CN104151549B - A kind of thermosetting comb-type structure polyimide resin and preparation method thereof - Google Patents
A kind of thermosetting comb-type structure polyimide resin and preparation method thereof Download PDFInfo
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Abstract
The present invention is to provide a kind of thermosetting comb-type structure polyimide resin and preparation method thereof.The present invention is to solve that existing thermoset polyimide resin structure is single, processing performance is poor and the problem such as price is higher.Its preparation method of the thermosetting comb-type structure polyimide resin of the present invention, mainly used: one, mixed dissolution；Two, the synthesis of combed unit；Three, polymerization；Four, the process that concentration adjusts, obtains thermosetting comb-type structure polyimide resin.Present invention is mainly used for preparing thermosetting comb-type structure polyimide resin.The synthesis technique of the present invention is simple, prepares composite technology better performances, and storage period is longer；Thermosetting comb-type structure polyimide resin has higher physicochemical property, has broad application prospects in fields such as high-temperature fibre composites；Synthetic line is rationally, raw material is easy to get, price is relatively cheap and synthesis technique simple, has important promotion and application and is worth.
Description
Technical field
The present invention relates to a kind of fibrous composite resin matrix and preparation method thereof, particularly fire resistant resin
And preparation method thereof.
Background technology
Polyimides (PI) refers to the base polymer on main chain containing imide ring.As far back as 1908 just it has been reported that
But until the mid-40 in 20th century just has some patent documentations (US2710853) to occur, but real as a kind of macromolecule material
Material development then starts from the fifties.E.I.Du Pont Company had applied for a series of patent at that time, and in the mid-1960s, first by polyamides
Imines thin film (Kapton) and varnish (Pyre ML) commercialization, thus started polyimides flourish epoch.Acyl
Imine structure is:
Polyimides, because having high temperature resistant, high intensity, high-modulus, high tenacity and the insulating properties etc. of excellence, becomes
The important structural material in the field such as space flight and aviation and microelectronics and polymeric film material.But, owing to thermoplasticity polyamides is sub-
Amine typically exhibits high melt viscosity and the most poor dissolubility so that they pass through compression molding, injection
The biggest difficulty is often there is when the methods such as molding manufacture composite and binding agent.In order to solve high-performance polymer
High melt viscosity, low-solubility etc. are difficult to the problem of processing, and the heat cured polyimides of the performed polymer containing reactive group is opened
Send out the extensive concern causing people.This method uses and can introduce instead on processing structure to low-molecular-weight performed polymer or thermoplasticity
Answer group as cross-linking precursor, utilize the excellent processability of this kind of cross-linking precursor after being processed, to make its crosslinking curing become again
For temperature high performance high thermosets.Due to good by processing characteristics excellent for thermoplastic and thermosets of this method
Good machinery and hot property are organically unified have been arrived in the middle of commaterial, the most more and more receives material
The concern of material developers.But, it is relatively big that current thermoset polyimide resin still suffers from resin viscosity, and resin cured matter
The problems such as toughness is poor limit the extensive application of thermoset polyimide resin.
Summary of the invention
It is an object of the invention to provide a kind of thermosetting comb-type structure polyamides with excellent mechanical property, heat resistance
Imide resin.The present invention also aims to provide the thermosetting combed knot that a kind of technological process is simple, be suitable for industrialized production
The preparation method of structure polyimide resin.
