CN108250748A - A kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material and preparation method thereof - Google Patents
A kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material and preparation method thereof Download PDFInfo
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- CN108250748A CN108250748A CN201810052550.6A CN201810052550A CN108250748A CN 108250748 A CN108250748 A CN 108250748A CN 201810052550 A CN201810052550 A CN 201810052550A CN 108250748 A CN108250748 A CN 108250748A
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- OEAKLENMZGIVFR-UHFFFAOYSA-N Cc(cc1)ccc1Oc(cc1)ccc1C(c(cc1)ccc1Oc1ccc(C)cc1)=O Chemical compound Cc(cc1)ccc1Oc(cc1)ccc1C(c(cc1)ccc1Oc1ccc(C)cc1)=O OEAKLENMZGIVFR-UHFFFAOYSA-N 0.000 description 1
- OJBAVCNPZFYPGL-UHFFFAOYSA-N Cc(cc1)ccc1Oc1ccc(C(c(cc2)ccc2Oc2ccc(C)cc2)(NC)NC)cc1 Chemical compound Cc(cc1)ccc1Oc1ccc(C(c(cc2)ccc2Oc2ccc(C)cc2)(NC)NC)cc1 OJBAVCNPZFYPGL-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
One kind side chain containing acid imide cage-type silsesquioxane/polyimide nano-composite material of the present invention and preparation method thereof belongs to polyimides preparation field.The cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material is the cage-type silsesquioxane of side chain containing acid imide by dispersed phase and continuous phase composition, dispersed phase, and continuous phase is polyimides.The preparation method of the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material is that phthalic anhydride is reacted with eight amino cage-type silsesquioxanes, obtains the cage-type silsesquioxane of amide containing acid branch；The cage-type silsesquioxane of amide containing acid branch is carried out solution with polyamic acid in proportion to mix, hot imidization is carried out, obtains the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material.The cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material of the present invention has excellent anti-atomic oxygen performance, easily prepared, and yield is high, and synthesis cost is low.
Description
Technical field
The present invention relates to polyimides preparation fields, and in particular to a kind of cage-type silsesquioxane of side chain containing acid imide/poly-
Acid imide nanocomposite and preparation method thereof.
Background technology
Low Earth Orbit is the important running track of aircraft, between the outer space of 200~700 kms.Space station, height
It differentiates the aircraft such as earth observation systems and runs on the track, elemental oxygen, plasma, ultraviolet irradiation, thermal cycle, high vacuum
The normal operation of aircraft is influenced with hazardous environments factors such as space junks.Wherein, elemental oxygen is known as " most dangerous factor ".
Elemental oxygen has the characteristics that high-temperature oxydation, high velocity impact, corrodes the polymer material outside spacecraft, is given birth to by DuPont Corporation
The Kapton polyimide materials of production are widely used in the outermost layer of the multistory steel structure of spacecraft, make spacecraft from too
Sun irradiation.Polyimide material is shown coarse carpet-like pattern after atomic oxygen erosion, mass loss is apparent, eventually leads to
The declines such as mechanical performance and optical property influence its functional performance.Therefore, corresponding to the polymer material outside spacecraft
Protection is carried out to be necessary.
Cagelike silsesquioxane (POSS) has carried out a large amount of research as the structural unit of resistance to elemental oxygen, and Minton etc. is adopted
Main chain and side chain type POSS polyimides are prepared for, and comment using space flight test and ground simulating with the method for copolymerization
The valency anti-atomic oxygen performance of the material, the results showed that the anti-atomic oxygen performance of the material significantly improve (Tomczak S.J.,
Vij V.,Minton T.K.,Brunsvold A.L.,Marchant D.,Wright M.E.,Petteys B.J.,
Guenthner A.J.,Yandek G.R.and Mabry J.M.,Acs Symposium,2008,978,140-152；
Minton T.K.,Wright M.E.,Tomczak S.J.,Marquez S.A.,Shen L.,Brunsvold A.L.,
Cooper R.,Zhang J.,Vij V.and Guenthner A.J.,ACS applied materials&interfaces,
2012,4,492).But preparation containing double amino POSS makes copoly type normally due to the reaction of multi-step causes its yield relatively low
The cost of POSS polyimides greatly increases, and is difficult to commercialization.
