CN107903430A - A kind of preparation method of isocyanate group polyimides rigid foam - Google Patents
A kind of preparation method of isocyanate group polyimides rigid foam Download PDFInfo
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- CN107903430A CN107903430A CN201711305372.5A CN201711305372A CN107903430A CN 107903430 A CN107903430 A CN 107903430A CN 201711305372 A CN201711305372 A CN 201711305372A CN 107903430 A CN107903430 A CN 107903430A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a kind of preparation method of isocyanate group polyimides hard foam, using aromatic dianhydride and isocyanates as main Material synthesis.Its preparation process mainly includes：The control technique of the preparation of performed polymer, foaming process and high-temperature post-treatment.Different structure and the foamed material of performance are obtained by the proportioning for adjusting organic tin catalyst and amines catalyst.Compared with other polyimide foams, present invention gained foam manufacture is of low cost, and preparation process is simple, and equipment requirement is loose, not only with good mechanical property, and shows excellent heat endurance and fire resistance, limited oxygen index is up to 49.2%.The present invention uses deionized water as foaming agent, foamed by mechanical agitation and polyimide foam is made, preparation process does not produce pernicious gas, it is suitable for industrializing continuous production, obtained end product is expected in high temperature resistant heat insulation material and fire proofing etc. large-scale application, have broad application prospects and huge commercial value.
Description
Technical field
The present invention relates to a kind of preparation method of isocyanate group polyimides rigid foam, belong to polymeric foamed material
Field, falls within high performance material field.
Background technology
Polyimides (PI) foamed material is one of material that heat endurance is best in polymer foam, is had excellent
From fire resistance and good mechanical property, can be used as structural material.But the more difficult control of its production technology, it is not easy to be processed
Manufacture, production cost is high, is mainly used in the high-tech areas such as aerospace, electronics industry, greatly limit its extensive use.
Isocyanate group Polyimide foams preparation process is simple, and equipment requirement is loose, and manufacture cost is low, is closed in recent years
Note.However, the reaction of formation of polyimides is a complicated chemical reaction system, with the generation of a variety of reactions, prepare
The control of technique is undoubtedly the most key and important.Suitable preparation process can not only obtain having the PI of excellent properties to steep
Foam, and can be cost-effective, realize that production maximizes.The type and proportioning of catalyst play in the preparation process of PI foams
Important effect, it is not only controlled between chain propagation reaction (dianhydride and isocyanates) and foamable reaction (isocyanates and water)
Balance, and affect foamed time and the hardening time of system, and then influence the performance of product.
In existing polyimides synthetic technology, the method for preparing polyimide foam is mainly one-step method and powder
Method.One-step method is to sequentially add required raw material, and reaction directly obtains final products；Powder method is first by required Material synthesis
Precursor powder, after powder inserted into foamable in mould obtain final products.There are following defect：Different types of catalysis
Agent adds at the same time, and chain propagation reaction occurs at the same time with foamable reaction, and foaming structure is difficult to control.Thus, polyimide foam system
The optimization of standby technique and the regulation and control to its structure and performance become important research direction.
To solve problems of the prior art, the present invention needs to provide a kind of isocyanate group polyimides hard bubble
The preparation method of foam, by the optimization and regulation and control to existing preparation process, can obtain different structure and the PI foams of performance, and
Realize the technique effect for widening its application field.
The content of the invention
The invention discloses a kind of preparation method of isocyanate group polyimides rigid foam, can obtain having excellent
The PI foams of structure and performance.
A kind of preparation method of isocyanate group polyimides rigid foam, it is characterised in that comprise the following steps：By virtue
Fragrant dianhydride adds reaction in polar solvent according to functional group's molar ratio 1: 1 with alcohols and extremely clarifies, rear gradually heating, in temperature-rise period
Middle addition is 1: 1 isocyanates with aromatic dianhydride functional group molar ratio, and adds organic tin catalyst, at 80 DEG C~95 DEG C
Under the conditions of reaction 4~6 it is small when, obtain prepolymer solution and be cooled to room temperature, sequentially add isocyanates and amines catalyst stirs
Mix 2~4 minutes, it is rear to add 10~30 seconds free foamings of foam stabiliser and deionized water high-speed stirred, foam intermediate is made,
Finally foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of ladder-elevating temperature processing 4~6 are small, obtains polyimides
Rigid foam.
Preferably, the aromatic dianhydride include pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ',
Double (3, the 4- phthalate anhydride) hexafluoropropane of 4,4 '-two methyl phenyl ethers anisole tetracarboxylic dianhydrides, 2,2- or 1,3- are double (3,4- phthalate anhydride)
One or more in hexafluoropropane.