The thermosetting comb-type structure polyimide resin of the present invention has a following structural formula:
Wherein: the integer of n ＞ 1；
R1For the one in the isomers of following several structures and each structure,
R2For the one in the isomers of following several structures and each structure,
A is the one in the isomers of following several structure and each structure,
The preparation method of the thermosetting comb-type structure polyimide resin of the present invention is:
Step one, mixed dissolution: be placed in container by polymerizable anhydride, add ethanol, temperature be 80 DEG C～200 DEG C,
It is stirred at reflux to being completely dissolved and obtains polymerizable acid anhydride solution；Dibasic acid anhydride is placed in container, adds ethanol, be 80 in temperature
DEG C～200 DEG C, be stirred at reflux to being completely dissolved and obtain dibasic acid anhydride solution；Tertiary amine is placed in container, adds ethanol, obtain
Tertiary amine ethanol solution；
Step 2, the synthesis of combed unit: tertiary amine ethanol solution step one obtained is constant temperature under conditions of stirring
To 80 DEG C～200 DEG C；The polymerizable acid anhydride solution that step one obtains is dripped, in polymerizable acid anhydride solution in 0.5～12 hour
Polymerizable anhydride is 0.5～10:1 with the mass ratio of tertiary amine in tertiary amine ethanol solution, continues constant temperature and returns to 80 DEG C～200 DEG C
Stream reaction 0.5～12 hour, the speed of 0.5-5 DEG C/min is cooled to room temperature and obtains the ethanol solution of combed unit；
Step 3, polymerization: by the ethanol solution constant temperature under agitation of the combed unit obtained by step 2 to 80 DEG C
～200 DEG C；In 0.5～12 hour, drip the dibasic acid anhydride solution that obtains of step one, in dibasic acid anhydride solution dibasic acid anhydride with
In tertiary amine ethanol solution, the mass ratio of tertiary amine is 0.5～10:1；Continue constant temperature to 80 DEG C～200 DEG C of back flow reaction 0.5～
12 hours；The polymerizable acid anhydride solution that step one obtains, polymerizable anhydride in dibasic acid anhydride solution is dripped in 0.5～12 hour
It is 0.05～1:1 with the mass ratio of tertiary amine in tertiary amine ethanol solution；Continue constant temperature to 80 DEG C～200 DEG C of back flow reaction 0.5
～obtain comb-shaped polymer ethanol solution in 12 hours；
Step 4, concentration adjust: by the comb-shaped polymer ethanol solution obtained by step 3 stirring ,-0.03～-
Under conditions of 0.09MPa, constant temperature 80 DEG C～200 DEG C decompression distillation 0.5～12 hour, then heat to 80 DEG C～200 DEG C ,-
Continue decompression distillation under conditions of 0.03～-0.09MPa and reach 100～100000mPa S to solution viscosity, 0.5-5 DEG C/min
Speed be cooled to room temperature and obtain thermosetting comb-type structure polyimide resin.
In step one, ethanol and polymerizable anhydride mass ratio are 1～10:1；Ethanol and dibasic acid anhydride mass ratio are 1～10:
1；Ethanol and tertiary amine mass ratio are 1～10:1.
Described in each step, the mixing speed of stirring is 500 revs/min～2500 revs/min.
The present invention is to solve that existing polyimide resin manufacturability is poor and the problem such as toughness is poor, and propose one
Plant technological process simple, be suitable for industrialized production, and have the polyimides of excellent mechanical property, heat resistance and processing performance
Resin and preparation method thereof.
Advantages of the present invention is mainly reflected in: one, one thermosetting comb-type structure polyimide resin of the present invention solves mesh
The shortcoming that front polyimide resin manufacturability is poor；Two, one thermosetting comb-type structure polyimide resin of the present invention has conjunction
Become technique simple, prepare composite technology better performances, the advantages such as storage period is longer；Three, one thermosetting combed of the present invention
Structure polyimide resin has higher physicochemical property, before there is wide application in the fields such as high-temperature fibre composite
Scape；Four, synthetic line of the present invention is rationally, raw material is easy to get, price is relatively cheap and synthesis technique simple, have important popularization and
Using value.
Accompanying drawing explanation
Fig. 1 is differential scanning thermometric analysis (DSC) collection of illustrative plates of the polyimide resin of test one preparation；
Fig. 2 is infrared spectrum (IR) collection of illustrative plates of the polyimide resin of test one preparation；
Fig. 3 is thermal weight loss (TG) collection of illustrative plates of the polyimide resin after test one solidification；
Fig. 4 is H nuclear magnetic resonance, NMR (NMR) collection of illustrative plates of the polyimide resin of test one preparation；
Fig. 5 a to Fig. 5 c is dynamic thermal analysis (DMA) collection of illustrative plates of the polyimide resin of test one preparation.