Opposite copolymerization, blending are that another improves the effective method of polyimides anti-atomic oxygen performance.But it is mixed in solution
During preparing polyimides, general POSS such as octaphenyl POSS, is more likely in the form of a kind of larger aggregation
It is present in polymeric substrate.Reunion will cause the discontinuous of material structure, lead to stress concentration.Simultaneously because POSS nanoparticles
Son is lost its effect as high-performance filler there is no uniformly dispersing in the material.Therefore, a kind of blending type is developed
The POSS polyimide nano-composite materials that can be uniformly dispersed are to realize POSS polyimides low cost as anti-atomic oxygen material
The effective ways of preparation.
Invention content
It is high the technical problem to be solved by the present invention is to, copoly type POSS polyimides production cost, commercialization it is difficult and
The problem of POSS nano-particles and matrix are easily separated and reunite in blending type POSS polyimides preparation process be
This, the present invention provides a kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material and preparation methods.
The technical solution adopted by the present invention is that a kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano is multiple
Condensation material, the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material is by dispersed phase and continuous phase group
Into；The preparation method of the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material is, by phthalic anhydride and eight amino
Cage-type silsesquioxane reacts, and obtains the cage-type silsesquioxane of amide containing acid branch；By the cage model sesquialter of amide containing acid branch
Siloxanes carries out solution with polyamic acid in proportion and mixes, and obtains the cage-type silsesquioxane of side chain containing acid imide/polyimides and receives
Nano composite material presoma；The cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material presoma is using warm
Imidization method carries out hot imidization, obtains the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material.
The specific technical solution that the present invention uses is that a kind of cage-type silsesquioxane of side chain containing acid imide/polyimides is received
Nano composite material, it is characterized in that, the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material is by disperseing
Mutually and continuous phase composition, dispersed phase are the cage-type silsesquioxane of side chain containing acid imide, and structural formula is：
Wherein R ' is Even
Continuous is mutually polyimides, and structural formula is：Ar ' is In one kind；Ar is
In one kind；Wherein, dispersed phase and the mass ratio of continuous phase are 2.1~10：97.9~90；N is 60-80.
The preparation method of the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material, it is characterized in that：
(1) under room temperature and nitrogen protection, eight amino POSS are dissolved in solvent 1, stirs 15~30 minutes, obtains eight
Amino POSS solution；Divide 3~5 addition phthalic anhydrides, the reaction was continued 12~24 hours；Vacuum distillation removal solvent 1, obtains amide containing
The POSS of sour branch；The 1 preferred N-Methyl pyrrolidone (NMP) of solvent, DMAC N,N' dimethyl acetamide (DMAc) or N, N- bis-
One kind in methylformamide (DMF)；One kind in eight amino POSS preferably eight aminophenyl POSS, eight aminopropyl POSS；
The mass ratio of 1 and eight amino POSS of solvent is 1: 9~19；The molar ratio of phthalic anhydride and eight amino POSS are 8:1；
(2) under room temperature and nitrogen protection, diamines is added in solvent 2, stirring obtains diamine solution in 15~30 minutes；
Divide 3~5 addition dianhydrides, add in solvent 3, stirring polymerization 12~24 hours obtains polyamic acid；Diamines is preferably 4,4'- bis-
Bis- [4- (4- amino-benzene oxygens) phenyl] propane of amino-diphenylethers, 2,2-, bis- (4- amino-benzene oxygens) benzophenone and 2 of 4,4'-,
One kind in bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane of 2-；Dianhydride is preferably pyromellitic acid anhydride, 3,3,4',
4'- biphenyltetracarboxylic dianhydride, 3,3', 4,4'- benzophenone tetrabasic carboxylic acid dicarboxylic anhydrides, 4,4'- oxygen double phthalic anhydride, 3,3', 4,
4'- diphenyl sulfone tetrabasic carboxylic acids dicarboxylic anhydride, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and 4,4'- (4,4' isopropyl diphenoxies)
One kind in bis- (phthalic anhydrides)；The molar ratio of diamines and dianhydride is 1: 1；One in solvent 2 preferred NMP, DMAc and DMF
Kind；One kind in solvent 3 preferred NMP, DMAc and DMF；The mass ratio of diamines and solvent 2 is 1: 9~19；Dianhydride and solvent 3
Mass ratio is 1: 9~19；
(3) POSS of amide containing acid branch is dissolved in solvent 4, stirring obtains amide containing acid branch in 15~30 minutes
POSS solution；By the POSS solution of amide containing acid branch in being slowly added in the polyamic acid solution in 10~15 minutes, stir
It mixes 8~16 hours, obtains the POSS/ polyimide nano-composite material presomas of side chain containing acid imide；Ladder-elevating temperature removes solvent
And hot imidization is completed, program is 40 DEG C, 4~8 hours；60 DEG C, 4~8 hours；80 DEG C, 1~3 hour；100 DEG C, 1~3 is small
When；120 DEG C, 2~4 hours；200 DEG C, 1~2 hour；250 DEG C, 1~2 hour；300 DEG C, 0.5~1 hour；After cooling, spend
Ionized water impregnates, and is washed with ethyl alcohol or acetone, and the POSS/ polyimide nano-composite materials of side chain containing acid imide are obtained after dry；
One kind in the preferred NMP of solvent, DMAc or DMF；The mass fraction of the POSS of the amide containing acid branch for 2.1%~
10%.