Preferably, the isocyanates includes polyphenyl polymethylene polyisocyanates, paraphenylene diisocyanate, diphenyl
Methane -4, the one or more in 4 '-diisocyanate, 1,5- naphthalene diisocyanates or dimethyl diphenyl diisocyanate.
Preferably, the alcohols includes the one or more in methanol, ethanol or ethylene glycol.
Preferably, the polar solvent includes tetrahydrofuran, dimethylformamide, dimethylacetylamide or N- methylpyrroles
One or more in alkanone.
Preferably, the organic tin catalyst includes dibutyltin diacetate, dibutyl tin dilaurate or octanoic acid
One or more in stannous.
Preferably, the amines catalyst includes triethanolamine, triethylamine, triethylene diamine, dimethylethanolamine, Sanya
One kind in ethyldiamine.
Preferably, the foam stabiliser include silicone polyether copolymer, organosilicon, one kind in silicone stabilizer or
It is a variety of.
Preferably, stir speed (S.S.) during high-speed stirred is 1500-2000r/min, and mixing time is 15~20s.
Preferably, the organic tin catalyst is dibutyl tin dilaurate, and the amines catalyst is triethanolamine.
Further, the dibutyl tin dilaurate content is 1.85wt%, and the content of the triethanolamine is
1.48wt%.
Beneficial effect：
Isocyanate group polyimides rigid foam is made using synthesis performed polymer, the method for two steps foaming in the present invention.This
Performed polymer synthetic method the advantage is that compared with one-step method used by invention：Foaming structure can be controlled effectively, gained foam power
It is high to learn intensity, it is good from excellent fireproof performance, high and low temperature resistance；Compared with powder method, it the advantage is that：Molecular weight is controllable,
Simple to operate, relatively low to equipment requirement, manufacture cost is low, does not produce pernicious gas, is suitable for industrial continuous production.This
The novelty of invention is the not same-action using catalyst, and substep adds catalyst, can Effective Regulation foam structure and performance.
The type of catalyst directly affects the structure and performance of polyimide foam with proportioning.It is used in the present invention organic
Catalytic mechanism of the tin catalyst from tertiary amine catalyst in polyimide foam is different, and organic tin catalyst is for pre-polymerization
Gel reaction in production procedure is more sensitive, can effectively increase chain propagation reaction speed, to the heat of polyimide foam
Stability and fire resistance effect are notable；Tertiary amine catalyst is more sensitive for foaming process, and it is anti-can to effectively facilitate foaming
Should, play the role of adjusting cell morphology in the engineering that foams, it is larger to the density and Effect on Mechanical Properties of foam.Organic tin
Catalyst includes dibutyl tin dilaurate (DBTDL) and stannous octoate, and tertiary amine catalyst includes triethanolamine (TEOA), three
Ethamine (TEA), triethylene diamine and dimethylethanolamine.Particularly, the uncle of the hydroxyl such as dimethylethanolamine and triethanolamine
Amine catalyst is easily reacted with isocyanates, is closely coupled in main polymer chain, not only plays the role of catalysis foaming, Er Qieshi
Preferable crosslinking agent or chain extender.The preferred dibutyl tin dilaurate of catalyst and triethanolamine of the present invention.By adjusting two
The proportioning of kind catalyst, can obtain different structure and the polyimide foam of performance.The present invention uses deionized water as foaming
Agent, is foamed by mechanical agitation and polyimide foam is made, and preparation process does not produce pernicious gas, is suitable for industrializing continuous life
Production, obtained end product are expected in high temperature resistant heat insulation material and fire proofing etc. large-scale application, have wide answer
With prospect and huge commercial value.
Brief description of the drawings
The present invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the scanning electron microscope diagram piece of the polyimide foam obtained by embodiment 3.
Fig. 2 show respectively the thermogravimetric curve that one-step method, powder method and prepolymer method prepare polyimide foam.
Embodiment
In order to which the technical characteristic of the present invention is more clearly understood, now technical scheme is carried out following detailed
Describe in detail it is bright, but it is not intended that to the present invention can practical range restriction.
Embodiment 1
100g pyromellitic dianhydrides (PMDA) and 25g methanol are added in 100g n,N-Dimethylformamide (DMF) one
Determining reaction at temperature, to clarifying, rear gradually heating, during temperature rises to 80 DEG C, adds 130g polyphenyl polymethylene polyisocyanates
Cyanate (PAPI), it is rear to add 2g stannous octoate catalysts, when reaction 3~7 is small under the conditions of 80~95 DEG C, it is molten to obtain performed polymer
Liquid is simultaneously cooled to room temperature, sequentially adds 40g PAPI and 2g triethylamine (TEA) and stirs evenly, rear to add 30g foam stabilisers AK-
8805 and 15g deionized waters 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made bubble
Foam intermediate, is finally placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small by foam intermediate so that bubble
The abundant imidizate of foam intermediate, obtains polyimides rigid foam.