Detailed description of the invention
Illustrate below and the present invention is described in more detail.
Detailed description of the invention one:
Polymerizable anhydride described in present embodiment is phenylacetylene benzoic anhydride, naphthalene acetylene anhydride, phenylacetylene anhydride naphthalene, naphthalene acetylene naphthalene
One in acid anhydride etc..
Tertiary amine described in present embodiment be Triaminopyrimidine, triamido pyridine, triaminobenzene, triamido diphenyl ether ,-
Triaminotriphenyl-methane, quinazoline triamine, 2-vinyl-4,6-diaminostilbene, the one in 3,5-triazine etc..
Dibasic acid anhydride described in present embodiment be pyromellitic dianhydride, biphenyl tetracarboxylic anhydride, benzophenone tetracarboxylic dianhydride (BTDA),
One in diphenyl ether tetraformic dianhydride etc..
A kind of thermosetting comb-type structure polyimide resin described in present embodiment solves current polyimide resin work
The shortcoming that skill is poor.
It is simple that a kind of thermosetting comb-type structure polyimide resin described in present embodiment has synthesis technique, and preparation is multiple
Condensation material processing performance is preferable, the advantages such as storage period is longer.
A kind of thermosetting comb-type structure polyimide resin described in present embodiment has higher physicochemical property, at resistance to height
The fields such as temperature fibrous composite have broad application prospects.
A kind of thermosetting comb-type structure polyimide resin synthetic line described in present embodiment is reasonable, raw material is easy to get,
Price is relatively cheap and synthesis technique simple, has important promotion and application and is worth.
It is specifically realized by the following steps:
One, mixed dissolution: be placed in flask by polymerizable anhydride, adds ethanol, and ethanol with polymerizable anhydride mass ratio is
(1～10:1), temperature be 80 DEG C～200 DEG C, mixing speed be 500 revs/min～2500 revs/min under conditions of be stirred at reflux
Polymerizable acid anhydride solution is obtained to being completely dissolved；Being placed in flask by dibasic acid anhydride, add ethanol, ethanol closes anhydride matter with binary
Amount than for (1～10:1), temperature be 80 DEG C～200 DEG C, mixing speed be 500 revs/min～2500 revs/min under conditions of stir
Mix to be back to be completely dissolved and obtain dibasic acid anhydride solution；Tertiary amine is placed in flask, adds ethanol, ethanol and tertiary amine quality
Than being (1～10:1), obtain tertiary amine ethanol solution.Two, the synthesis of combed unit: tertiary amine ethanol step one obtained is molten
Low whipping speed be 500 revs/min～2500 revs/min under conditions of constant temperature to 80 DEG C～200 DEG C；Dripped in 0.5～12 hour
The polymerizable acid anhydride solution that step one obtains, polymerizable anhydride and tertiary amine in tertiary amine ethanol solution in polymerizable acid anhydride solution
Mass ratio be (0.5～10:1), continue constant temperature to 80 DEG C～200 DEG C of back flow reaction 0.5～12 hours, 0.5-5 DEG C/min's
Speed is cooled to room temperature and obtains the ethanol solution of combed unit；Three, polymerization: by molten for the ethanol of the combed unit obtained by step 2
Liquid low whipping speed be 500 revs/min～2500 revs/min under conditions of constant temperature to 80 DEG C～200 DEG C；Dripped in 0.5～12 hour
Add the dibasic acid anhydride solution that step one obtains, dibasic acid anhydride and the matter of tertiary amine in tertiary amine ethanol solution in dibasic acid anhydride solution
Amount ratio is (0.5～10:1)；Continue constant temperature to 80 DEG C～200 DEG C of back flow reaction 0.5～12 hours；Dripped in 0.5～12 hour
Add the polymerizable anhydride R2 solution that step one obtains, polymerizable anhydride and ternary in tertiary amine ethanol solution in dibasic acid anhydride solution
The mass ratio of amine is (0.05～1:1)；Continue constant temperature and to 80 DEG C～200 DEG C of back flow reaction 0.5～obtain comb polymers in 12 hours
Thing ethanol solution；Four, concentration adjusts: be 500 revs/min by the comb-shaped polymer ethanol solution low whipping speed obtained by step 3
～2500 revs/min ,-0.03～-0.09MPa, under conditions of constant temperature 80 DEG C～200 DEG C, decompression distillation 0.5～12 hour, then rises
Temperature to 80 DEG C～200 DEG C, under conditions of-0.03～-0.09MPa continue decompression distillation to solution viscosity reach 100～
100000mPa S, the speed of 0.5-5 DEG C/min is cooled to room temperature and obtains thermosetting comb-type structure polyimide resin.