Anti-atomic oxygen side chain containing acid imide POSS/ polyimide nano-composite materials provided by the present invention and the side of copolymerization
POSS polyimides prepared by method is likewise supplied with excellent anti-atomic oxygen performance；Anti-atomic oxygen provided by the present invention contains acid imide
Side chain POSS/ polyimide nano-composite materials using eight amino POSS due to, as raw material, compared with diamino POSS, being easy to
It prepares, yield is high, substantially reduces material preparation cost；Anti-atomic oxygen side chain containing acid imide POSS/ provided by the present invention gathers
Acid imide nanocomposite preparation method is simple, easily prepared.Anti-atomic oxygen side chain containing acid imide provided by the present invention
POSS/ polyimide nano-composite materials maintain the original heat resistance of polyimides and high glass transition temperature；The present invention
Anti-atomic oxygen side chain containing the acid imide POSS/ polyimide nano-composite materials provided using amide containing acid branch POSS with
Polyamic acid is mixed with presoma, and the branch of amic acid increases the compatibility of POSS and polyamic acid, promotes POSS's
It is homodisperse.
Description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of the POSS1 of amide containing acid branch prepared in embodiment 1；
Fig. 2 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
Infrared spectrogram；
Fig. 3 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
DSC figure；
Fig. 4 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
TGA figure；
Fig. 5 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
With the XRD diagram of ODA-BPDA type polyimides；
Fig. 6 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
Element silicon distribution map；
Fig. 7 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
The SEM figures on surface；
Fig. 8 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
It is 1.33 × 10 to undergo fluence20atoms/cm2Elemental oxygen irradiation rear surface SEM figure.
Specific embodiment
Illustrate the present invention below by specific embodiment, but it is not limited to this.
Embodiment 1
(1) under room temperature and nitrogen protection, eight aminophenyl POSS of 1.153g are dissolved in 10.4gN- methyl pyrrolidones
(NMP) it in, stirs 15 minutes, obtains eight aminophenyl POSS solution 1；1.185g phthalic anhydrides are added three times, it is 12 small that the reaction was continued
When；(NMP obtains the POSS1 of amide containing acid branch to vacuum distillation removal N-Methyl pyrrolidone；
(2) under room temperature and nitrogen protection, by 2.002g 4,4'- diaminodiphenyl ethers are added in 18gNMP, stirring 15
Minute obtains 4,4'- diaminodiphenyl ether solution；3.042g 3,3,4' is added three times, 4'- biphenyltetracarboxylic dianhydride adds in
27.4gNMP, stirring polymerization 12 hours, obtains polyamic acid 1；
(3) POSS1 of 0.504g amide containing acid branches is dissolved in 4.5gNMP, stirring obtains amide containing acid branch in 15 minutes
The POSS1 solution of chain；By the POSS1 solution of amide containing acid branch in being slowly added in 10 minutes in 1 solution of polyamic acid,
Stirring 8 hours, obtains 1 presoma of the POSS/ of side chain containing acid imide polyimide nano-composite materials；Ladder-elevating temperature removal solvent is simultaneously
Hot imidization is completed, program is 40 DEG C, 4 hours；60 DEG C, 4 hours；80 DEG C, 1 hour；100 DEG C, 1 hour；120 DEG C, 2 hours；
200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 0.5 hour；It after cooling, is impregnated with deionized water, is washed with ethyl alcohol, after dry
Obtain the POSS/ of side chain containing acid imide polyimide nano-composite materials 1.