Embodiment 2
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add 2g dibutyl tin dilaurates (DBTDL) catalyst, 80
When reaction 3~7 is small under the conditions of~95 DEG C, obtains prepolymer solution and be cooled to room temperature, sequentially add tri- second of 40g PAPI and 2g
Hydramine (TEOA) stirs evenly, and rear 30g foam stabiliser AK-8805 and the 15g deionized waters that add turn in 1000~2000r/min
10~20s of high-speed stirred and free foaming under the conditions of speed, are made foam intermediate, foam intermediate finally are placed in vacuum drying
In case when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant imidizate of foam intermediate, obtains polyimides hard
Foam.
Embodiment 3
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
0.74wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 0.74wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, the electron scanning micrograph for obtaining polyimides rigid foam are as shown in Figure 1.
Embodiment 4
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
1.11wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 0.74wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 5
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
1.48wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 0.74wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 6
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
1.85wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 0.74wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 7
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
0.74wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 1.11wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 8
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
0.74wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 1.48wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 9
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
0.74wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 1.85wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains polyimides rigid foam.
Embodiment 10
100g PMDA and 25g methanol are added reaction at a certain temperature in 100g DMF extremely to clarify, rear gradually heating,
During temperature rises to 80 DEG C, 130g PAPI are added, it is rear to add catalyst dibutyl tin dilaurate (content is
1.85wt%), when reaction 3~7 is small under the conditions of 80~95 DEG C, obtain prepolymer solution and be cooled to room temperature, sequentially add 40g
PAPI and triethanolamine (content 1.48wt%) stir evenly, rear to add 30g foam stabiliser AK-8805 and 15g deionizations
Water 10~20s of high-speed stirred and free foaming under 1000~2000r/min speed conditions, are made foam intermediate, finally will
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acyl of foam intermediate is sub-
Amination, obtains the thermogravimetric curve of polyimides rigid foam as shown in Figure 2 (prepolymer method).
Comparative example 1
100g PMDA and 25g methanol are added into reaction at a certain temperature in 100g DMF and, to clarifying, add 2g dibutyl
Tin dilaurate tin, 2g triethanolamine 30g foam stabiliser AK-8805 and 15g deionized waters stir evenly, and add 170g afterwards
PAPI, high-speed stirred and free foaming under 1000~2000r/min speed conditions, is made foam intermediate, finally by foam
Intermediate is placed in vacuum drying chamber when 160~220 DEG C of high-temperature process 4~6 are small so that the abundant acid imide of foam intermediate
Change, obtain the thermogravimetric curve of polyimide foam as shown in Figure 2 (one-step method).
Comparative example 2
By 100g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is added in 100g DMF certain with 25g methanol
At a temperature of reaction to clarify, be heated to reflux obtaining two acid diesters, after cooling add 110g 4,4 '-diaminodiphenyl ether (ODA),
2g dibutyl tin dilaurates, 2g triethanolamines, 20g foam stabiliser AK-8805 hybrid reactions, obtain precursor solution, so
Afterwards by precursor solution drying, crushing, solid precursor powder is obtained, then precursor powder is put into foamable in mould,
Obtain the thermogravimetric curve of Polyimide foams as shown in Figure 2 (powder method).
Table 1.
| Group | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 10 |
| Limited oxygen index | 41.7% | 47.3% | 48.6% | 49.2% | 49.1% |
Table 2.
| Group | Embodiment 3 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 |
| Mean cell diameter | 422μm | 374μm | 352μm | 321μm | 320μm |
Embodiment 1 and embodiment 2 change the type of catalyst, preferably dibutyl tin dilaurate and triethanolamine；It is real
Apply example 3,4,5,6 and 10 obtain polyimide foam limited oxygen index numerical value it is as shown in table 1, it can be seen that catalyst dibutyl
The increase of tin dilaurate Theil indices can effectively improve the fire resistance of material；Embodiment 3,7,8,9 and 10 obtains polyimides
The mean cell diameter of foam is as shown in table 2, it can be seen that when triethanolamine content increases, cell morphology is more fine and close, power
Performance is learned to be lifted therewith；Embodiment 10, comparative example 1 and the different preparation methods of 2 three kinds of comparative example obtain the heat of polyimide foam
Weight-loss curve as shown in Fig. 2, the heat endurance that prepolymer method prepares polyimide foam is significantly larger than one-step method, and with it is complicated
The heat endurance that powder method prepares polyimide foam is not much different.