A kind of thermosetting comb-type structure polyimide resin described in present embodiment solves current polyimide resin work
The shortcoming that skill is poor.
It is simple that a kind of thermosetting comb-type structure polyimide resin described in present embodiment has synthesis technique, and preparation is multiple
Condensation material processing performance is preferable, the advantages such as storage period is longer.
A kind of thermosetting comb-type structure polyimide resin described in present embodiment has higher physicochemical property, at resistance to height
The fields such as temperature fibrous composite have broad application prospects.
A kind of thermosetting comb-type structure polyimide resin synthetic line described in present embodiment is reasonable, raw material is easy to get,
Price is relatively cheap and synthesis technique simple, has important promotion and application and is worth.
Detailed description of the invention two: present embodiment is unlike detailed description of the invention one: gathering described in step one
Conjunction anhydride is one or more mixture in phenylacetylene benzoic anhydride, naphthalene acetylene anhydride, phenylacetylene anhydride naphthalene, naphthalene acetylene naphthalene acid anhydride etc..Its
He is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is unlike detailed description of the invention one or two: described in step 2
Tertiary amine is Triaminopyrimidine, triamido pyridine, triaminobenzene, triamido diphenyl ether ,-triaminotriphenyl-methane, quinazoline three
Amine, 2-vinyl-4,6-diaminostilbene, one or more mixture in 3,5-triazine etc..He with detailed description of the invention one or
Two is identical.
Detailed description of the invention four: present embodiment is unlike one of detailed description of the invention one to three: institute in step 3
Stating dibasic acid anhydride is in pyromellitic dianhydride, biphenyl tetracarboxylic anhydride, benzophenone tetracarboxylic dianhydride (BTDA), diphenyl ether tetraformic dianhydride etc.
One or more mixture.Other are identical with one of detailed description of the invention two to four.
Use the effect of the following verification experimental verification present invention:
Test one: the preparation method of a kind of thermosetting comb-type structure polyimide resin, is specifically realized by the following steps
:
One, mixed dissolution: be placed in flask by phenylacetylene benzoic anhydride, adds ethanol, and ethanol with phenylacetylene benzoic anhydride mass ratio is
5:1, temperature be 80 DEG C, mixing speed be 1500 revs/min under conditions of be stirred at reflux to being completely dissolved and obtain phenylacetylene benzene
Anhydride solution；By in bibenzene tetracarboxylic dianhydride flask, adding ethanol, ethanol and bibenzene tetracarboxylic dianhydride mass ratio are 5:1, in temperature
Be 80 DEG C, mixing speed be 1500 revs/min under conditions of be stirred at reflux to being completely dissolved and obtain bibenzene tetracarboxylic dianhydride solution；
Being placed in flask by Triaminopyrimidine, add ethanol, ethanol and tertiary amine mass ratio are 3:1, obtain Triaminopyrimidine ethanol molten
Liquid.Two, the synthesis of combed unit: Triaminopyrimidine ethanol step one obtained is dissolved in the bar that mixing speed is 1500 revs/min
Under part, constant temperature is to 100 DEG C；The phenylacetylene benzoic anhydride solution that step one obtains, benzene second in phenylacetylene benzoic anhydride solution is dripped in 1 hour
Alkynes phthalic anhydride and the amount of the material of Triaminopyrimidine in Triaminopyrimidine solution ratio for 1:3, continues constant temperature little to 80 DEG C of back flow reaction 2