N=60 in embodiment 1
Fig. 1 is the nucleus magnetic hydrogen spectrum of the POSS1 of amide containing acid branch prepared in embodiment 1, and as shown in Figure 1, δ changes for 5.0
The characteristic peak of amino disappears at displacement study, in δ to there is the characteristic peak of amic acid carboxyl at 10.4 chemical shifts, illustrates us
The POSS1 of the obtained amide containing acid branch of success；
Fig. 2 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
Infrared spectrogram, 1710,1760 and 1380cm-1For acid imide absorption peak, and 1718cm-1Carboxyl absorbs in the amic acid at place
Peak completely disappears, and 1060 the characteristic peak of Si-O-Si occur, illustrates the cage model sesquialter silica of side chain containing acid imide that we prepare
1 imidization of alkane/polyimide nano-composite material is complete, and the cage-type silsesquioxane of side chain containing acid imide is introduced into polyimides
In matrix；
Fig. 3 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
DSC figures, glass transition temperature is 257 DEG C, maintains the high glass-transition temperature of polyimides；
Fig. 4 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
TGA figures under air conditions, 5% thermal weight loss is 499 DEG C, and 10% thermal weight loss is 534 DEG C, it can be seen that, containing acid imide
Side chain cage-type silsesquioxane/polyimide nano-composite material 1 has excellent thermal stability；
Fig. 5 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
With the XRD diagram of ODA-BPDA type polyimides, the diffraction maximum of the two is close, is amorphous materials, the cage modle of side chain containing acid imide
Silsesquioxane/polyimide nano-composite material 1 does not occur the crystal diffraction peak of cage-type silsesquioxane, illustrates embodiment 1
Nano-particle in the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material 1 of middle preparation is uniformly dispersed,
There is no agglomeration.
Fig. 6 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
Element silicon distribution map, it will be appreciated from fig. 6 that element silicon is evenly distributed in polyimide matrix；
Fig. 7 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
The SEM figures on surface, the surfacing of material do not have defect；
Fig. 8 is the cage-type silsesquioxane of side chain containing the acid imide/polyimide nano-composite material 1 prepared in embodiment 1
It is 1.33 × 10 to undergo fluence20atoms/cm2Elemental oxygen irradiation rear surface SEM figure, elemental oxygen irradiation after, surface production
Pin-hole like defects are given birth to, compared with the carpet-like pattern of Kapton, roughness is substantially reduced；Undergo fluence for 1.33 ×
1020atoms/cm2Elemental oxygen irradiation after, the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material 1
Mass loss is 0.075mg/cm2.In conclusion anti-atomic oxygen side chain containing the acid imide POSS/ polyamides prepared in embodiment 1 is sub-
POSS polyimides prepared by amine nanocomposite and the method for copolymerization is likewise supplied with excellent anti-atomic oxygen performance；It maintains
The original heat resistance of polyimides and high glass transition temperature；System is mixed with polyamic acid using the POSS of amide containing acid branch
Standby presoma, the branch of amic acid increase the compatibility of POSS and polyamic acid, promote the homodisperse of POSS.
