in that the foam
Material is made of the raw material of following parts by weight:
100 parts of aromatic dianhydride,
80~200 parts of polar solvent,
5~20 parts of fatty alcohol,
10~15 parts of deionized water,
15 parts of foam stabiliser,
5 parts of composite catalyst,
5~20 parts of Halogenless composite fire retardant,
150~300 parts of polyisocyanates.
6. a kind of Halogen composite flame-proof Polyimide foams according to claim 1, it is characterised in that: the fragrance
Dianhydride is selected from 3,3 ', 4,4 '-diphenyl ether tetracid dianhydrides, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydrides, 3,3 ', 4,4 '-hexichol first
Ketone tetracarboxylic dianhydride, pyromellitic acid dianhydride, bisphenol A dianhydride, 2,3,3 ', 4 '-xenyl tetracarboxylic dianhydrides, pentamethylene tetracid two
Acid anhydride, 3,3 ', one of 4,4 '-diphenylsulfone acid's dianhydrides, 4,4 '-hexafluoroisopropyli,enes-phthalic anhydride or a variety of；Institute
It states polar solvent and is selected from N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or dimethyl sulfoxide；Institute
Stating fatty alcohol is methanol or ethyl alcohol；The foam stabiliser is non-hydrolytic type water soluble polyether siloxanes and polyvinyl alcohol with 1:0
The mixing of~2 weight ratios；The composite catalyst is isoquinolin, triethanolamine, triethylenediamine, stannous octoate and tin dilaurate
One of dibutyl tin is a variety of；The polyisocyanates is polyphenyl polymethylene polyisocyanates, diphenyl methane two
One of isocyanates, toluene di-isocyanate(TDI) and hexamethylene diisocyanate are a variety of.
7. a kind of preparation method of Halogen composite flame-proof Polyimide foams as described in claim 1, which is characterized in that
Include the following steps:
1) aromatic dianhydride is heated to 70~100 DEG C with polar solvent and be uniformly dispersed, add fatty alcohol at 60~80 DEG C
Reflux carries out 0.2~1 h of esterification, obtains solution A；
2) deionized water, foam stabiliser and composite catalyst are uniformly dispersed in solution A in 50~70 DEG C, are then added
Halogenless composite fire retardant obtains uniformly mixed suspension B；
3) polyisocyanates is rapidly added in suspension B and stirs 4~15 s to obtain mixture, mixture is quickly poured into
Free foaming obtains foam intermediate in mold；
4) foam intermediate first passes through 140~200 DEG C of 1~2 h of heating in vacuum, then dries by 250~300 DEG C of heat and carries out acyl
0.5~2 h of imidization finally obtains Halogen composite flame-proof Polyimide foams.
8. a kind of preparation method of Halogen composite flame-proof Polyimide foams according to claim 7, feature exist
In: in step 1), aromatic dianhydride is heated to 80~100 DEG C with polar solvent and is uniformly dispersed, and fatty alcohol reflux is added and carries out ester
Change 0.5~1 h of reaction.
9. a kind of preparation method of Halogen composite flame-proof Polyimide foams according to claim 8, feature exist
In: after adding Halogenless composite fire retardant in solution A in step 2,0.5~2 h is stirred under the revolving speed of 1000~20000 rpm
It is uniformly mixed.
10. a kind of preparation method of Halogen composite flame-proof Polyimide foams according to claim 7, feature exist
In: suspension B is maintained between -20~30 DEG C of ranges in step 3), after then being mixed with polyisocyanates 1000~
Free foaming after mixing evenly under the revolving speed of 20000 rpm.
11. a kind of preparation method of Halogen composite flame-proof Polyimide foams according to claim 10, feature
Be: foam intermediate first passes through 150~180 DEG C of progress vacuum heating treatments in step 4), and initial temperature is 15~35
DEG C, heating rate is 1~10 DEG C/min.
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| KR102248134B1 (en) * | 2019-11-15 | 2021-05-04 | 미쓰이케미칼앤드에스케이씨폴리우레탄 주식회사 | Non-combustible foam and manufacturinng method thereof |
| CN111234300B (en) * | 2020-03-30 | 2022-11-08 | 北京市射线应用研究中心有限公司 | Porous polyimide material and preparation method thereof |
| 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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