Time, the speed of 3 DEG C/min is cooled to room temperature and obtains the ethanol solution of combed unit；Three, polymerization: by the combed obtained by step 2
The ethanol solution low whipping speed of unit be 1500 revs/min under conditions of constant temperature to 80 DEG C；In 1 hour, drip step one obtain
Bibenzene tetracarboxylic dianhydride solution, ternary in bibenzene tetracarboxylic dianhydride and tertiary amine ethanol solution in bibenzene tetracarboxylic dianhydride solution
The mass ratio of amine is 4:5；Continue constant temperature to 100 DEG C of back flow reaction 2 hours；The benzene second that step one obtains is dripped in 0.5 hour
Alkynes phthalic anhydride solution, phenylacetylene benzoic anhydride solution and the material of tertiary amine in Triaminopyrimidine ethanol solution in phenylacetylene benzoic anhydride solution
Amount ratio is 2:5；Continue constant temperature and within 4 hours, obtain comb-shaped polymer ethanol solution to 80 DEG C of back flow reaction；Four, concentration adjusts: will step
Comb-shaped polymer ethanol solution low whipping speed obtained by rapid three is 1500 revs/min ,-0.03～-0.09MPa, and constant temperature 80 DEG C
Under conditions of decompression distillation 2 hours, then heat to 120 DEG C, under conditions of-0.03～-0.09MPa continue decompression distillation extremely
Solution viscosity reaches 100～100000mPa S, and the speed of 5 DEG C/min is cooled to room temperature and obtains thermosetting comb-type structure polyamides Asia
Polyimide resin.
Using differential scanning amount thermal analyzer (DSC) to detect the polyimide resin of this test one preparation, testing result is such as
Shown in Fig. 1, Fig. 1 is differential scanning thermometric analysis (DSC) collection of illustrative plates of the polyimide resin of test one preparation, it can be seen that in figure
Only 350 DEG C of exothermic peaks that come into existence, illustrate that polyimide resin starts to crosslink curing reaction at about 350 DEG C.
Using infrared spectrum (IR) to detect polyimide resin prepared by this test one, testing result is as in figure 2 it is shown, Fig. 2
It is infrared spectrum (IR) collection of illustrative plates of the polyimide resin of test one preparation, it can be seen that the polyamides of test one preparation of synthesis is sub-
Polyimide resin polyimides (BPMR) although and some peak type of infared spectrum of KH370 slightly different, but the position at peak is essentially identical,
Illustrate that BPMR has the polyimide structures similar with KH370.
Polyimide resin after using thermal weight loss (TG) to detect solidification prepared by this test one, testing result such as Fig. 3 institute
Showing, Fig. 3 is thermal weight loss (TG) collection of illustrative plates of the polyimide resin after test one solidification, and result shows solidification prepared by this test one
After polyimide resin heat decomposition temperature higher than 500 DEG C, 5% thermal weight loss temperature is 530 DEG C, and 800 DEG C of thermal weight losses are
35.76%.
Using H nuclear magnetic resonance, NMR (NMR) to detect the polyimide resin of this test one preparation, testing result is as shown in Figure 4.
Use dynamic thermal analysis (DMA) detect this test one prepare polyimide resin, testing result as it is shown in figure 5,
Fig. 5 is dynamic thermal analysis (DMA) collection of illustrative plates of the polyimide resin of test one preparation, and 10 DEG C/min of heating rate, DMA result shows
Show that plexiglas transition temperature is about 396 DEG C, polyimides II generation (371 DEG C) higher than NASA.Resin storage modulus (E ')
Without significant change before 350 DEG C, illustrate that resin can use at 350 DEG C.