Embodiment 2
(1) under room temperature and nitrogen protection, eight aminopropyl POSS of 1.072g are dissolved in 20.4gN, N- dimethylacetamides
In amine (DMAc), stir 30 minutes, obtain eight aminopropyl POSS solution 2；Points of 5 times addition 1.185g phthalic anhydrides, the reaction was continued 24
Hour；Vacuum distillation removal DMAc, obtains the POSS2 of amide containing acid branch；
(2) under room temperature and nitrogen protection, by 2.002g 4,4'- diaminodiphenyl ethers are added in 38g DMAc, stirring
Obtain within 30 minutes 4,4'- diaminodiphenyl ether solution；Divide 5 addition 3.016g 3,3,4', 4'- biphenyltetracarboxylic dianhydride adds in
57.3gDMAc, stirring polymerization 24 hours, obtains polyamic acid 2；
(3) POSS2 of 0.105g amide containing acid branches is dissolved in 2g DMAc, stirring obtains amide containing acid branch in 30 minutes
The POSS2 solution of chain；By the POSS2 solution of amide containing acid branch in being slowly added in 15 minutes in 2 solution of polyamic acid,
Stirring 16 hours, obtains 2 presoma of the POSS/ of side chain containing acid imide polyimide nano-composite materials；Ladder-elevating temperature removes solvent
And hot imidization is completed, program is 40 DEG C, 8 hours；60 DEG C, 8 hours；80 DEG C, 3 hours；100 DEG C, 3 hours；120 DEG C, 4 is small
When；200 DEG C, 2 hours；250 DEG C, 2 hours；300 DEG C, 1 hour；It after cooling, is impregnated with deionized water, is washed with acetone, it is dry
After obtain the POSS/ of side chain containing acid imide polyimide nano-composite materials 2；
N in embodiment 2 is 80, and experience fluence is 1.3 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl Asia
The mass loss of amine side chain cage-type silsesquioxane/polyimide nano-composite material 2 is 0.13mg/cm2.Embodiment 2 its
His characterization result is similar to Example 1.
Embodiment 3
(1) under room temperature and nitrogen protection, eight aminophenyl POSS of 1.153g are dissolved in 10.4g N, N- dimethyl methyls
In amide (DMF), stir 15 minutes, obtain eight aminophenyl POSS solution 3；1.185g phthalic anhydrides are added three times, the reaction was continued 12
Hour；Vacuum distillation removal DMF, obtains the POSS3 of amide containing acid branch；
(2) under room temperature and nitrogen protection, by 4.105g 2, bis- [4- (4- amino-benzene oxygens) phenyl] propane of 2- are added to
In 36.9g NMP, stirring obtains bis- [4- (4- amino-benzene oxygens) phenyl] the propane solution of 2,2- in 15 minutes；It is added three times
2.255g pyromellitic acid anhydrides, add in 20.3g NMP, and stirring polymerization 12 hours obtains polyamic acid 3；
(3) POSS1 of 0.318g amide containing acid branches is dissolved in 2.86g NMP, stirring obtains amide containing acid for 15 minutes
The POSS3 solution of branch；By the POSS3 solution of amide containing acid branch in being slowly added to 3 solution of polyamic acid in 10 minutes
In, it stirs 8 hours, obtains 3 presoma of the POSS/ of side chain containing acid imide polyimide nano-composite materials；Ladder-elevating temperature removal is molten
Agent simultaneously completes hot imidization, and program is 40 DEG C, 4 hours；60 DEG C, 4 hours；80 DEG C, 1 hour；100 DEG C, 1 hour；120 DEG C, 2 is small
When；200 DEG C, 1 hour；250 DEG C, 1 hour；300 DEG C, 0.5 hour；It after cooling, is impregnated with deionized water, is washed with ethyl alcohol, done
The POSS/ of side chain containing acid imide polyimide nano-composite materials 3 are obtained after dry.
N in embodiment 3 is 60, and experience fluence is 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl
The mass loss of imines side chain cage-type silsesquioxane/polyimide nano-composite material 3 is 0.097mg/cm2.Embodiment 3
Other characterization results are similar to Example 1.