Polyimide foam form obtained by the present invention is as shown in Figure 1, abscess is mostly open-celled structure；Catalyst dibutyl
Tin dilaurate tin can effectively lift the heat endurance and fire resistance of polyimide foam, and catalyst triethanolamine was foaming
Play the role of crosslinking agent or chain extender in journey so that cell morphology is comparatively dense, and mechanical property is significantly lifted, and passes through adjusting
The content of two kinds of catalyst of dibutyl tin dilaurate and triethanolamine can prepare different structure and the polyimides of performance steeps
Foam.Within research range of the present invention, when dibutyl tin dilaurate content is 1.85wt%, triethanolamine content is
During 1.48wt%, polyimide foam not only has good heat endurance and fire resistance, and cell morphology is fine and close, mechanics
Excellent performance, comprehensive performance reach optimal.
Claims (10)
1. a kind of preparation method of isocyanate group polyimides rigid foam, it is characterised in that comprise the following steps：By fragrance
Dianhydride adds reaction in polar solvent according to functional group's molar ratio 1: 1 with alcohols and extremely clarifies, rear gradually heating, in temperature-rise period
Add and be 1: 1 isocyanates with aromatic dianhydride functional group molar ratio, and add organic tin catalyst, in 80 DEG C~95 DEG C bars
When reaction 4~6 is small under part, obtains prepolymer solution and be cooled to room temperature, sequentially add isocyanates and amines catalyst stirring 2
It is~4 minutes, rear to add 10~30 seconds free foamings of foam stabiliser and deionized water high-speed stirred, foam intermediate is made, most
Foam intermediate is placed in vacuum drying chamber when 160~220 DEG C of ladder-elevating temperature processing 4~6 are small afterwards, it is hard to obtain polyimides
Matter foam.
A kind of 2. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The aromatic dianhydride includes pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-two methyl phenyl ethers anisoles four
One kind in double (3, the 4- phthalate anhydride) hexafluoropropane of acid dianhydride, 2,2- or double (3, the 4- phthalate anhydride) hexafluoropropane of 1,3-
It is or a variety of.
A kind of 3. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The isocyanates includes polyphenyl polymethylene polyisocyanates, paraphenylene diisocyanate, diphenyl methane -4, and 4 '-two is different
One or more in cyanate, 1,5- naphthalene diisocyanates or dimethyl diphenyl diisocyanate.
A kind of 4. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The alcohols includes the one or more in methanol, ethanol or ethylene glycol.
A kind of 5. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The polar solvent include tetrahydrofuran, dimethylformamide, dimethylacetylamide or 1-methyl-2-pyrrolidinone in one kind or
It is a variety of.
A kind of 6. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The organic tin catalyst includes one kind or more in dibutyltin diacetate, dibutyl tin dilaurate or stannous octoate
Kind.
A kind of 7. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
The amines catalyst includes one in triethanolamine, triethylamine, triethylene diamine, dimethylethanolamine, triethylenediamine
Kind is a variety of.
8. according to claim 1 existed with a kind of preparation method of isocyanate group polyimides rigid foam, its feature
In the foam stabiliser includes the one or more in silicone polyether copolymer, organosilicon, silicone stabilizer.
A kind of 9. preparation method of isocyanate group polyimides rigid foam according to claim 1, it is characterised in that
Stir speed (S.S.) during high-speed stirred is 1500-2000r/min, and mixing time is 15~20s.
10. a kind of preparation method of isocyanate group polyimides rigid foam according to claim 1, its feature exist
In the organic tin catalyst is dibutyl tin dilaurate, and the amines catalyst is triethanolamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880145A (en) * | 2019-03-07 | 2019-06-14 | 中国科学院长春应用化学研究所 | A kind of fire-retardant Polyimide foams of low smell and preparation method thereof |
| CN111748094A (en) * | 2020-06-24 | 2020-10-09 | 哈尔滨工程大学 | Preparation method and product of density-adjustable flexible polyimide foam |
| CN111848903A (en) * | 2019-10-16 | 2020-10-30 | 宁波途锐达休闲用品有限公司 | Microporous polyurethane foam material and its production process |
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| CN114369244A (en) * | 2022-01-10 | 2022-04-19 | 北京理工大学 | Ultra-light environment-friendly porous electromagnetic cloud damage composite material and preparation method and application thereof |
| CN114369244B (en) * | 2022-01-10 | 2023-03-31 | 北京理工大学 | Ultra-light environment-friendly porous electromagnetic cloud damage composite material and preparation method and application thereof |
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