Claims (4)
1. a thermosetting comb-type structure polyimide resin, is characterized in that having following structural formula:
Wherein: the integer of n ＞ 1；
R1For the one in the isomers of following several structures and each structure,
R2For the one in the isomers of following several structures and each structure,
A is the one in the isomers of following several structure and each structure,
2. a preparation method for thermosetting comb-type structure polyimide resin as claimed in claim 1, is characterized in that:
Step one, mixed dissolution: be placed in container by polymerizable anhydride, add ethanol, is 80 DEG C～200 DEG C, stirring in temperature
It is back to be completely dissolved and obtains polymerizable acid anhydride solution；Dibasic acid anhydride is placed in container, add ethanol, temperature be 80 DEG C～
200 DEG C, it is stirred at reflux to being completely dissolved and obtains dibasic acid anhydride solution；Tertiary amine is placed in container, adds ethanol, obtain ternary
Amine ethanol solution；
Step 2, the synthesis of combed unit: the tertiary amine ethanol solution that step one is obtained stirring under conditions of constant temperature to 80
DEG C～200 DEG C；In 0.5～12 hour, drip the polymerizable acid anhydride solution that step one obtains, polymerizable acid anhydride solution can gather
Closing anhydride with the mass ratio of tertiary amine in tertiary amine ethanol solution is 0.5～10:1, continues constant temperature anti-to 80 DEG C～200 DEG C backflows
Answering 0.5～12 hour, the speed of 0.5-5 DEG C/min is cooled to room temperature and obtains the ethanol solution of combed unit；
Step 3, polymerization: by the ethanol solution constant temperature under agitation of the combed unit obtained by step 2 to 80 DEG C～200
℃；The dibasic acid anhydride solution that step one obtains, dibasic acid anhydride and tertiary amine in dibasic acid anhydride solution is dripped in 0.5～12 hour
In ethanol solution, the mass ratio of tertiary amine is 0.5～10:1；Continue constant temperature to 80 DEG C～200 DEG C of back flow reaction 0.5～12 hours；
The polymerizable acid anhydride solution that step one obtains, polymerizable anhydride and ternary in dibasic acid anhydride solution is dripped in 0.5～12 hour
In amine ethanol solution, the mass ratio of tertiary amine is 0.05～1:1；Continue constant temperature little to 80 DEG C～200 DEG C of back flow reaction 0.5～12
Time obtain comb-shaped polymer ethanol solution；
Step 4, concentration adjust: by the comb-shaped polymer ethanol solution obtained by step 3 stirring ,-0.03～-0.09MPa,
Under conditions of constant temperature 80 DEG C～200 DEG C decompression distillation 0.5～12 hour, then heat to 80 DEG C～200 DEG C ,-0.03～-
Continue decompression distillation under conditions of 0.09MPa and reach 100～100000mPa S, the speed of 0.5-5 DEG C/min to solution viscosity
It is cooled to room temperature and obtains thermosetting comb-type structure polyimide resin.
The preparation method of thermosetting comb-type structure polyimide resin the most according to claim 2, is characterized in that: step one
In, ethanol and polymerizable anhydride mass ratio are 1～10:1；Ethanol and dibasic acid anhydride mass ratio are 1～10:1；Ethanol and tertiary amine
Mass ratio is 1～10:1.
4. according to the preparation method of the thermosetting comb-type structure polyimide resin described in Claims 2 or 3, it is characterized in that: each
Described in step, the mixing speed of stirring is 500 revs/min～2500 revs/min.
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| US5606014A (en) * | 1995-08-04 | 1997-02-25 | The United States Of America As Represented By The United States National Aeronautics And Space Administration | Imide oligomers and co-oligomers containing pendent phenylethynyl groups and polymers therefrom |
| US6911519B2 (en) * | 2002-03-26 | 2005-06-28 | University Of Connecticut | Low viscosity melt processable high temperature polyimides |
| CN1597734A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院长春应用化学研究所 | Synthesis of biphenyl type polyimide resin with phenyl ethyne dead-end |
| CN100586931C (en) * | 2008-04-25 | 2010-02-03 | 中国科学院长春应用化学研究所 | Method for synthesizing 2,4-diamino[4'-(4-phenylacetylenylphthalimido)]diphenyl ether |
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