Embodiment 4
(1) under room temperature and nitrogen protection, eight aminopropyl POSS of 1.072g are dissolved in 20.4g N, N- dimethyl second
In amide (DMAc), stir 20 minutes, obtain eight aminopropyl POSS solution；Points of 4 times addition 1.185g phthalic anhydrides, the reaction was continued 18
Hour；Vacuum distillation removal DMAc, obtains the POSS4 of amide containing acid branch；
(2) under room temperature and nitrogen protection, by 3.964g 4, bis- (4- amino-benzene oxygens) benzophenone of 4'- are added to
In 75.3g DMAc, stirring obtains bis- (4- amino-benzene oxygens) the benzophenone solution of 4,4'- in 30 minutes；Divide 5 addition 3.308g
3,3', 4,4'- benzophenone tetrabasic carboxylic acid dicarboxylic anhydrides, add in 62.8g DMAc, and stirring polymerization 24 hours obtains polyamic acid 4；
(3) POSS4 of 0.727g amide containing acid branches is dissolved in 13.8gDMAc, stirring obtains amide containing acid for 30 minutes
The POSS4 solution of branch；By the POSS4 solution of amide containing acid branch in being slowly added to 4 solution of polyamic acid in 15 minutes
In, it stirs 16 hours, obtains 4 presoma of the POSS/ of side chain containing acid imide polyimide nano-composite materials；Ladder-elevating temperature removal is molten
Agent simultaneously completes hot imidization, and program is 40 DEG C, 8 hours；60 DEG C, 8 hours；80 DEG C, 3 hours；100 DEG C, 3 hours；120 DEG C, 4 is small
When；200 DEG C, 2 hours；250 DEG C, 2 hours；300 DEG C, 1 hour；It after cooling, is impregnated with deionized water, is washed with acetone, it is dry
After obtain the POSS/ of side chain containing acid imide polyimide nano-composite materials 4；
N in embodiment 4 is 80, and experience fluence is 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl
The mass loss of imines side chain cage-type silsesquioxane/polyimide nano-composite material 4 is 0.0079mg/cm2.Embodiment 4
Other characterization results it is similar to Example 1.
Embodiment 5
4,4'- diaminodiphenyl ethers are replaced with bis- [4- (4- amino-benzene oxygens) phenyl] hexafluoropropane of 2,2-, with 4,4'- oxygen
Double phthalic anhydrides replace 3,3,4', 4'- biphenyltetracarboxylic dianhydride to repeat embodiment 1, obtain the POSS/ polyamides of side chain containing acid imide
Imine nanometer composite material 5.
N in embodiment 5 is 60, and experience fluence is 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl
The mass loss of imines side chain cage-type silsesquioxane/polyimide nano-composite material 5 is 0.076mg/cm2.Embodiment 5
Other characterization results are similar to Example 1.
Embodiment 6
With 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acids dicarboxylic anhydride replaces 3,3,4', and 4'- biphenyltetracarboxylic dianhydride repeats embodiment
2, obtain the POSS/ of side chain containing acid imide polyimide nano-composite materials 6.
N in embodiment 6 is 80, and experience fluence is 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl
The mass loss of imines side chain cage-type silsesquioxane/polyimide nano-composite material 6 is 0.135mg/cm2.Embodiment 6
Other characterization results are similar to Example 1.
Embodiment 7
3,3,4', 4'- biphenyltetracarboxylic dianhydride is replaced to repeat embodiment 3 with 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids, obtained
The POSS/ of side chain containing acid imide polyimide nano-composite materials 7.
N in embodiment 7 is 60, and experience fluence is 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl
The mass loss of imines side chain cage-type silsesquioxane/polyimide nano-composite material 7 is 0.113mg/cm2.Embodiment 7
Other characterization results are similar to Example 1.
Embodiment 8
3,3,4', 4'- biphenyltetracarboxylic dianhydride are replaced with 4,4'- (4,4' isopropyl diphenoxies) bis- (phthalic anhydrides)
Embodiment 1 is repeated, obtains the POSS/ of side chain containing acid imide polyimide nano-composite materials 8.
N in embodiment 8 is that 60 experience fluences are 1.33 × 1020atoms/cm2Elemental oxygen irradiation after, containing acyl Asia
The mass loss of amine side chain cage-type silsesquioxane/polyimide nano-composite material 8 is 0.081mg/cm2.Embodiment 8 its
His characterization result is similar to Example 1.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, it is impossible to assert
The specific implementation of the present invention is confined to these explanations.It for those of ordinary skill in the art, can be according to the present invention
Technical solution and inventive concept, make it is corresponding change and substitute, and performance or use is identical, should all be considered as the present invention's
Protection domain.
Claims (2)
1. a kind of cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material, it is characterized in that, it is described sub- containing acyl
For amine side chain cage-type silsesquioxane/polyimide nano-composite material by dispersed phase and continuous phase composition, dispersed phase is containing acyl Asia
Amine side chain cage-type silsesquioxane, structural formula are：
Wherein R ' is Continuous phase
For polyimides, structural formula is：Ar ' is In one kind；Ar is
In one kind；Wherein, dispersed phase and the mass ratio of continuous phase are 2.1~10: 97.9~90；N is 60~80.
2. a kind of preparation side of the cage-type silsesquioxane of side chain containing acid imide/polyimide nano-composite material of claim 1
Method, it is characterized in that：
(1) under room temperature and nitrogen protection, eight amino cagelike silsesquioxanes are dissolved in solvent 1, are stirred 15~30 minutes,
Obtain eight amino cagelike silsesquioxane solution；Divide 3~5 addition phthalic anhydrides, the reaction was continued 12~24 hours；Vacuum distillation removal
Solvent 1 obtains the cagelike silsesquioxane of amide containing acid branch；The solvent 1 is N-Methyl pyrrolidone, N, N- dimethyl second
One kind in amide or N,N-dimethylformamide；Eight amino cagelike silsesquioxanes are eight aminophenyl cage type silsesquioxanes
One kind in alkane, eight aminopropyl cagelike silsesquioxanes；The mass ratio of 1 and eight amino cagelike silsesquioxane of solvent is 1: 9
~19；The molar ratio of phthalic anhydride and eight amino cagelike silsesquioxanes is 8:1；
(2) under room temperature and nitrogen protection, diamines is added in solvent 2, stirring obtains diamine solution in 15~30 minutes；Divide 3
~5 addition dianhydrides, add in solvent 3, and stirring polymerization 12~24 hours obtains polyamic acid；Diamines is 4,4'- diamino hexichol
Bis- [4- (4- amino-benzene oxygens) phenyl] propane of ether, 2,2-, bis- (4- amino-benzene oxygens) benzophenone of 4,4'- and the bis- [4- of 2,2-
(4- amino-benzene oxygens) phenyl] one kind in hexafluoropropane；Dianhydride is pyromellitic acid anhydride, 3,3,4', 4'- biphenyl tetracid two
Acid anhydride, 3,3', 4,4'- benzophenone tetrabasic carboxylic acid dicarboxylic anhydrides, 4,4'- oxygen double phthalic anhydride, 3,3', 4,4'- diphenyl sulfones four
Carboxylic diacid acid anhydride, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and 4,4'- (4,4' isopropyl diphenoxies) bis- (phthalic acids
Acid anhydride) in one kind；The molar ratio of diamines and dianhydride is 1: 1；Solvent 2 for N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or
One kind in N,N-dimethylformamide；Solvent 3 is N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or N, N- dimethyl methyl
One kind in amide；The mass ratio of diamines and solvent 2 is 1: 9~19；The mass ratio of dianhydride and solvent 3 is 1: 9~19；
(3) cagelike silsesquioxane of amide containing acid branch is dissolved in solvent 4, stirring obtains amide containing acid branch in 15~30 minutes
The cagelike silsesquioxane solution of chain；By the cagelike silsesquioxane solution of amide containing acid branch in 10~15 minutes slowly plus
Enter in the polyamic acid solution, stir 8~16 hours, obtain the cagelike silsesquioxane of side chain containing acid imide/polyimides and receive
Nano composite material presoma；Ladder-elevating temperature removes solvent and completes hot imidization, and program is 40 DEG C, 4~8 hours；60 DEG C, 4~8
Hour；80 DEG C, 1~3 hour；100 DEG C, 1~3 hour；120 DEG C, 2~4 hours；200 DEG C, 1~2 hour；250 DEG C, 1~2 is small
When；300 DEG C, 0.5~1 hour；It after cooling, is impregnated with deionized water, is washed with ethyl alcohol or acetone, obtained after dry containing acid imide
Side chain cagelike silsesquioxane/polyimide nano-composite material；The solvent is N-Methyl pyrrolidone, N, N- dimethyl second
One kind in amide or N,N-dimethylformamide；The mass fraction of the cagelike silsesquioxane of the amide containing acid branch is
2.1%~10%.
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| CN116023657A (en) * | 2023-02-10 | 2023-04-28 | 中国科学院化学研究所 | Silicon-boron synergistic modified atomic oxygen resistant polyimide composite film and preparation method and application thereof |
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